Arylamine compound and use thereof

Abstract

To provide arylamine compounds that have good solubility in organic solvents, provide a varnish having good storage stability and a thin film having good optical properties, and enable the realization of an organic EL element having good properties when the thin film is applied to a hole injection layer or the like.SOLUTION: Provided is an arylamine compound represented, for example, by the following formula B2d.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an arylamine compound and its use. [Background technology]

[0002] Organic electroluminescence (hereinafter referred to as OLED) elements are expected to be put to practical use in fields such as displays and lighting, and various developments are being made on materials and element structures with the aim of achieving low-voltage operation, high brightness, long life, etc. This organic EL element uses several functional thin films. One of these, the hole injection layer, is responsible for the exchange of charges between the anode and the hole transport layer or the light-emitting layer, and plays an important role in achieving low-voltage operation and high brightness of the organic EL element.

[0003] The methods for producing this hole injection layer are roughly divided into dry processes, such as deposition, and wet processes, such as spin coating. Compared to these processes, wet processes are more efficient at producing thin films with high flatness over a large area. For this reason, as organic EL displays are currently being made larger in area, there is a demand for hole injection layers that can be formed by wet processes.

[0004] In view of these circumstances, the present inventors have developed charge transport materials that are applicable to various wet processes and that, when applied to the hole injection layer of an organic EL element, give thin films that can realize excellent EL element characteristics, as well as compounds that have good solubility in organic solvents used therein (see Patent Documents 1 to 3).

[0005] Meanwhile, various efforts have been made to improve the performance of organic EL elements, including efforts to adjust the refractive index of the functional thin film used for the purpose of improving light extraction efficiency, etc. Specifically, attempts have been made to improve the efficiency of elements by using hole injection layers and hole transport layers with relatively high or low refractive indices, taking into account the overall configuration of the element and the refractive indices of other adjacent members (see Patent Documents 4 and 5). Thus, the refractive index is an important factor in the design of an organic EL device, and is considered to be an important physical property that should be taken into consideration for materials for organic EL devices.

[0006] Furthermore, because coloration of a charge-transporting thin film used in an organic EL element reduces the color purity and color reproducibility of the organic EL element, in recent years, it has been desired that a charge-transporting thin film for an organic EL element has high transmittance in the visible region and high transparency (see Patent Document 6). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2008 / 129947 [Patent Document 2] International Publication No. 2015 / 050253 [Patent Document 3] International Publication No. 2017 / 217457 [Patent Document 4] Special Publication No. 2007-536718 [Patent Document 5] Special Publication No. 2017-501585 [Patent Document 6] International Publication No. 2013 / 042623 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide an arylamine compound that has good solubility in organic solvents and can give a thin film with good optical properties, and that can realize an organic EL device having good properties when the thin film is applied to a hole injection layer or the like. [Means for solving the problem]

[0009] As a result of intensive research into achieving the above-mentioned object, the inventors have found that a compound having an aryldiamine skeleton at the center, with at least one arylcarbazole bonded to each of its two amino groups via a spacer having a specific arylene skeleton, has good solubility in organic solvents, and a varnish obtained by dissolving this in an organic solvent gives a thin film with excellent optical properties, and when this thin film is applied to a hole injection layer or the like, an organic EL device with good properties is obtained, thereby completing the present invention.

[0010] That is, the present invention provides 1. An arylamine compound represented by any one of the following formulas (1) to (6) (excluding the compounds represented by the following formulas (P1) to (P4)), [ka] [In the formula, Ar c each independently represents a group represented by formula (Q), X's each independently represent an arylene group which may be substituted and which may contain a heteroatom; Each Y independently represents an optionally substituted phenylene group. Each g independently represents an integer of 1 to 10. [ka] (In the formula, R 1 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 each independently represents an aryl group which may be substituted and may contain a heteroatom; Ar s each independently represents an arylene group which may be substituted and may contain a heteroatom. [ka] 2. The Ars an arylamine compound represented by any one of the following formulas (101) to (118): [ka] [ka] [ka] (In the formula, R 3 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; V 1 are each independently C(R 4 )2(R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; NR 5 (R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; represents S, O, or SO2; V 2 is NR 5 (R 5 has the same meaning as above. ), S or O. 3. The Ar s an arylamine compound represented by any one of the following formulas (101A) to (118A): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, R 3 , V 1 and V 2 has the same meaning as above.) 4. The Ar s 3, an arylamine compound represented by any one of the following formulas (101A-1) to (118A-3): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, R 4 and R 5 has the same meaning as above.) 5. An arylamine compound according to any one of 1 to 4, wherein X is represented by any one of the following formulas (201) to (207): [ka] (In the formula, R 6 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; W 1 are each independently a single bond, C(R 7 )2(R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; 2 is C(R 7 )2(R 7Each independently has the same meaning as above.) NR 8 (R 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; ), S, O, or SO2; W 3 is NR 8 (R 8 has the same meaning as above. ), S or O. 6. An arylamine compound according to claim 5, wherein X is represented by any one of the following formulas (201A) to (207A): [ka] (In the formula, R 6 , W 1 , W 2 and W 3 has the same meaning as above.) 7. An arylamine compound according to claim 6, wherein X is represented by any one of the following formulas (201A-1) to (207A-1): [ka] [ka] [ka] (In the formula, R 7 , R 8 and W 3 has the same meaning as above.) 8. The above-mentioned Ar c any one of the arylamine compounds represented by 1 to 7, 9. A charge-transporting varnish comprising an arylamine compound according to any one of 1 to 8 and an organic solvent. 10. The charge transport varnish of 9 containing a dopant material; 11. A charge-transporting thin film produced by using the charge-transporting varnish of 9 or 10. 12. Electronic devices using the charge transport thin films of 11 to provide. Effect of the Invention

[0011] The arylamine compound of the present invention has good solubility in organic solvents, and by using a charge-transporting varnish containing this arylamine compound, a charge-transporting thin film having high transparency and a high refractive index can be obtained. This charge transporting thin film can be suitably used as a thin film for electronic devices such as organic EL devices, particularly as a thin film for electronic devices in which a thin film is laminated on top by a wet process. By applying the charge transporting thin film of the present invention to the hole injection layer of an organic EL device, etc., a device having good characteristics can be produced. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-1. [Diagram 2] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-2. [Diagram 3] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-2. [Figure 4] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-2. [Diagram 5] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-3. [Figure 6] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-3. [Figure 7] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-4. [Figure 8] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-4. [Figure 9] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-5. [Figure 10] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-5. [Figure 11] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-6. [Figure 12]FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-6. [Figure 13] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-7. [Figure 14] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-7. [Figure 15] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-8. [Figure 16] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-8. [Figure 17] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-9. [Figure 18] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 1-9. [Figure 19] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 2-1. [Figure 20] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 2-2. [Figure 21] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 2-2. [Figure 22] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 2-3. [Diagram 23] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 2-4. [Figure 24] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Production Example 2-4. [Diagram 25] FIG. 1H-NMR spectrum of the compound obtained in Production Example 2-5. [Figure 26] FIG. 1H-NMR spectrum of the compound obtained in Production Example 2-5. [Figure 27] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Example 1-1. [Figure 28] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Example 1-2. [Figure 29] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Example 1-3. [Diagram 30] FIG. 1H-NMR spectrum of the compound obtained in Example 1-4. [Diagram 31] FIG. 1H-NMR spectrum of the compound obtained in Example 1-5. [Diagram 32] FIG. 1H-NMR spectrum of the compound obtained in Example 1-6. [Diagram 33] FIG. 1H-NMR spectrum of the compound obtained in Example 1-7. [Diagram 34] FIG. 1H-NMR spectrum of the compound obtained in Example 1-8. [Diagram 35] FIG. 1H-NMR spectrum of the compound obtained in Example 1-9. [Diagram 36] FIG. 1H-NMR spectrum of the compound obtained in Example 1-10. [Figure 37] FIG. 1H-NMR spectrum of the compound obtained in Example 1-11. [Figure 38] FIG. 1H-NMR spectrum of the compound obtained in Example 1-12. [Figure 39] FIG. 1H-NMR spectrum of the compound obtained in Example 1-12. [Diagram 40] FIG. 1H-NMR spectrum of the compound obtained in Example 1-13. [Diagram 41] FIG. 1H-NMR spectrum of the compound obtained in Example 1-13. [Diagram 42] FIG. 1H-NMR spectrum of the compound obtained in Example 1-14. [Diagram 43] FIG. 1H-NMR spectrum of the compound obtained in Example 1-15. [Diagram 44] FIG. 1H-NMR spectrum of the compound obtained in Example 1-16. [Diagram 45] FIG. 1H-NMR spectrum of the compound obtained in Example 1-17. [Figure 46] FIG. 1H-NMR spectrum of the compound obtained in Example 1-17. [Figure 47] FIG. 1H-NMR spectrum of the compound obtained in Example 1-18. [Figure 48] FIG. 1H-NMR spectrum of the compound obtained in Example 1-19. [Figure 49] FIG. 1H-NMR spectrum of the compound obtained in Example 1-20. [Figure 50] FIG. 1H-NMR spectrum of the compound obtained in Example 1-21. [Figure 51] FIG. 1H-NMR spectrum of the compound obtained in Example 1-22. [Figure 52] FIG. 1H-NMR spectrum of the compound obtained in Example 1-23. [Figure 53] FIG. 1 is a 1H-NMR spectrum of the compound obtained in Comparative Example 1-1. [Figure 54] FIG. 1H-NMR spectrum of the compound obtained in Comparative Example 1-2. [Figure 55] FIG. 1H-NMR spectrum of the compound obtained in Comparative Example 1-3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in further detail below. The arylamine compound according to the present invention is characterized by being represented by any one of the following formulas (1) to (6), but does not include the compounds represented by the formulas (P1) to (P4) as described above.

[0014] [ka]

[0015] In formulas (1) to (6), Ar ceach independently represents a group represented by the following formula (Q), each X independently represents an arylene group which may be substituted and which may contain a heteroatom, each Y independently represents a phenylene group which may be substituted, and each g independently represents an integer of 1 to 10, preferably Ar c each independently represents a group represented by the following formula (Q') or (Q'').

[0016] [ka]

[0017] In formulas (Q), (Q') and (Q''), R 1 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 each independently represents an aryl group which may be substituted and may contain a heteroatom; Ar s each independently represents an arylene group which may be substituted and which may contain a heteroatom.

[0018] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclic alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl groups.

[0019] The alkoxy group having 1 to 20 carbon atoms may have a linear, branched, or cyclic alkyl group, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, n-decyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, 2-n-propylhexyloxy, 2-n-butylhexyloxy, 2-ethyldecyloxy, and 3-ethylhexyloxy groups.

[0020] Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

[0021] The halogenated alkyl group having 1 to 20 carbon atoms is a group in which at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, and 2-(perfluorohexyl)ethyl groups.

[0022] R 1 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and even more preferably all are hydrogen atoms.

[0023] R in the above formulas (Q), (Q') and (Q'') 2 The aryl group which may be substituted and may contain a heteroatom is an arylene group which may contain a heteroatom as a constituent atom, and may have a structure in which rings are condensed or linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, more preferably 30 or less. R 2 Specific examples of the substituent of the aryl group which may be substituted and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above.

[0024] Specific examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl groups.

[0025] Specific examples of alkynyl groups having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecinyl, and n-1-eicosynyl groups.

[0026] R 2 As the alkyl group, an aryl group having 6 to 10 carbon atoms which may be substituted and which may contain a heteroatom is preferable, an optionally substituted phenyl group or an optionally substituted naphthyl group is more preferable, a phenyl group or a naphthyl group is even more preferable, and a phenyl group is still more preferable. Below, R 2 Specific examples of suitable groups are listed below, but the present invention is not limited thereto.

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] Ar in the above formulas (Q), (Q') and (Q'') sThe arylene group which may be substituted and may contain a heteroatom is an arylene group which may contain a heteroatom as a constituent atom, and may have a structure in which rings are condensed or linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, more preferably 30 or less. Ar s Specific examples of the substituent of the arylene group which may be substituted and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above. In a preferred embodiment, Ar s is a group represented by any one of the following formulas (101) to (118).

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] R 3 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; V 1 are each independently C(R 4 )2(R 4each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; NR 5 (R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; represents S, O, or SO2; V 2 is NR 5 (R 5 has the same meaning as above. ), S or O. R 3 ~R 5 In the above, examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the halogenated alkyl group having 1 to 20 carbon atoms include the same as those mentioned above.

[0039] In particular, R 3 are each independently preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. 3 is preferably an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms, and in consideration of this, a trifluoromethyl group is more preferable. R 4 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and all the more preferably a methyl group. R 5 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, and still more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0040] Also, all R 3 If is not an electron-withdrawing group, V1 is preferably S, O, or SO2. 1 If S, O, or SO2, then R 3 Electron-withdrawing groups may be present in the In addition, all R 3 If is not an electron-withdrawing group, V 2 is preferably S or O. 2 If S, O, then R 3 Electron-withdrawing groups may be present in the

[0041] Ar s is preferably a group represented by any one of the following formulas (101A) to (118A).

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka] (In the formula, R 3 , V 1 and V 2 has the same meaning as above.)

[0050] Below, Ar s Preferred specific examples are given below, but the present invention is not limited to these.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0056] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0057] [ka] (In the formula, R4 and R 5 has the same meaning as above.)

[0058] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0059] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0060] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0061] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0062] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0063] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0064] [ka] (In the formula, R4 and R 5 has the same meaning as above.)

[0065] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0066] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0067] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0068] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0069] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0070] [ka] (In the formula, R 4 and R 5 has the same meaning as above.)

[0071] [ka]

[0072] [ka] (In the formula, R 5 has the same meaning as above.)

[0073] [ka] (In the formula, R 5 has the same meaning as above.)

[0074] The arylene group of X in the above formulas (1) and (2), which may be substituted and may contain a heteroatom, is not particularly limited, and may be a structure in which rings are condensed or linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, more preferably 30 or less. Specific examples of the substituent of the arylene group of X which may be substituted and may contain a heteroatom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above.

[0075] In particular, taking into consideration the balance of refractive index, transparency, and electrical properties, the arylene group which may be substituted and which may contain a heteroatom, represented by X in the above formulas (1) and (2), is preferably a divalent group represented by any of the following formulas (201) to (207).

[0076] [ka]

[0077] In formulas (201) to (207), R 6each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; W 1 are each independently a single bond, C(R 7 )2(R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; 2 is C(R 7 )2(R 7 has the same meaning as above.) NR 8 (R 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; ), S, O, or SO2; W 3 is NR 8 (R 8 has the same meaning as above. ), S or O. R 6 ~R 8 In the above, examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the halogenated alkyl group having 1 to 20 carbon atoms include the same as those mentioned above.

[0078] In particular, R 6 are each independently preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. 6 is preferably an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms, and in consideration of this, a trifluoromethyl group is more preferable. R 7 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and all the more preferably a methyl group. R 8 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, and still more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0079] Also, all R 6 When W is not an electron-withdrawing group, it reduces the extinction coefficient of the resulting thin film. 1 is preferably S, O, or SO2. 1 If S, O, or SO2, then R 6 Electron-withdrawing groups may be present in the

[0080] Also, all R 6 When W is not an electron-withdrawing group, it reduces the extinction coefficient of the resulting thin film. 2 is preferably S, O, or SO2. 2 If S, O, or SO2, then R 6 Electron-withdrawing groups may be present in the In addition, all R 6 When W is not an electron-withdrawing group, it reduces the extinction coefficient of the resulting thin film. 3 is preferably S or O. 3 If S, O, or SO2, then R 6 Electron-withdrawing groups may be present in the

[0081] Furthermore, in the above formulas (201) to (207), the amino group on the aromatic ring and the spacer W 1 The bonding position of is not particularly limited, but a divalent group represented by any one of the following formulae (201A) to (207A) is preferable.

[0082] [ka] (In the formula, R 6 , W 1 , W 2 and W 3 has the same meaning as above.)

[0083] From the viewpoint of improving the storage stability of a varnish using the arylamine compound of the present invention, it is preferable that the aromatic ring in the above formulas (201) to (207) has at least one substituent, and from this viewpoint, a divalent group represented by any of the following formulas (201A') to (207A') is preferred.

[0084] [ka] (In the formula, W 1 , W 2 and W 3 has the same meaning as above.)

[0085] In formulas (201A') to (207A'), R 6’ each independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above. Among these, R 6’ is preferably an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group or a trifluoromethyl group.

[0086] Suitable X in the present invention includes, but is not limited to, those represented by the following formulae:

[0087] [ka]

[0088] [ka]

[0089] [ka] (In the formula, R 7 , R 8 and W 3 has the same meaning as above.)

[0090] Examples of the optionally substituted phenylene group for Y in the above formulas (3) to (6) include a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group which may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or the like. In consideration of the balance between refractive index, transparency, and electrical properties, an optionally substituted 1,4-phenylene group or a 1,3-phenylene group is preferred, and an unsubstituted 1,4-phenylene group or a 1,3-phenylene group is more preferred.

[0091] In the above formulas (3) to (6), g each independently represents an integer of 1 to 10. Taking into consideration the solubility of the compound in an organic solvent and the transparency of the resulting thin film, an integer of 1 to 7 is preferred, an integer of 1 to 5 is more preferred, an integer of 1 to 3 is even more preferred, and 1 or 2 is even more preferred. Taking into consideration the availability of the raw material compounds, 1 is optimal.

[0092] In the present invention, Ar s is preferably a group represented by formula (107), more preferably a group represented by any one of formulas (107A) to (107C), still more preferably a group represented by any one of formulas (107A-1) to (107C-5), and further preferably a group represented by formula (107B-1) or (107C-1).

[0093] In the present invention, from the viewpoint of ease of synthesis, in each of the formulas (1) to (6), Ar c are preferably the same group. In particular, Ar c is preferably a group represented by formula (Q-1) (Ar C1 ), more preferably a group represented by formula (Q-2) (Ar C2) or a group represented by formula (Q-3) (Ar C3 ).

[0094] [ka]

[0095] In a preferred embodiment, the arylamine compound of the present invention is represented by any one of the following formulas (1-1) to (6-1), and in a more preferred embodiment, is represented by any one of the following formulas (1-2) to (6-2) and (1-3) to (6-3).

[0096] [ka] (In the formula, X, Y, Ar C1 and g have the same meaning as above.)

[0097] [ka] (In the formula, X, Y, Ar C2 and g have the same meaning as above.)

[0098] [ka] (In the formula, X, Y, Ar C3 and g have the same meaning as above.)

[0099] The arylamine compound represented by formula (1) or (2) of the present invention (hereinafter also referred to as arylamine compound (1) or (2)) can be produced by reacting an aryldiamine compound [I] with an aryl halide compound [II] in the presence of a catalyst, as shown in the following scheme.

[0100] [ka] (In the formula, Z represents a halogen atom or a pseudohalogen group; X, R 1 , R 2and Ar s has the same meaning as above.)

[0101] The halogen atom includes the same as those mentioned above. Examples of the pseudohalogen group include (fluoro)alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy, and nonafluorobutanesulfonyloxy groups; and aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy groups.

[0102] The charge ratio of the aryl diamine compound [I] to the aryl halide compound [II] is determined appropriately depending on whether the compound to be synthesized is the aryl amine compound (1) or (2), and taking into consideration the reactivity, bulkiness, etc. of the raw material compounds, usually in the range of about 1.2 to 0.6 equivalents of the aryl halide compound relative to the substance amount of all NH groups of the aryl diamine compound [I]. When synthesizing the aryl amine compound (1), it is preferable to use 1.0 equivalent or more of the aryl halide compound.

[0103] Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; and palladium catalysts such as Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium), Pd(PPh3)2Cl2 (bis(triphenylphosphine)dichloropalladium), Pd(dba)2 (bis(dibenzylideneacetone)palladium), Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium), Pd(Pt-Bu3)2 (bis(tri(t-butylphosphine))palladium), and Pd(OAc)2 (palladium acetate). These catalysts may be used alone or in combination of two or more. These catalysts may also be used together with a known suitable ligand.

[0104] Examples of such ligands include tertiary phosphines such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl(phenyl)phosphine, di-t-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, and 1,1'-bis(diphenylphosphino)ferrocene; tertiary phosphites such as trimethylphosphite, triethylphosphite, and triphenylphosphite; JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, Examples of biphenylphosphine compounds include tBuDavePhos, PhDavePhos, 2'-Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me3(OMe)tBuXPhos, (2-Biphenyl)di-1-adamantylphosphine, RockPhos, and CPhos.

[0105] The amount of the catalyst used may be about 0.01 to 0.5 mol, preferably about 0.05 to 0.2 mol, per mol of the halogenated aryl compound [II]. When a ligand is used, the amount of the ligand used may be 0.1 to 5 equivalents relative to the metal complex used, and preferably 1 to 2 equivalents.

[0106] In addition, a base may be used in the above reaction. Examples of the base include alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, sodium t-butoxy, potassium t-butoxy, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, alkali metal hydrides, alkali metal hydroxides, alkoxy alkali metals, alkali metal carbonates, and alkali metal hydrogen carbonates; alkaline earth metal carbonates such as calcium carbonate; organic lithiums such as n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), and lithium hexamethyldisilazane (LHMDS); and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine. When a base is used, the amount of the base used may be 0.1 to 5 equivalents relative to the amount of the halogenated aryl compound [II] used, and preferably 1 to 2 equivalents.

[0107] When all the raw material compounds are solid or from the viewpoint of efficiently obtaining the desired arylamine compound, each of the above reactions is carried out in a solvent. When using a solvent, there is no particular limitation on the type of solvent as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethyoxyphenyl ether, tetrahydrofuran, dioxane, tetrahydrofuran, di ... Examples of suitable solvents include dimethyl ketones (dimethyl ether, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), ureas (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents may be used alone or in combination of two or more.

[0108] The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, and is preferably about 0 to 200° C., more preferably 20 to 150° C. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compounds, and the like, and is usually about 30 minutes to 50 hours. After completion of the reaction, the reaction mixture is worked up in a conventional manner to give the desired arylamine compound.

[0109] The arylamine compounds of the present invention represented by formulas (3) to (5) (hereinafter also referred to as arylamine compounds (3), (4) or (5)) can be produced by reacting an aryldiamine compound [I'] with an aryl halide compound [II] in the presence of a catalyst, as shown in the following scheme.

[0110] [ka] (In the formula, Y, R 1 , R 2 , Z, Ar s and g have the same meaning as above.)

[0111] The charge ratio of the aryl diamine compound [I'] and the halogenated aryl compound [II] is not particularly limited as long as the target product can be obtained. Usually, the halogenated aryl compound is appropriately determined within a range of 1.2 equivalents or less relative to the amount of the total NH groups of the aryl diamine compound [I'] depending on whether the compound to be synthesized is the aryl amine compound (3) to (5) and taking into consideration the reactivity and bulkiness of the raw material compounds. When synthesizing the aryl amine compound (3), the halogenated aryl compound is preferably 1.0 equivalents or more relative to the amount of the total NH groups of the aryl diamine compound [I']. When synthesizing the aryl amine compound (4), the halogenated aryl compound can be 2.0 equivalents or more relative to the amount of the aryl diamine compound [I'], but 2.0 to 2.4 equivalents are preferred. When synthesizing the halogenated aryl amine compound (5), the halogenated aryl compound can be 4.0 equivalents or more relative to the amount of the aryl diamine compound [I'], but 4.0 to 4.8 equivalents are preferred. Other coupling reaction conditions and preferred conditions regarding catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by formula (1) or (2).

[0112] The arylamine compound represented by formula (6) of the present invention (hereinafter also referred to as arylamine compound (6)) can be produced by the following method. First, a dinitro compound [I″-1] is reacted with an aryl halide compound [II] to obtain a dinitro compound [I″-2].

[0113] [ka] (In the formula, R 1 , R 2 , Y, Z, Ar s and g have the same meaning as above.)

[0114] The charging ratio of the dinitro compound [I″-1] and the halogenated aryl compound [II] can be 1 equivalent or more of the halogenated aryl compound relative to the amount of all NH groups of the dinitro compound, and is preferably about 1 to 1.2 equivalents. Other reaction conditions and preferred conditions regarding catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those explained for the arylamine compound represented by formula (1) or (2).

[0115] Next, the nitro group in the dinitro compound [I"-2] is reduced by hydrogenation to obtain the amine compound [I"-3]. The hydrogenation can be carried out by a known method, such as a hydrogenation reaction using Pd / C or the like.

[0116] [ka] (In the formula, Y, Ar c and g have the same meaning as above.)

[0117] Next, the amine compound [I″-3] is reacted with an aryl halide compound [II] to obtain an arylamine compound (6).

[0118] [ka] (In the formula, R 1 , R 2 , Y, Z, Ar c , Ar sand g have the same meaning as above.)

[0119] The charging ratio of the amine compound [I″-3] to the aryl halide compound [II] can be 2 equivalents or more of the aryl halide compound relative to the amine compound, and is preferably about 2 to 2.4 equivalents. Other reaction conditions and preferred conditions regarding catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those explained for the arylamine compound represented by formula (1) or (2).

[0120] The aryl halide compound [II], which is a raw material used in the production of the arylamine compound of the present invention, can be produced by reacting an arylcarbazole compound [III] with a dihalogenated aryl compound [IV] in the presence of a catalyst.

[0121] [ka] (In the formula, R 1 , R 2 , Z and Ar s has the same meaning as above.)

[0122] Z B each independently represents a group represented by the following formula (E1) or (E2).

[0123] [ka]

[0124] Z' represents a halogen atom or a pseudohalogen group, and examples of the halogen atom and pseudohalogen group include the same as those mentioned above. Here, Z and Z' may be the same, but from the viewpoint of efficiently obtaining the desired halogenated aryl compound [II], it is preferable that the reactivity of the atom (group) of Z' is higher than the reactivity of the atom (group) of Z. By providing such a difference in reactivity, Z in the arylcarbazole compound [III] can be obtained. BThe group reacts preferentially with the atom (group) of Z' rather than with the atom (group) of Z, thereby efficiently giving the desired aryl halide compound [II].

[0125] D 1 and D. 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; D 3 represents an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above.

[0126] Examples of the alkanediyl group having 1 to 20 carbon atoms include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, 2,2-dimethylpropane-1,3-diyl, 2-ethyl-2-methylpropane-1,3-diyl, 2,2-diethylpropane-1,3-diyl, 2-methyl-2-propylpropane-1,3-diyl, butane-1,3-diyl, butane-2,3-diyl, butane- 1,4-diyl, 2-methylbutane-2,3-diyl, 2,3-dimethylbutane-2,3-diyl, pentane-1,3-diyl, pentane-1,5-diyl, pentane-2,3-diyl, pentane-2,4-diyl, 2-methylpentane-2,3-diyl, 3-methylpentane-2,3-diyl, 4-methylpentane-2,3-diyl, 2,3-dimethylpentane-2,3-diyl, 3-methyl Examples of the alkyl group include pentane-2,4-diyl, 3-ethylpentane-2,4-diyl, 3,3-dimethylpentane-2,4-diyl, 3,3-dimethylpentane-2,4-diyl, 2,4-dimethylpentane-2,4-diyl, hexane-1,6-diyl, hexane-1,2-diyl, hexane-1,3-diyl, hexane-2,3-diyl, hexane-2,4-diyl, hexane-2,5-diyl, 2-methylhexane-2,3-diyl, 4-methylhexane-2,3-diyl, 3-methylhexane-2,4-diyl, 2,3-dimethylhexane-2,4-diyl, 2,4-dimethylhexane-2,4-diyl, 2,5-dimethylhexane-2,4-diyl, 2-methylhexane-2,5-diyl, 3-methylhexane-2,5-diyl, and 2,5-dimethylhexane-2,5-diyl groups.

[0127] Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,2-anthrylene, 2,3-anthrylene, 1,2-phenanthrylene, 3,4-phenanthrylene, and 9,10-phenanthrylene groups.

[0128] The molar ratio of the arylcarbazole compound [III] to the dihalogenated aryl compound [IV] can be 1:1.0 or more, preferably about 1.0 to 1.2.

[0129] When all the raw material compounds are solid or from the viewpoint of efficiently obtaining the desired halogenated arylamine compound, each of the above reactions is carried out in a solvent. When using a solvent, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction. Specific examples include cyclic ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); ketones such as methyl isobutyl ketone and cyclohexanone; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene; and aromatic hydrocarbons such as benzene, toluene, and xylene. These solvents can be used alone or in combination of two or more. Among these, 1,4-dioxane, toluene, xylene, and the like are particularly preferred.

[0130] Examples of the catalyst used in the above reaction include palladium catalysts such as [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (PdCl2(dppf)), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), bis(triphenylphosphine)dichloropalladium (Pd(PPh3)2Cl2), bis(benzylideneacetone)palladium (Pd(dba)2), tris(benzylideneacetone)dipalladium (Pd2(dba)3), bis(tri-t-butylphosphine)palladium (Pd(Pt-Bu3)2), and palladium(II) acetate (Pd(OAc)2).

[0131] The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, and is preferably about 0 to 200° C., more preferably 20 to 150° C. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compounds, and the like, and is usually about 30 minutes to 50 hours. After completion of the reaction, the reaction mixture is worked up in a conventional manner to obtain the desired halogenated arylamine compound.

[0132] The dihalogenated aryl compound [IV] can be obtained by reacting a compound represented by the formula [IV'] with a halogenating agent, as shown in the following scheme.

[0133] [ka] (In the formula, Ar s , Z and Z' have the same meanings as above.)

[0134] The halogenating agent may be a known agent, and specific examples thereof include, but are not limited to, N-bromosuccinimide, etc. The amount of the halogenating agent is about 1 to 1.5 in molar ratio relative to the compound represented by formula [IV']. The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent that can be used in this type of reaction. The reaction temperature is usually appropriately selected from the range of 0 to 140° C., and the reaction time is usually appropriately selected from the range of 0.1 to 100 hours.

[0135] The arylcarbazole compound [III] can be obtained by reacting a compound represented by the formula [III'] with a compound represented by the formula [V], as shown in the following scheme.

[0136] [ka] (In the formula, R 1 , R 2 , Z and Z B has the same meaning as above.)

[0137] The compound represented by the formula [III'] and the compound represented by the formula [V] are charged in a molar ratio of about 1 part of the compound represented by the formula [III'] to about 1 to 3 parts of the compound represented by the formula [V]. The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent that can be used in this type of reaction. The reaction temperature is usually appropriately selected from the range of 0 to 140° C., and the reaction time is usually appropriately selected from the range of 0.1 to 100 hours.

[0138] Furthermore, the compound represented by formula [III'] can be produced by reacting the compound represented by formula [III'-2] with a halogenated aryl compound (R 2 Z) and then treated with a halogenating agent, or the compound represented by formula [III'-2] is treated with a halogenating agent and then reacted with a halogenated aryl compound (R 2 Z), but the latter reaction is preferred from the viewpoint of avoiding halogenation of the aryl group at the N-position of the carbazole skeleton and obtaining the target compound more efficiently.

[0139] [ka] (In the formula, R 1 , R 2 and Z have the same meaning as above.)

[0140] As the halogenating agent used in the above reaction, a known agent can be used, and the amount of the halogenating agent is, in molar ratio, about 1 to 1.5 relative to 1 of the compound represented by formula [III'-1-1] or [III'-2]. The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent that can be used in this type of reaction. The above temperature is usually appropriately selected within the range of 0 to 140° C., and the time is usually appropriately selected within the range of 0.1 to 100 hours.

[0141] Also, Ar SThe compound represented by formula [VI] having two alkyl groups or the like at the 9-position of the fluorene ring, which is the raw material of the spacer skeleton, can be obtained by reacting a compound represented by formula [VI'] with a compound represented by formula [VII] in the presence of a base, as shown in the following scheme.

[0142] [ka] (In the formula, R 3 , Z and Z' have the same meanings as above, R 4’ each independently represents an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.

[0143] The compound represented by the formula [VI'] and the compound represented by the formula [VII] are charged in a molar ratio of about 1 part of the compound represented by the formula [VI'] to about 1 to 1.5 parts of the compound represented by the formula [VII]. The base that can be used in the above reaction is not particularly limited as long as it is a base that can be used in this type of reaction. Specific examples include t-BuOK, t-BuONa, CsCO3, K2CO3, Na2CO3, n-BuLi, t-BuLi, s-BuLi, NaOH, KOH, LiOH, etc., with t-BuOK, t-BuONa, n-BuLi, t-BuLi, s-BuLi, NaOH, and KOH being preferred. The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent that can be used in this type of reaction. The reaction temperature is usually appropriately selected from the range of 0 to 140° C., and the reaction time is usually appropriately selected from the range of 0.1 to 100 hours.

[0144] As shown in the following scheme, an amine compound that can be used as a raw material for the arylamine compound of the present invention can be obtained by (A) a coupling reaction between an amine compound [I'''] or [I''''] and an aryl compound [VIII], and (B) a reduction reaction of the nitro group by hydrogenation. By repeating the reactions (A) and (B), the chain length (number of phenylenes) can be extended.

[0145] [ka] (In the formula, Y, Z and g have the same meanings as above.)

[0146] [ka] (In the formula, Y, Z, and g have the same meanings as above.)

[0147] To give a more specific example, the amine compounds included in the amine compound [I'] can be obtained by (A) a coupling reaction between m-phenylenediamine or 3-nitroaniline and 3-halonitrobenzene, and (B) a reduction reaction of the nitro group by hydrogenation, as shown in the following scheme. By repeating the reactions (A) and (B), the chain length (the number of m-phenylenes) can be extended.

[0148] [ka] (In the formula, Z has the same meaning as above.)

[0149] By selecting either the upper or lower reaction in the above scheme, it is possible to produce an even or odd number of phenylenes. Therefore, it is possible to freely produce an amine compound [I'] having a desired number of phenylenes without using a synthetically difficult method such as protecting one of the amino groups with a protecting group.

[0150] In this case, the ratio of the raw material compounds in each reaction is determined appropriately depending on whether the number of phenylenes to be added is 1 or 2, within a range of about 1 to 2.4 of the raw material compound having a nitro group (raw material compound containing a halogen atom (pseudohalogen group)) to the raw material compound having an amino group, in terms of the amount of substance.

[0151] The palladium catalyst used in the coupling reaction may be the same as those mentioned above. In this case, a ligand may also be used. As the ligand, in addition to the above-mentioned examples, biphenylphosphine compounds such as JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2'-Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me3(OMe)tBuXPhos, (2-Biphenyl)di-1-adamantylphosphine, RockPhos, and CPhos, which are commercially available from Aldrich, may be suitably used.

[0152] Examples of the base used in the coupling reaction include alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, sodium t-butoxy, potassium t-butoxy, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, alkali metal hydrides, alkali metal hydroxides, alkoxy alkali metals, alkali metal carbonates, and alkali metal hydrogen carbonates; alkaline earth metal carbonates such as calcium carbonate; organic lithiums such as n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), and lithium hexamethyldisilazane (LHMDS); and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.

[0153] Other conditions and preferred conditions for the coupling reaction, such as catalyst, solvent, reaction temperature and time, are the same as those described for the arylamine compound represented by formula (1) or (2). The hydrogenation reaction using Pd / C can be carried out by a known method. When a paraphenylene group or an orthophenylene group is introduced instead of a metaphenylene group, 4-halonitrobenzene or 2-halonitrobenzene may be used instead of 3-halonitrobenzene.

[0154] Specific examples of the arylamine compound of the present invention are listed below, but the present invention is not limited to these. In the table, H represents a hydrogen atom, Ph represents a phenyl group, Me represents a methyl group, n-Hex represents an n-hexyl group, p-Toly represents a p-tolyl group, 2-Thie represents a 2-thienyl group, 1,3-Ph represents a 1,3-phenylene group, and 1,4-Ph represents a 1,4-phenylene group. For example, the arylamine compounds numbered 1 and 865 are the following compounds.

[0155] [ka]

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3]

[0159] [Table 4]

[0160]

Table 5

[0161]

Table 6

[0162]

Table 7

[0163]

Table 8

[0164]

Table 9

[0165]

Table 10

[0166]

Table 11

[0167]

Table 12

[0168]

Table 13

[0169]

Table 14

[0170]

Table 15

[0171] [Table 16]

[0172] [Table 17]

[0173] [Table 18]

[0174] [Table 19]

[0175] [Table 20]

[0176] [Table 21]

[0177] [Table 22]

[0178] The above-mentioned arylamine compound of the present invention can be suitably used as a charge transporting material.In this case, it can be used as a charge transporting varnish containing the arylamine compound of the present invention and an organic solvent, and this charge transporting varnish may contain a dopant material for the purpose of improving its charge transporting ability, etc., depending on the application of the thin film obtained.In addition, the arylamine compound of the present invention can also be used in combination with other conventionally known charge transporting materials such as aniline derivatives and thiophene derivatives, but it is preferable to use the arylamine compound of the present invention alone as a charge transporting material. In the present invention, the term "charge transporting property" is synonymous with "electrical conductivity." The charge transporting varnish may be one which itself has charge transporting property, or one which produces a solid film having charge transporting property.

[0179] There are no particular limitations on the dopant substance, so long as it dissolves in at least one solvent used in the varnish, and both inorganic and organic dopant substances can be used. The inorganic and organic dopant substances may be used alone or in combination of two or more. Furthermore, the dopant substance may be a substance whose function as a dopant substance is first expressed or improved by, for example, removing a part of its molecule due to an external stimulus, such as heating during baking, in the process of obtaining a charge-transporting thin film, which is a solid film, from the varnish, such as an arylsulfonate compound protected by a group from which the sulfonic acid group is easily removed.

[0180] In the present invention, heteropolyacids are particularly preferred as inorganic dopant substances. Heteropolyacids are polyacids that have a structure in which a heteroatom is located at the center of the molecule, typically represented by the chemical structure of the Keggin type represented by formula (H1) or the Dawson type represented by formula (H2), and are formed by condensing an isopolyacid, which is an oxyacid of vanadium (V), molybdenum (Mo), tungsten (W), etc., with an oxyacid of a different element. Examples of such oxyacids of different elements include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).

[0181] [ka]

[0182] Specific examples of heteropolyacids include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, etc., which may be used alone or in combination of two or more. These heteropolyacids are commercially available, or may be synthesized by known methods. In particular, when one type of heteropolyacid is used, the one type of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and is most preferably phosphotungstic acid. When two or more types of heteropolyacids are used, one of the two or more types of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and is more preferably phosphotungstic acid. In addition, the heteropolyacid may be used in the present invention even if the number of elements in the structure represented by the general formula is large or small in quantitative analysis such as elemental analysis, as long as it is a commercially available product or is appropriately synthesized according to a known synthesis method. That is, for example, phosphotungstic acid is generally represented by the chemical formula H3(PW 12 O 40 )·nH2O, and phosphomolybdic acid has the chemical formula H3(PMo 12 O 40 )·nH2O, but in quantitative analysis, those having a large or small number of P (phosphorus), O (oxygen), W (tungsten), or Mo (molybdenum) in this formula can be used in the present invention as long as they are commercially available or appropriately synthesized according to a known synthesis method. In this case, the mass of the heteropolyacid specified in the present invention does not mean the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthesized or commercially available product, but the total mass including water of hydration and other impurities in a commercially available form or in a form that can be isolated by a known synthesis method.

[0183] The amount of the heteropolyacid used may be about 0.001 to 50.0 parts by mass per 1 part of the charge transporting substance, but is preferably about 0.01 to 20.0 parts, and more preferably about 0.1 to 10.0 parts.

[0184] On the other hand, as organic dopant substances, in particular, tetracyanoquinodimethane derivatives and benzoquinone derivatives can be used. Specific examples of the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and a halotetracyanoquinodimethane represented by the formula (H3). Specific examples of the benzoquinone derivative include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).

[0185] [ka]

[0186] In the formula, R 500 ~R 503 each independently represents a hydrogen atom or a halogen atom, with at least one being a halogen atom, preferably at least two being halogen atoms, more preferably at least three being halogen atoms, and most preferably all being halogen atoms. Examples of the halogen atom include the same as those mentioned above, but a fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred.

[0187] Specific examples of such halotetracyanoquinodimethanes include 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro-7,7,8,8-tetracyanoquinodimethane, and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ).

[0188] The amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative used is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and even more preferably 1 to 20 equivalents, relative to the charge transporting substance.

[0189] Furthermore, as the organic dopant substance, electrically neutral onium borate salts consisting of a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by any of the formulae (c1) to (c5) can also be used.

[0190] [ka] (In the formula, each Ar independently represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent; L represents an alkylene group having 1 to 20 carbon atoms, -NH-, an oxygen atom, a sulfur atom, or -CN + - stands for

[0191] [ka]

[0192] In formula (a1), the alkylene group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene groups. Examples of the aryl group and heteroaryl group include the same as those mentioned above.

[0193] Suitable examples of the anion of the above formula (a1) include those represented by formula (a2), but are not limited thereto.

[0194] [ka]

[0195] The amount of the onium borate salt used can be about 0.1 to 10 in terms of the substance amount (molar) ratio to the charge transporting substance. The onium borate salt can be synthesized by referring to known methods described in, for example, JP-A-2005-314682.

[0196] As the organic dopant material, an arylsulfonic acid compound or an arylsulfonic acid ester compound can also be suitably used.

[0197] Specific examples of the arylsulfonic acid compound include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, and 7-hexyl-1-naphthalenesulfonic acid. Examples of suitable sulfonic acids include taresulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, 2,7-dinonyl-4,5-naphthalene disulfonic acid, 1,4-benzodioxanedisulfonic acid compounds described in WO 2005 / 000832, arylsulfonic acid compounds described in WO 2006 / 025342, and arylsulfonic acid compounds described in WO 2009 / 096352.

[0198] Preferred examples of the arylsulfonic acid compound include arylsulfonic acid compounds represented by formula (H4) or (H5).

[0199] [ka]

[0200] A 1 represents O or S, with O being preferred. A 2 represents a naphthalene ring or an anthracene ring, with a naphthalene ring being preferred. A 3 represents a divalent to tetravalent perfluorobiphenyl group, and p is A 1 and A 3 p is an integer that satisfies 2≦p≦4, but A 3It is preferred that p is a perfluorobiphenyldiyl group, preferably a perfluorobiphenyl-4,4'-diyl group, and p is 2. q is A 2 represents the number of sulfonic acid groups bonded to q, and is an integer satisfying 1≦q≦4, with 2 being optimal.

[0201] A 4 ~A 8 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms; 4 ~A 8 At least three of the are halogen atoms.

[0202] Examples of the halogenated alkyl group having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl groups.

[0203] Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), and perfluorobutenyl groups. Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include those similar to those mentioned above, with the halogen atom being preferably a fluorine atom.

[0204] Among these, A 4 ~A 8 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms, and A 4 ~A 8At least three of A are preferably fluorine atoms, and are each a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkenyl group having 2 to 5 carbon atoms; and 4 ~A 8 At least three of A are preferably fluorine atoms, and A is preferably a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkenyl group having 1 to 5 carbon atoms. 4 , A 5 and A 8 It is even more preferred that is a fluorine atom. The perfluoroalkyl group is an alkyl group in which all hydrogen atoms have been substituted with fluorine atoms, and the perfluoroalkenyl group is an alkenyl group in which all hydrogen atoms have been substituted with fluorine atoms.

[0205] r represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1≦r≦4, preferably 2 to 4, and most preferably 2.

[0206] The molecular weight of the arylsulfonic acid compound used as a dopant substance is not particularly limited, but taking into consideration the solubility in organic solvents when used together with the arylamine compound of the present invention, the molecular weight is preferably 2000 or less, more preferably 1500 or less.

[0207] Specific examples of suitable arylsulfonic acid compounds are listed below, but the invention is not limited thereto.

[0208] [ka]

[0209] [ka]

[0210] [ka]

[0211] The amount of the arylsulfonic acid compound used is preferably about 0.01 to 20.0, and more preferably about 0.4 to 5.0, per 1 part of the charge transporting substance, in terms of mole ratio. Although commercially available arylsulfonic acid compounds may be used, they can also be synthesized by known methods described in WO 2006 / 025342, WO 2009 / 096352, WO 2015 / 111654, WO 2015 / 053320, WO 2015 / 115515, and the like.

[0212] On the other hand, examples of the arylsulfonic acid ester compound include the arylsulfonic acid ester compounds disclosed in WO 2017 / 217455, the arylsulfonic acid ester compounds disclosed in WO 2017 / 217457, and the arylsulfonic acid ester compounds described in Japanese Patent Application No. 2017-243631 (WO 2019 / 124412). Specifically, those represented by any of the following formulae (H6) to (H8) are preferred.

[0213] [ka] (In the formula, m is an integer satisfying 1≦m≦4, and is preferably 2. n is an integer satisfying 1≦n≦4, and is preferably 2.)

[0214] In formula (H6), A 11 is an m-valent group derived from perfluorobiphenyl. A 12 is -O- or -S-, with -O- being preferred. A 13 is an (n+1)-valent group derived from naphthalene or anthracene, with the group derived from naphthalene being preferred. R s1 ~R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; R s5is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.

[0215] Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-hexyl groups, with alkyl groups having 1 to 3 carbon atoms being preferred. The monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups; and aryl groups such as phenyl, naphthyl, and phenanthryl groups.

[0216] In particular, R s1 ~R s4 Of these, R s1 or R s3 is a linear alkyl group having 1 to 3 carbon atoms, and the rest are hydrogen atoms, or R s1 is a linear alkyl group having 1 to 3 carbon atoms, and R s2 ~R s4 is preferably a hydrogen atom. In this case, the linear alkyl group having 1 to 3 carbon atoms is preferably a methyl group. Also, R s5 As the alkyl group, a linear alkyl group having 2 to 4 carbon atoms or a phenyl group is preferable.

[0217] In formula (H7), A 14 represents an optionally substituted hydrocarbon group having 6 to 20 carbon atoms, containing one or more aromatic rings, and having a valence of m, and this hydrocarbon group is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms and containing one or more aromatic rings. Examples of such hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene. In addition, the above-mentioned hydrocarbon groups may have some or all of their hydrogen atoms further substituted with a substituent. Examples of such substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, nitro, cyano, hydroxy, amino, silanol, thiol, carboxy, sulfonate ester, phosphoric acid, phosphate ester, ester, thioester, amide, organooxy, organoamino, organosilyl, organothio, acyl, sulfo, and a monovalent hydrocarbon group. Among these, A 14 As the alkyl group, groups derived from benzene, biphenyl, etc. are preferred.

[0218] Also, A 15 is -O- or -S-, with -O- being preferred. A 16 is an aromatic hydrocarbon group having 6 to 20 carbon atoms and a valence of (n+1), which is obtained by removing (n+1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among them, A 16 As the alkyl group, a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.

[0219] R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group; R s8 is a linear or branched monovalent aliphatic hydrocarbon group, where R s6 , R s7 and R s8 The total number of carbon atoms in R is 6 or more. s6 , R s7 and R s8 The upper limit of the total number of carbon atoms is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. Specific examples of the linear or branched monovalent aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl groups; and alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl groups. Among these, R s6 is preferably a hydrogen atom, and R s7 and R s8 are each preferably an alkyl group having 1 to 6 carbon atoms.

[0220] In formula (H8), R s9 ~R s13 are each independently a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups.

[0221] The halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms have been substituted with halogen atoms, and specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl groups.

[0222] The halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of an alkenyl group having 2 to 10 carbon atoms have been substituted with halogen atoms, and specific examples thereof include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, and perfluoro-3-butenyl groups.

[0223] Among these, R s9 As the alkyl group, a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms is preferable, a nitro group, a cyano group, a halogenated alkyl group having 1 to 4 carbon atoms, or a halogenated alkenyl group having 2 to 4 carbon atoms is more preferable, and a nitro group, a cyano group, a trifluoromethyl group, or a perfluoropropenyl group is even more preferable. R s10 ~R s13 As the halogen atom, a halogen atom is preferable, and a fluorine atom is more preferable.

[0224] A 17 is -O-, -S- or -NH-, with -O- being preferred. A 18 is an aromatic hydrocarbon group having 6 to 20 carbon atoms and a valence of (n+1), which is obtained by removing (n+1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among these, A 18 As the alkyl group, a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.

[0225] R s14 ~R s17 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. Specific examples of monovalent aliphatic hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups; and alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl groups. Of these, alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 8 carbon atoms are even more preferred.

[0226] R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 R s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms. R s18 Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include the same as those mentioned above. R s18 is a monovalent aliphatic hydrocarbon group, R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 8 carbon atoms. R s19 Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms include the above-mentioned monovalent aliphatic hydrocarbon groups other than the methyl group, as well as aryl groups such as phenyl, naphthyl, and phenanthryl groups. Among these, R s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group. Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.

[0227] Specific examples of suitable arylsulfonate compounds include, but are not limited to, those shown below.

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] The amount of the arylsulfonic acid ester compound used is preferably about 0.01 to 20, and more preferably about 0.05 to 10, in terms of the molar ratio per 1 part of the charge transporting substance. Although commercially available arylsulfonic acid ester compounds may be used, they can also be synthesized by known methods described in WO 2017 / 217455, WO 2017 / 217457, WO 2019 / 124412, etc.

[0232] In the present invention, in consideration of producing a charge transporting thin film having excellent transparency and a high refractive index, it is preferable to use an aryl sulfonic acid compound or an aryl sulfonate compound as a dopant substance, and in consideration of solubility in a solvent and obtaining a thin film having a smaller extinction coefficient, it is more preferable to use an aryl sulfonate compound.

[0233] Furthermore, when the obtained thin film is used as a hole injection layer of an organic EL device, the charge transporting varnish may contain an organosilane compound for the purpose of improving the injection property into the hole transporting layer, improving the life characteristics of the device, etc. The content of the organosilane compound is usually about 1 to 30% by mass based on the total mass of the charge transporting substance and the dopant substance.

[0234] The organic solvent used in preparing the charge transport varnish of the present invention can be a highly polar solvent that can dissolve the arylamine compound of the present invention well. The arylamine compound of the present invention can be dissolved in a solvent regardless of the polarity of the solvent. If necessary, a low polar solvent may be used because it has better process compatibility than a high polar solvent. In the present invention, a low polar solvent is defined as a solvent having a dielectric constant of less than 7 at a frequency of 100 kHz, and a high polar solvent is defined as a solvent having a dielectric constant of 7 or more at a frequency of 100 kHz.

[0235] Examples of low polarity solvents include Chlorinated solvents such as chloroform and chlorobenzene; Aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; Aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; Ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; Ester solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. etc.

[0236] Examples of highly polar solvents include Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; Ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; Cyano solvents such as acetonitrile and 3-methoxypropionitrile; Polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols, such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; Sulfoxide solvents such as dimethyl sulfoxide etc.

[0237] The viscosity of the charge-transporting varnish is determined appropriately depending on the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa s at 25° C. In the present invention, the solid content means the components other than the solvent contained in the charge-transporting varnish of the present invention. The solids concentration of the charge-transporting varnish is appropriately set taking into consideration the viscosity and surface tension of the varnish and the thickness of the thin film to be produced, but is usually about 0.1 to 20.0 mass %, and in order to improve the coatability of the varnish, it is preferably about 0.5 to 10.0 mass %, and more preferably about 1.0 to 5.0 mass %.

[0238] The method for preparing the charge-transporting varnish is not particularly limited, but examples thereof include a method in which all solid contents, such as the charge-transporting substance containing the arylamine compound of the present invention, are dissolved in an organic solvent at once, and a method in which a portion of the solid contents is dissolved in an organic solvent and then the remaining solid contents are dissolved.

[0239] In particular, when preparing a charge-transporting varnish, from the viewpoint of reproducibly obtaining a thin film with higher flatness, it is desirable to dissolve the charge-transporting substance, dopant substance, etc. in an organic solvent and then filter the resultant solution using a filter of the submicrometer order.

[0240] The charge transporting varnish described above can be used to easily produce a charge transporting thin film, and is therefore suitable for use in producing electronic devices, particularly organic EL devices. In this case, the charge transporting thin film can be formed by applying the above-mentioned charge transporting varnish onto a substrate and baking it. The method for applying the varnish is not particularly limited, and examples thereof include dipping, spin coating, transfer printing, roll coating, brush coating, inkjet coating, spraying, and slit coating. It is preferable to adjust the viscosity and surface tension of the varnish depending on the application method.

[0241] Furthermore, the atmosphere in which the charge-transporting varnish is baked after application is not particularly limited, and a thin film having a uniform film surface and high charge transport properties can be obtained not only in an air atmosphere but also in an inert gas such as nitrogen or in a vacuum. However, depending on the type of dopant substance used, a thin film having higher charge transport properties may be reproducibly obtained by baking the varnish in an air atmosphere.

[0242] The baking temperature is appropriately set within a range of about 100 to 260° C., taking into consideration the use of the resulting thin film, the degree of charge transport property to be imparted to the resulting thin film, the type and boiling point of the solvent, etc. When the resulting thin film is used as a hole injection layer of an organic EL device, the baking temperature is preferably about 140 to 250° C., and more preferably about 145 to 240° C.; however, when the arylamine compound of the present invention is used as a charge transport material, a thin film having good charge transport property can be formed even by baking at a low temperature of 200° C. or less. During firing, the temperature may be changed in two or more stages in order to achieve a more uniform film formation or to promote the reaction on the substrate. Heating may be performed using a suitable device such as a hot plate or an oven.

[0243] The thickness of the charge transport thin film is not particularly limited, but is preferably 5 to 300 nm when used as a hole injection layer, hole transport layer, or hole injection transport layer of an organic EL device. Methods for changing the thickness include changing the solid concentration in the varnish, changing the amount of solution (amount of varnish) on the substrate during application, and the like.

[0244] The charge-transporting thin film of the present invention described above usually exhibits a refractive index (n) of 1.60 or more and an extinction coefficient (k) of 0.100 or less, as average values ​​in the wavelength region of 400 to 800 nm; in some embodiments, it exhibits a refractive index of 1.65 or more, and in some other embodiments, it exhibits a refractive index of 1.70 or more, and in some embodiments, it exhibits an extinction coefficient of 0.050 or less, and in some other embodiments, it exhibits an extinction coefficient of 0.010 or less.

[0245] When the charge transporting thin film is applied to an organic EL device, the organic EL device may be configured to include the charge transporting thin film between a pair of electrodes. Representative configurations of the organic EL element include, but are not limited to, the following (a) to (f). In the following configurations, an electron blocking layer or the like can be provided between the light-emitting layer and the anode, and a hole (positive hole) blocking layer or the like can be provided between the light-emitting layer and the cathode, if necessary. In addition, the hole injection layer, the hole transport layer, or the hole injection transport layer may also function as an electron blocking layer, etc., and the electron injection layer, the electron transport layer, or the electron injection transport layer may also function as a hole (positive hole) blocking layer, etc. Furthermore, an arbitrary functional layer can be provided between each layer, if necessary. (a) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / cathode (c) Anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (d) Anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (e) Anode / hole injection layer / hole transport layer / light emitting layer / cathode (f) Anode / hole injection transport layer / light emitting layer / cathode

[0246] The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light-emitting layer and the anode, and have the function of transporting holes from the anode to the light-emitting layer. When only one layer of a hole transport material is provided between the light-emitting layer and the anode, it is the "hole injection transport layer". When two or more layers of a hole transport material are provided between the light-emitting layer and the anode, the layer closest to the anode is the "hole injection layer" and the other layers are the "hole transport layers". In particular, the hole injection (transport) layer is a thin film that is excellent not only in terms of hole acceptance from the anode but also in terms of hole injection into the hole transport (light-emitting) layer. An "electron injection layer," "electron transport layer," and "electron injection transport layer" are layers formed between a light-emitting layer and a cathode and have the function of transporting electrons from the cathode to the light-emitting layer. When only one layer of an electron transporting material is provided between the light-emitting layer and the cathode, it is the "electron injection transport layer." When two or more layers of an electron transporting material are provided between the light-emitting layer and the cathode, the layer closest to the cathode is the "electron injection layer," and the other layers are "electron transport layers." The "light-emitting layer" is an organic layer having a light-emitting function, and contains a host material and a dopant material when a doping system is adopted. In this case, the host material mainly has a function of promoting the recombination of electrons and holes and confining the excitons in the light-emitting layer, and the dopant material has a function of efficiently emitting the excitons obtained by the recombination. In the case of a phosphorescent element, the host material mainly has a function of confining the excitons generated by the dopant in the light-emitting layer.

[0247] The charge-transporting thin film prepared from the charge-transporting varnish of the present invention can be used as a functional layer such as a hole injection layer, a hole transport layer, or a hole injection transport layer provided between the anode and the light-emitting layer of an organic EL device, but as described above, it is usually suitable as a hole injection layer over which an upper layer is formed by a coating method.

[0248] When an organic EL device is produced using the charge transporting varnish of the present invention, the materials to be used and the production method thereof may be, but are not limited to, those described below. An example of a method for producing an OLED device having a hole injection layer made of a thin film obtained from the charge transporting varnish is as follows. Note that it is preferable to previously perform surface treatment of the electrodes, such as washing with alcohol, pure water, etc., or UV ozone treatment, oxygen plasma treatment, etc., within a range that does not adversely affect the electrodes. A hole injection layer is formed on an anode substrate by the above-mentioned method using the charge transport varnish. This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer / hole blocking layer, an electron injection layer, and a cathode metal are sequentially deposited. Alternatively, instead of forming a hole transport layer and a light emitting layer by deposition in the method, these layers are formed by a wet process using a hole transport layer forming composition containing a hole transport polymer and a light emitting layer forming composition containing a light emitting polymer. If necessary, an electron blocking layer may be provided between the light emitting layer and the hole transport layer.

[0249] Examples of anode materials include transparent electrodes such as indium tin oxide (ITO) and indium zinc oxide (IZO), metals such as aluminum, and metal anodes made of alloys thereof, and it is preferable to use those that have been subjected to planarization treatment. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used. Other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

[0250] Examples of materials for forming the hole transport layer include triarylamines such as (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine (α-NPD), 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), and 4,4',4"-tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), and oligothiophenes such as 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-terthiophene (BMA-3T).

[0251] Materials for forming the light-emitting layer include, but are not limited to, low molecular weight light-emitting materials such as metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl)benzothiazole, and silole derivatives; and systems in which a light-emitting material and an electron transfer material are mixed with a polymer compound such as poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkylthiophene), or polyvinylcarbazole. In addition, when forming a light-emitting layer by vapor deposition, it may be co-deposited with a light-emitting dopant. Examples of the light-emitting dopant include, but are not limited to, metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy)3), naphthacene derivatives such as rubrene, quinacridone derivatives, and condensed polycyclic aromatic rings such as perylene.

[0252] Examples of materials for forming the electron transport layer / hole block layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, pyrimidine derivatives, and the like.

[0253] Materials for forming the electron injection layer include, but are not limited to, metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), and alumina (Al2O3), and metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF). Cathode materials include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like. Examples of materials for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole)iridium.

[0254] The hole-transporting polymers include poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], and poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-endcapped with Examples thereof include polysilcisquinoxane and poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)].

[0255] Examples of the luminescent polymer include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), polyphenylenevinylene derivatives such as poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene) (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

[0256] The charge transporting thin film obtained from the charge transporting varnish of the present invention can be used as a functional layer such as a hole injection layer, a hole transport layer, or a hole injection transport layer provided between the anode and the light emitting layer of an organic EL device, but can also be used as a charge transporting thin film in electronic devices such as organic photoelectric conversion devices, organic thin film solar cells, organic perovskite photoelectric conversion devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic optical inspectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells, quantum dot light emitting diodes, quantum lasers, organic laser diodes, and organic plasmon light emitting devices. EXAMPLES

[0257] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The apparatus and reagents used are as follows. [Device] (1) MALDI-TOF-MS: Bruker Autoflex III Smartbeam (2) 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd. (3) Substrate cleaning: Substrate cleaning equipment (low pressure plasma method) manufactured by Choshu Sangyo Co., Ltd. (4) Varnish application: Spin coater MS-A100 manufactured by Mikasa Co., Ltd. (5) Film thickness measurement: Kosaka Laboratory Co., Ltd. Micro-shape measuring instrument Surfcorder ET-4000 (6) Fabrication of element: Multi-function deposition system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd. (7) Measurement of current density and luminance of element: Multi-channel IVL measurement device manufactured by EHC Corporation (8) EL element lifetime measurement (luminance half-life measurement): EHC Corporation, Organic EL luminance lifetime evaluation system PEL-105S (9) Measurement of refractive index (n) and extinction coefficient (k): Multi-angle spectroscopic ellipsometer VASE manufactured by J.A. Woollam Japan

[0258] [reagent] RuPhos Aldrich t-BuXPhos Aldrich t-Bu3PHBF4 Fujifilm Wako Chemical Co., Ltd. Copper(I) iodide (FUJIFILM Wako Chemical Co., Ltd.) Ethylenediamine Fujifilm Wako Chemical Co., Ltd. Pd(DBA)2 manufactured by Tokyo Chemical Industry Co., Ltd. Pd(OAc)2 (Tokyo Chemical Industry Co., Ltd.) Pd[P(C6H5)3)]4 Tokyo Chemical Industry Co., Ltd. Pd(dppf)Cl2 manufactured by Tokyo Chemical Industry Co., Ltd. 3-Bromo-9-phenylcarbazole manufactured by Tokyo Chemical Industry Co., Ltd. 3-Bromocarbazole manufactured by Tokyo Chemical Industry Co., Ltd. 4-Iodotoluene manufactured by Tokyo Chemical Industry Co., Ltd. 4-Iodoanisole manufactured by Tokyo Chemical Industry Co., Ltd. 18-Crown-6 Tokyo Chemical Industry Co., Ltd. Bis(pinacolato)diboron manufactured by Tokyo Chemical Industry Co., Ltd. 3,3',5,5'-Tetramethylbenzidine Tokyo Chemical Industry Co., Ltd. Lithium hexamethyldisilazide (LHMDS) 1.3 mol / L tetrahydrofuran solution manufactured by Tokyo Chemical Industry Co., Ltd. 2-Bromo-7-iodofluorene Tokyo Chemical Industry Co., Ltd. Benzyltriethylammonium chloride (Tokyo Chemical Industry Co., Ltd.) 3-Nitroaniline manufactured by Tokyo Chemical Industry Co., Ltd. 1-Bromo-3-nitrobenzene Tokyo Chemical Industry Co., Ltd. Hydrogen chloride (approximately 1 mol / L ethyl acetate solution) manufactured by Tokyo Chemical Industry Co., Ltd. 4,4'-Diaminodiphenylamine Tokyo Chemical Industry Co., Ltd. t-BuONa manufactured by Tokyo Chemical Industry Co., Ltd. (9-Phenyl-9H-carbazol-3-yl)boronic acid, manufactured by Tokyo Chemical Industry Co., Ltd. 1,4-Dioxane Kanto Chemical Co., Ltd. 2,2'-Bis(trifluoromethyl)benzidine Kanto Chemical Co., Ltd. Bis(4-aminophenyl)sulfone Kanto Chemical Co., Ltd. 1,4-Bis(4-amino-2-trifluoromethylphenoxy)benzene Kanto Chemical Co., Ltd. Silica gel N60 manufactured by Kanto Chemical Co., Ltd. Dimethyl sulfoxide Junsei Chemical Co., Ltd. Iodomethane Junsei Chemical Co., Ltd. Potassium carbonate Junsei Chemical Co., Ltd. Potassium acetate manufactured by Tokyo Chemical Industry Co., Ltd. Toluene Junsei Chemical Co., Ltd. Tetrahydrofuran Junsei Chemical Co., Ltd. Ethyl acetate Junsei Chemical Co., Ltd. Methanol Junsei Chemical Co., Ltd. Hexane Junsei Chemical Co., Ltd. m-Tolidine Wakayama Seika Kogyo Co., Ltd. N,N'-bis(4-aminophenyl)terephthalamide Wakayama Seika Kogyo Co., Ltd. Pd / C CGS-10DR [H2O]=54.40% NE Chemcat 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole manufactured by Beijing Aglaia Technology Development Co., Ltd.

[0259] [1] Synthesis of compounds [Production Example 1-1] [ka]

[0260] 30 mmol (11.1 g) of 2-bromo-7-iodofluorene and 3 mmol (683.3 mg) of benzyltriethylammonium chloride were weighed into a 100 mL reaction flask, and then 60 mL of dimethyl sulfoxide was added and the mixture was stirred for 10 minutes while replacing with nitrogen. 14 g of a 50% by mass aqueous solution of sodium hydroxide prepared separately was added thereto and stirred for 10 minutes, after which 72.5 mmol (10.3 g) of iodomethane was added dropwise and stirred at room temperature overnight. During the reaction, a small amount of the solution in the flask was sampled and the reaction was tracked using liquid chromatography. The area of ​​the peak attributable to the raw material decreased, while the area of ​​the peak attributable to the target product increased. No noticeable peaks corresponding to by-products were observed. The resulting reaction mixture was added to 800 mL of a mixed solvent of methanol and water (3 / 1 (v / v)), and the precipitated solid was separated by filtration using a membrane filter. Finally, the collected solid was dried under reduced pressure at 60° C. to obtain 6.26 g (78.4%) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene. 1 The H-NMR spectrum (measurement solvent: deuterated DMSO) is shown in Figure 1.

[0261] [Production Example 1-2] [ka]

[0262] A 200 mL two-necked flask was charged with 20 mmol (4.93 g) of 3-bromocarbazole, 44 mmol (9.61 g) of 4-iodotoluene, 16 mmol (3.05 g) of copper(I) iodide, 50 mmol (16.3 g) of cesium carbonate, and 100 mL of toluene, and the mixture was stirred at room temperature for 5 minutes under a nitrogen stream. Then, 30 mmol (1.82 g) of ethylenediamine was added, and the mixture was stirred overnight under heating and reflux. After the reaction mixture was cooled to room temperature, the insoluble matter was removed by filtration through Celite. The filtrate was concentrated, and the concentrate was purified by column chromatography to obtain 2.84 g (42.2%) of 3-bromo-9-(4-tolyl)carbazole. 1 H-NMR spectra (measurement solvent: deuterated THF) are shown in Figures 2 to 4.

[0263] [Production Example 1-3] [ka]

[0264] Except for using 88 mmol (20.6 g) of 4-iodoanisole instead of 44 mmol of 4-iodotoluene and doubling the amount of other reagents, the reaction and purification were carried out in the same manner as in Production Example 1-2, to obtain 11.1 g (78.7%) of 3-bromo-9-(4-methoxyphenyl)carbazole. 1 The H-NMR spectra are shown in Figures 5 and 6.

[0265] [Production Example 1-4] [ka]

[0266] In a 200mL two-neck flask, 60mmol (14.76g) of 3-bromocarbazole, 4.5mmol (0.86g) of copper(I) iodide, 63mmol (8.71g) of potassium carbonate, and 61.5mmol (16.2g) of 18-crown-6 were added, and the atmosphere in the flask was replaced with nitrogen. Then, 100mL of N,N-dimethylacetamide was added and stirred at room temperature for 10 minutes. The mixture was then heated to 160℃ and stirred for 2 hours, after which 63mmol (13.23g) of 2-iodothiophene was added and stirred for another 70 hours. After the reaction mixture was cooled to room temperature, the insoluble matter was removed by filtration through Celite. The filtrate was concentrated, and the concentrate was purified by column chromatography (eluent: n-hexane / ethyl acetate = 100 / 0 → 95 / 5) to obtain 5.80 g (29.5%) of 3-bromo-9-(thiophen-2-yl)carbazole. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 7 and 8.

[0267] [Production Example 1-5] [ka]

[0268] Except for using 60 mmol (14.76 g) of 2-bromocarbazole instead of 3-bromocarbazole, the reaction and purification were carried out in the same manner as in Production Example 1-4, and 7.36 g (37.2%) of 2-bromo-9-(thiophen-2-yl)carbazole was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 9 and 10.

[0269] [Production Example 1-6] [ka]

[0270] Into a 100 mL reaction flask were added 5 mmol (1.68 g) of 3-bromo-9-(p-tolyl)carbazole, 5.05 mmol (1.28 g) of bis(pinacolato)diboron, 15 mmol (1.47 g) of potassium acetate, 0.15 mmol (0.125 g) of Pd(dppf)Cl2, and 50 mL of N,N-dimethylformamide. The mixture was stirred at room temperature for 10 minutes while replacing with nitrogen, then the temperature was raised to 90°C and the mixture was stirred overnight. The reaction mixture was mixed with 75 mL of water and 75 mL of methylene chloride and extracted, and the organic layer was collected. The collected organic layer was dried over magnesium sulfate and filtered to remove the magnesium sulfate. The obtained filtrate was concentrated, and the concentrate was purified by column chromatography to obtain 1.42 g (74.3%) of 9-(p-tolyl)carbazole-3-boronic acid pinacolate. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 11 and 12.

[0271] [Production Example 1-7] [ka]

[0272] Except for using 10 mmol (3.522 g) of 3-bromo-9-(p-methoxyphenyl)carbazole instead of 5 mmol of 3-bromo-9-(p-tolyl)carbazole and doubling the amount of other reagents used, the reaction and purification were carried out in the same manner as in Production Example 1-6, to obtain 1.53 g (38.3%) of 9-(p-methoxyphenyl)carbazole-3-boronic acid pinacolate. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 13 and 14.

[0273] [Production Example 1-8] [ka]

[0274] Except for using 15 mmol (4.92 g) of 3-bromo-9-(thiophen-2-yl)carbazole instead of 5 mmol of 3-bromo-9-(p-tolyl)carbazole and using three times the equivalent of other reagents, the reaction and purification were carried out in the same manner as in Production Example 1-6, and 2.53 g (44.9%) of 9-(thiophen-2-yl)carbazole-3-boronic acid pinacolate was obtained. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 15 and 16.

[0275] [Production Example 1-9] [ka]

[0276] Except for using 5 mmol (1.64 g) of 2-bromo-9-(thiophen-2-yl)carbazole instead of 3-bromo-9-(p-tolyl)carbazole, the reaction and purification were carried out in the same manner as in Production Example 1-6, to obtain 1.26 g (67.2%) of 9-(thiophen-2-yl)carbazole-2-boronic acid pinacolate. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 17 and 18.

[0277] [Production Example 2-1] [ka]

[0278] In a 100 mL reaction flask, 5 mmol (1.44 g) of (9-phenyl-9H-carbazol-3-yl)boronic acid, 5.25 mmol (2.95 g) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene, 15 mmol (600 mg) of sodium hydroxide, 75 mL of a mixed solvent of tetrahydrofuran and water (2 / 1 (v / v)), and 40.15 mmol (173.5 mg) of Pd[P(C6H5)3)] were placed, and the mixture was stirred at room temperature for 10 minutes while replacing with nitrogen, and then stirred at 60 °C for 5 hours. During the reaction, a small amount of the solution in the flask was collected, and the reaction was tracked using liquid chromatography. The area of ​​the peak attributable to the raw material decreased, and the area of ​​the peak attributable to the target product increased. At that time, no noticeable peaks corresponding to by-products were confirmed. The resulting reaction mixture was added to 400 mL of a mixed solvent of methanol and water (3 / 1 (v / v)), and the precipitated solid was filtered off using a membrane filter, and the filtered solid was dried at 60° C. under reduced pressure. Furthermore, the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of n-hexane, the precipitated solid was separated by filtration using a membrane filter, and the separated solid was dried at 60° C. under reduced pressure. Finally, the dried solid was dissolved in 20 mL of tetrahydrofuran, and the resulting solution was added to 200 mL of a mixed solvent of methanol and water (3 / 1 (v / v)), and the precipitated solid was filtered off using a membrane filter. The resulting solid was dried under reduced pressure at 60°C to obtain 1.28 g (49.8%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0279] [Production Example 2-2] [ka]

[0280] Into a 100 mL reaction flask were placed 2.5 mmol (0.958 g) of 9-(p-tolyl)carbazole-3-boronic acid pinacolatoate, 2.63 mmol (1.05 g) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene, 7.5 mmol (300 mg) of sodium hydroxide, 37.5 mL of a mixed solvent of tetrahydrofuran and water (2 / 1 (v / v)), and 40.075 mmol (86.7 mg) of Pd[P(C6H5)3)]. The mixture was stirred at room temperature for 10 minutes while replacing with nitrogen, and then stirred at 60°C overnight. The reaction mixture was cooled to room temperature, and the aqueous layer was removed. The organic layer was added dropwise to a mixed solvent of methanol and water (3 / 1 (v / v)), and the precipitated solid was filtered off using a membrane filter. The filtered solid was then dried under reduced pressure at 60°C. The dried solid was dissolved in 20 mL of tetrahydrofuran, and the resulting solution was added to 200 mL of n-hexane. The precipitated solid was filtered off using a membrane filter, and the filtered solid was dried under reduced pressure at 60°C. 1.10 g (83.3%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole was obtained. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 20 and 21.

[0281] [Production Example 2-3] [ka]

[0282] Instead of 9-(p-tolyl)carbazole-3-boronic acid pinacolate, 15 mmol (5.99 g) of 9-(p-methoxyphenyl)carbazole-3-boronic acid pinacolate was used, and the amount of other reagents used was 6 times that of the original amount. The reaction and purification were carried out in the same manner as in Production Example 2-2, and 5.80 g (70.4%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-methoxyphenyl)-9H-carbazole was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0283] [Production Example 2-4] [ka]

[0284] Instead of 9-(p-tolyl)carbazole-3-boronic acid pinacolate, 5 mmol (1.79 g) of 9-(thiophen-2-yl)carbazole-3-boronic acid pinacolate was used, and the amount of other reagents used was doubled. The reaction and purification were carried out in the same manner as in Production Example 2-2, and 1.86 g (76.8%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was obtained. 1 The H-NMR spectra are shown in Figures 23 and 24 (measurement solvent: deuterated THF).

[0285] [Production Example 2-5] [ka]

[0286] Instead of 9-(p-tolyl)carbazole-3-boronic acid pinacolate, 5 mmol (1.88 g) of 9-(thiophen-2-yl)carbazole-2-boronic acid pinacolate was used, and the amount of other reagents used was doubled. The reaction and purification were carried out in the same manner as in Production Example 2-2, and 2.0 g (77.7%) of 2-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was obtained. 1 The H-NMR spectra are shown in Figures 25 and 26 (measurement solvent: deuterated THF).

[0287] [Production Example 3] [ka]

[0288] In a 1000mL reaction flask equipped with a reflux tower, 25mmol (2.88g) Pd(DBA), 10mmol (4.25g) t-BuXPhos, 300mmol (41.46g) potassium carbonate, 100mmol (13.82g) 3-nitroaniline, 110mmol (22.22g) 1-bromo-3-nitrobenzene, and 1000mL toluene were added and the flask was replaced with nitrogen, and then stirred overnight in a bath at 80°C. During the reaction, a small amount of the solution in the flask was collected and the reaction was tracked using liquid chromatography. The area of ​​the peak attributable to the raw material decreased, while the area of ​​the peak attributable to the target product increased. No noticeable peaks corresponding to by-products were observed. The reaction solution was cooled to room temperature and filtered through a filter packed with 200 g of silica gel N60, the obtained filtrate was concentrated until the weight was 100 g, and the concentrate was dropped into 1000 mL of toluene and the resulting solid was filtered off. The obtained solid was dried to obtain 24.1 g of bis(3-nitrophenyl)amine (yield 93.1%).

[0289] [Production Example 4] [ka]

[0290] In a 300 mL reaction flask equipped with a reflux tower, 77.15 mmol (20 g) of bis(3-nitrophenyl)amine and 2 g of Pd / C CGS-10DR [H2O] = 54.40% were weighed and the atmosphere in the flask was replaced with hydrogen. 200 mL of tetrahydrofuran was added and the mixture was stirred overnight at 50 °C. The mixture was cooled to room temperature and filtered through a filter packed with 200 g of Celite, and the solvent was distilled off from the filtrate under reduced pressure. A small amount of the residue was collected and 1 After confirming the formation of 3,3'-diaminodiphenylamine using H-NMR, 100g of tetrahydrofuran was added to the residue, the resulting solution was cooled to 0°C in an ice bath, and after confirming that the temperature had stabilized, 50mL of hydrogen chloride solution (approximately 1mol / L ethyl acetate solution) was added and the precipitated solid was filtered off. The resulting solid was dried to obtain 19.8g (99.0%) of 3,3'-diaminodiphenylamine dihydrochloride.

[0291] [Example 1-1] [ka]

[0292] Into a 30 mL reaction flask equipped with a reflux tower, 20.1 mmol (57.6 mg) of Pd(DBA), 0.15 mmol (70.0 mg) of RuPhos, 0.5 mmol (120.2 mg) of 3,3',5,5'-tetramethylbenzidine, and 2.1 mmol (1080.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole were weighed out and replaced with nitrogen in the system. 10 mL of dioxane was added thereto and stirred at room temperature for 5 minutes, then 1.69 mL of a 1.3 mol / L LHMDS tetrahydrofuran solution (equivalent to 2.2 mmol of LHMDS) was added and stirred at room temperature for 5 minutes, followed by heating and stirring in a 110°C bath for 8 hours (internal temperature 92°C). During the reaction, a small amount of the solution in the flask was sampled and the reaction was tracked using liquid chromatography. The area of ​​the peak attributable to the raw material decreased, while the area of ​​the peak attributable to the target product increased. No noticeable peaks corresponding to by-products were observed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of saturated aqueous ammonium chloride solution and 50 mL of a mixed solvent of ethyl acetate and tetrahydrofuran (2 / 1 (v / v)) to carry out extraction, the organic layer was left in the separatory funnel, and the aqueous layer was collected. 50 mL of saturated saline was placed in the separatory funnel to wash the remaining organic layer, and the aqueous layer and organic layer were collected separately. Then, all of the collected aqueous layers were combined and placed in a separatory funnel, 20 mL of ethyl acetate was added thereto to carry out extraction, the organic layer was collected, and all of the collected organic layers were combined and dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and the solvent was removed from the filtrate using a rotary evaporator. The residue was dissolved in 3 mL of toluene, and the resulting solution was subjected to column chromatography (developing solvent: n-hexane / methylene chloride = 60 / 40 → 0 / 100) to separate and collect a fraction containing the target product. Finally, the solvent was removed from the collected fraction, and after drying under reduced pressure at 70°C, 0.56 g (>99%) of the arylamine compound C2d was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0293] [Example 1-2] [ka]

[0294] The same procedure as in Example 1-1 was carried out except that 0.5 mmol (123.2 mg) of N,N'-bis(4-aminophenyl)terephthalamide was used instead of 3,3',5,5'-tetramethylbenzidine, to obtain 0.43 g (70.9%) of arylamine compound D2d. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0295] [Examples 1-3] [ka]

[0296] The same procedure as in Example 1-1 was repeated except that 0.5 mmol (160.12 mg) of 2,2'-bis(trifluoromethyl)benzidine was used instead of 3,3',5,5'-tetramethylbenzidine, to obtain 0.46 g (44.8%) of arylamine compound A3d. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0297] [Examples 1-4] [ka]

[0298] The same procedure as in Example 1-1 was repeated except that 0.5 mmol (124.5 mg) of bis(4-aminophenyl)sulfone was used instead of 3,3',5,5'-tetramethylbenzidine, to obtain 0.35 g (35.3%) of the arylamine compound E3d. 1 The H-NMR spectrum (measurement solvent: CDCl3) is shown in Figure 30.

[0299] [Examples 1-5] [ka]

[0300] The same procedure as in Example 1-4 was carried out except that 2.1 mmol (1.375 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole was used instead of 3-(7-bromo-9,9-dihexyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and 0.71 g (55.8%) of arylamine compound E3i was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0301] [Examples 1-6] [ka]

[0302] The same procedure as in Example 1-1 was repeated except that 0.5 mmol (219.2 mg) of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene was used instead of 3,3',5,5'-tetramethylbenzidine, to obtain 0.35 g (32.4%) of an arylamine compound F3d. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0303] [Examples 1-7] [ka]

[0304] The same procedure as in Example 1-3 was carried out except that 2.1 mmol (836.4 mg) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and 0.32 g (40.3%) of arylamine compound A3b was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0305] [Examples 1-8] [ka]

[0306] The same procedure as in Example 1-3 was carried out except that 2.1 mmol (996.2 mg) of 3-(4'-bromo-[1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and 0.57 g (60.2%) of arylamine compound A3c was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0307] [Examples 1-9] [ka]

[0308] The same procedure as in Example 1-1 was repeated except that 0.5 mmol (106.1 mg) of m-tolidine was used instead of 3,3',5,5'-tetramethylbenzidine, to obtain 0.17 g (17.5%) of an arylamine compound G3d. 1The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0309] [Examples 1-10] [ka]

[0310] In a 200mL reaction flask equipped with a reflux tower, 2mmol (0.45g) of Pd(ОAc), 4mmol (1.16g) of t-Bu3PHBF, 40mmol (3.84g) of t-BuONa, 4mmol (797.0mg) of 4,4'-diaminodiphenylamine, and 20.6mmol (10.61g) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole were weighed and replaced with nitrogen. 50mL of toluene was added and stirred overnight in a bath at 110°C. During the reaction, a small amount of the solution in the flask was collected and the reaction was tracked using liquid chromatography. The area of ​​the peaks attributable to the raw materials decreased, while the area of ​​the peaks attributable to the target product increased. No noticeable peaks corresponding to by-products were observed. The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and the concentrate was diluted with 10 mL of toluene to obtain a solution, which was used for column chromatography (developing solvent: n-hexane / methylene chloride = 70 / 30 (v / v) → 55 / 45 (v / v)), and the target fraction was collected. The collected fraction was concentrated, and the concentrate was diluted with 10 mL of toluene to obtain a solution, which was used for column chromatography again under the same conditions to obtain the target fraction. The collected fraction was concentrated, and the concentrate was dissolved in 30 mL of tetrahydrofuran, and the obtained solution was dropped into a mixed solvent of ethyl acetate and methanol (1 / 1 (v / v)), and the precipitated solid was collected through a membrane filter. The obtained solid was dried to obtain 2.67 g (28.2%) of arylamine compound H3d. The obtained compound 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0311] [Examples 1-11] [ka]

[0312] In a 30mL reaction flask equipped with a reflux tower, 2.5mmol (0.56g) of Pd(OAc), 5mmol (1.45g) of t-Bu3PHBF, 25mmol (2.40g) of t-BuONa, 2.5mmol (80.4mg) of 3,3'-diaminodiphenylamine dihydrochloride, and 12.6mmol (6.49g) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole were weighed and replaced with nitrogen. 50mL of toluene was added and stirred overnight in a bath at 110°C. During the reaction, a small amount of the solution in the flask was collected and the reaction was tracked using liquid chromatography. The area of ​​the peaks attributable to the raw materials decreased, while the area of ​​the peaks attributable to the target product increased. No noticeable peaks corresponding to by-products were observed. The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and the concentrate was diluted with 5 mL of toluene to obtain a solution, which was used for column chromatography (developing solvent: n-hexane / methylene chloride = 70 / 30 (v / v) → 55 / 45 (v / v)), and the target fraction was collected. The collected fraction was concentrated, and the concentrate was diluted with 5 mL of toluene to obtain a solution, which was used for column chromatography again under the same conditions to obtain the target fraction. The collected fraction was concentrated, and the concentrate was dissolved in 30 mL of tetrahydrofuran, and the obtained solution was dropped into a mixed solvent of ethyl acetate and methanol (1 / 1 (v / v)), and the precipitated solid was collected through a membrane filter. The obtained solid was dried to obtain 2.34 g (39.5%) of arylamine compound I3d. The obtained compound 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0313] [Examples 1-12] [ka]

[0314] In a 50 mL flask, 0.4 mmol (108.9 mg) of 3,3'-diaminodiphenylamine dihydrochloride, 2.02 mmol (1067.5 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole, 0.4 mmol (89.8 mg) of Pd(OAc), 0.8 mmol (232.1 mg) of t-Bu3PHBF, and 4 mmol (384.4 mg) of t-BuONa were placed and substituted with nitrogen. Then, 8 mL of toluene was added and stirred for 10 minutes, and then stirred overnight under heating and refluxing conditions. After the reaction mixture was cooled to room temperature, the aqueous layer was removed from the cooled reaction mixture, and the resulting organic layer was added dropwise to a mixed solvent of methanol and water (methanol / water=3 / 1 (v / v)). The precipitated solid was collected by filtration, and the resulting solid was dissolved in tetrahydrofuran, and this solution was added dropwise to n-hexane. The resulting solid was collected by filtration and dried under reduced pressure to obtain 210 mg (21.5%) of arylamine compound I3e. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 38 and 39.

[0315] [Examples 1-13] [ka]

[0316] The same procedure as in Example 1-12 was repeated except that 2-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole (2.02 mmol / l, 1051.4 mg) was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole, to obtain 157.0 mg (16.4%) of arylamine compound I3h. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 40 and 41.

[0317] [Examples 1-14] [ka]

[0318] The same procedure as in Example 1-3 was carried out except that 2.1 mmol (1109.8 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and 323.8 mg (38.3%) of arylamine compound A3e was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0319] [Examples 1-15] [ka]

[0320] The same procedure as in Example 1-3 was carried out except that 2.1 mmol (1143.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-methoxyphenyl)-9H-carbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and 552.6 mg (50.8%) of arylamine compound A3f was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0321] [Example 1-16] [ka]

[0322] The same procedure as in Example 1-3 was carried out except that 2.1 mmol (1093.0 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and 499.9 mg (48.1%) of arylamine compound A3g was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0323] [Example 1-17] [ka]

[0324] The same procedure as in Example 1-3 was carried out except that 2-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole (2.1 mmol, 1093.0 mg) was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, and arylamine compound A3h (664.9 mg, 64.0%) was obtained. 1 The 1 H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figures 45 and 46.

[0325] [Example 1-18] [ka]

[0326] In a 50 mL reaction flask, 0.5 mmol (164 mg) of octafluorobiphenyl-4,4'-diamine, 2.1 mmol (836 mg) of 3-(4-bromophenyl)-9-phenylcarbazole, 0.2 mmol (45 mg) of Pd(OAc), 0.4 mmol (166 mg) of t-Bu3PHBF, and 4 mmol (385 mg) of t-BuONa were added and purged with nitrogen. Then, 10 mL of toluene was added and the mixture was stirred at room temperature for 5 minutes and then at 100°C for 6 hours. After the reaction mixture was cooled to room temperature, the cooled reaction mixture was filtered through a membrane filter, and activated carbon was added to the obtained filtrate and stirred for 1 hour. The activated carbon was removed by filtration, and the obtained filtrate was concentrated, and the concentrate was purified by silica gel chromatography (developing solvent: n-hexane / dichloromethane = 3 / 2 (v / v)) to obtain 311.8 mg (44.6%) of arylamine compound B3b. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0327] [Example 1-19] [ka]

[0328] The same procedure as in Example 1-18 was carried out except that 2.1 mmol (996.2 mg) of 3-(4'-bromo-[1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, to obtain 391 mg (41.1%) of arylamine compound B3c. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figure 48.

[0329] [Example 1-20] [ka]

[0330] The same procedure as in Example 1-18 was carried out except that 2.1 mmol (1080.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, and 535 mg (51.9%) of arylamine compound B3d was obtained. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in FIG.

[0331] [Example 1-21] [ka]

[0332] In a 50 mL reaction flask, 0.5 mmol (164 mg) of octafluorobiphenyl-4,4'-diamine, 2.1 mmol (836 mg) of 3-(4-bromophenyl)-9-phenylcarbazole, 20.1 mmol (57.5 mg) of Pd(DBA), 0.2 mmol (84 mg) of t-Bu3PHBF, and 2 mmol (193 mg) of t-BuONa were added and purged with nitrogen. Then, 10 mL of toluene was added and the mixture was stirred at room temperature for 5 minutes and then at 100°C for 6 hours. After the reaction mixture was cooled to room temperature, the cooled reaction mixture was filtered through a membrane filter, and activated carbon was added to the obtained filtrate and stirred for 1 hour. The activated carbon was removed by filtration, and the obtained filtrate was concentrated, and the concentrate was purified by silica gel chromatography (developing solvent: n-hexane / dichloromethane = 3 / 2 (v / v)) to obtain 419.0 mg (87.0%) of arylamine compound B2b. 1 The H-NMR spectrum (measurement solvent: deuterated DMSO) is shown in Figure 50.

[0333] [Example 1-22] [ka]

[0334] The same procedure as in Example 1-21 was repeated except that 2.1 mmol (996.2 mg) of 3-(4'-bromo-[1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, to obtain 72.9 mg (13.1%) of arylamine compound B2c. 1 The H-NMR spectrum (measurement solvent: deuterated DMSO) is shown in Figure 51.

[0335] [Example 1-23] [ka]

[0336] The same procedure as in Example 1-21 was repeated except that 2.1 mmol (1080.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, to obtain 114.0 mg (19.1%) of arylamine compound B2d. 1 The H-NMR spectrum (measurement solvent: deuterated DMSO) is shown in Figure 52.

[0337] [Comparative Example 1-1] [ka]

[0338] The same procedure as in Example 1-3 was carried out except that 2.1 mmol (676.6 mg) of 3-bromo-N-phenylcarbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, to obtain 0.45 g (70.0%) of arylamine compound A3a. 1 The H-NMR spectrum (measurement solvent: deuterated DMSO) is shown in Figure 53.

[0339] [Comparative Example 1-2] [ka]

[0340] The same procedure as in Example 1-18 was carried out except that 2.1 mmol (677 mg) of 3-bromo-N-phenylcarbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, to obtain 236.2 mg (36.6%) of arylamine compound B3a. 1 The H-NMR spectrum (measurement solvent: deuterated THF) is shown in Figure 54.

[0341] [Comparative Example 1-3] [ka]

[0342] The same procedure as in Example 1-21 was carried out except that 2.1 mmol (677 mg) of 3-bromo-9-phenylcarbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, to obtain 272.3 mg (67.2%) of arylamine compound B2a. 1 The H-NMR spectrum (measurement solvent: deuterated DMSO) is shown in Figure 55.

[0343] [2] Preparation of varnish for hole injection layer [Comparative Example 2-1] Arylamine compound A3a (0.025 g) and arylsulfonic acid ester A (0.025 g) represented by the following formula were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transporting varnish A3a-1.

[0344] [ka]

[0345] [Example 2-1] Arylamine compound A3b (0.028 g) and arylsulfonic acid ester A (0.022 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3b-1.

[0346] [Example 2-2] Arylamine compound A3c (0.030 g) and arylsulfonic acid ester A (0.020 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3c-1.

[0347] [Example 2-3] Arylamine compound A3d (0.031 g) and arylsulfonic acid ester A (0.019 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3d-1.

[0348] [Example 2-4] Arylamine compound A3e (0.031 g) and arylsulfonic acid ester A (0.019 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3e-1.

[0349] [Example 2-5] Arylamine compound A3f (0.032 g) and arylsulfonic acid ester A (0.018 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3f-1.

[0350] [Example 2-6] Arylamine compound A3g (0.031 g) and arylsulfonic acid ester A (0.019 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3g-1.

[0351] [Example 2-7] Arylamine compound A3h (0.031 g) and arylsulfonic acid ester A (0.019 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish A3h-1.

[0352] [Comparative Example 2-2] Arylamine compound B3a (0.026 g) and arylsulfonic acid ester A (0.024 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B3a-1.

[0353] [Example 2-8] Arylamine compound B3b (0.029 g) and arylsulfonic acid ester A (0.021 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter having a pore size of 0.2 μm to obtain charge-transporting varnish B3b-1.

[0354] [Example 2-9] Arylamine compound B3c (0.030 g) and arylsulfonic acid ester A (0.020 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B3c-1.

[0355] [Example 2-10] Arylamine compound B3d (0.031 g) and arylsulfonic acid ester A (0.019 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B3d-1.

[0356] [Comparative Example 2-3] Arylamine compound B2a (0.020 g) and arylsulfonic acid ester A (0.030 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B2a-1.

[0357] [Example 2-11] Arylamine compound B2b (0.022 g) and arylsulfonic acid ester A (0.028 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B2b-1.

[0358] [Example 2-12] Arylamine compound B2c (0.024 g) and arylsulfonic acid ester A (0.026 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B2c-1.

[0359] [Example 2-13] Arylamine compound B2d (0.025 g) and arylsulfonic acid ester A (0.025 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish B2d-1.

[0360] [Example 2-14] Arylamine compound H3d (0.033 g) and arylsulfonic acid ester A (0.017 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish H3d-1.

[0361] [Example 2-15] Arylamine compound I3d (0.033 g) and arylsulfonic acid ester A (0.017 g) were added to chloroform (10 g) and stirred at room temperature to dissolve. The resulting solution was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge-transporting varnish I3d-1.

[0362] [3] Preparation of varnish for hole transport layer [Comparative Example 3-1] The arylamine compound A3a (0.040 g) was added to chloroform (10 g) and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore size of 0.2 μm to obtain a charge transporting varnish A3a-2.

[0363] [Examples 3-1 to 3-11] Charge transporting varnishes A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2, H3d-2, or I3d-2 were obtained in the same manner as in Comparative Example 3-1, except that arylamine compound A3b, A3c, A3d, A3e, A3f, A3g, A3h, B3d, B2d, H3d, or I3d, respectively, were used instead of arylamine compound A3a.

[0364] [4] Thin film production and film property evaluation [Comparative Example 4-1, Examples 4-1 to 4-3] Charge-transporting varnishes A3a-1, A3b-1, A3c-1, and A3d-1 were each applied to a quartz substrate using a spin coater, and then dried in air at 120°C for 1 minute. The dried quartz substrate was then baked in air at 200°C for 15 minutes to form a uniform thin film of 50 nm on the quartz substrate. The obtained quartz substrate with the film was used to measure the average refractive index (n) in the visible region at wavelengths of 400 to 800 nm and the average extinction coefficient (k) in the visible region. The results are shown in Table 23.

[0365] [Table 23]

[0366] As shown in Table 23, the thin film obtained from the charge transporting varnish of the present invention has a refractive index that is equal to or higher than that of the thin film obtained from the charge transporting varnish of Comparative Example 4-1, and has an extinction coefficient that is equal to or lower than that of the thin film obtained from the charge transporting varnish of Comparative Example 4-1.

[0367] [5] Fabrication and characterization of hole-only devices (HODs) [Comparative Example 5-1] As the ITO substrate, a 25mm x 25mm x 0.7t glass substrate with indium tin oxide (ITO) patterned on the surface with a film thickness of 150 nm was used, and impurities on the surface were removed using an O2 plasma cleaning device (150W, 30 seconds) before use. Next, the composition for forming a hole injection layer obtained by the method described below was applied by spin coating, heated to 80°C on a hot plate in the air and dried for 1 minute, and then baked at 230°C for 15 minutes to form a hole injection layer (film thickness: 30 nm). Next, the charge transporting varnish A3a-2 was applied onto the hole injection layer using a spin coater, and then baked at 130° C. for 10 minutes in an air atmosphere to form a hole transporting layer (film thickness: 40 nm). On top of this, a deposition device (vacuum degree 1.0×10 -5 A hole-only device (HOD) was obtained by depositing an 80 nm aluminum thin film at 0.2 nm / sec using a 1000 keV dc laser. The composition for forming a hole injection layer was prepared by the following procedure. 0.137 g of an aniline derivative represented by formula (3) synthesized according to the method described in WO 2013 / 084664 and 0.271 g of an arylsulfonic acid represented by formula (4) synthesized according to the method described in WO 2006 / 025342 were dissolved in 6.7 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere. 10 g of cyclohexanol and 3.3 g of propylene glycol were added to the obtained solution in order and stirred to obtain a composition for forming a hole injection layer (hereinafter the same).

[0368] [ka]

[0369] [Examples 5-1 to 5-11] HOD was prepared in the same manner as in Example 5-1, except that charge transporting varnish A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2, H3d-2, or I3d-2 was used instead of charge transporting varnish A3a-2.

[0370] For each of the HODs produced in the above Examples and Comparative Examples, the current density was measured at a driving voltage of 4 V. The results are shown in Table 24.

[0371] [Table 24]

[0372] As shown in Table 24, the thin film prepared from the charge-transporting varnish of the present invention exhibits better charge transport properties than the thin film prepared from the charge-transporting varnish of the comparative example. This improvement in charge transport properties is believed to be due to an increase in the effective conjugation length of the conductive portion in the arylamine compound of the present invention.

[0373] [6] Preparation of single-layer elements (SLD) and HODs, and evaluation of the relative intensity of the current density of HODs to that of SLDs [Comparative Example 6-1] The ITO substrate was a 25 mm x 25 mm x 0.7 mm glass substrate with a 150 nm thick indium tin oxide (ITO) patterned on the surface, and impurities on the surface were removed using an O2 plasma cleaning device (150 W, 30 seconds) before use. The charge transporting varnish A3a-1 was applied onto an ITO substrate by spin coating, dried at 120° C. for 1 minute in air, and then baked at 200° C. for 15 minutes to form a hole injection layer (film thickness: 50 nm) on the ITO substrate. On top of this, a deposition device (vacuum degree 1.0×10 -5 A single-layer device (SLD) was obtained by depositing an 80 nm aluminum thin film at 0.2 nm / s using a 1000 MPa (100 MPa) laser.

[0374] [Examples 6-1 to 6-12, Comparative Example 6-2] SLDs were prepared in the same manner as in Comparative Example 6-1, except that charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1, B2d-1, H3d-1, I3d-1, or B3a-1 were used instead of charge-transporting varnish A3a-1.

[0375] [Comparative Example 7-1] The charge transporting varnish A3a-1 was applied to an ITO substrate using a spin coater, then dried at 120° C. for 1 minute in the atmosphere, and then baked at 200° C. for 15 minutes to form a 50 nm thin film on the ITO substrate. The ITO substrate used was the same as that used in Comparative Example 6-1. On top of that, a deposition device (vacuum degree 2.0×10 -5 Using a vacuum evaporation method, thin films of α-NPD and aluminum were successively laminated to obtain HOD. The deposition rate was 0.2 nm / sec. The thicknesses of the thin films of α-NPD and aluminum were 30 nm and 80 nm, respectively.

[0376] [Examples 7-1 to 7-12, Comparative Example 7-2] HODs were prepared in the same manner as in Comparative Example 7-1, except that charge transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1, B2d-1, H3d-1, I3d-1, or B3a-1 were used instead of charge transporting varnish A3a-1.

[0377] The current density was measured when the SLDs produced in Examples 6-1 to 6-12 and Comparative Examples 6-1 to 6-2, and the HODs produced in Examples 7-1 to 7-12 and Comparative Examples 7-1 to 7-2 were driven at a voltage of 4 V. The results are shown in Table 25. The relative intensity of the current density of the HOD to the current density of the SLD, calculated using these measured values, is also shown. Note that a high relative intensity indicates that holes are efficiently supplied to the hole transport layer.

[0378] [Table 25]

[0379] As shown in Table 25, the element using the hole injection layer prepared from the charge transport varnish of the present invention was found to have a higher relative intensity of HOD current density to SLD current density compared to the element prepared in the comparative example.

[0380] [7] Fabrication and characterization of organic electroluminescence devices [Comparative Example 8-1] The charge transporting varnish A3a-1 was applied to an ITO substrate using a spin coater, then dried at 120° C. for 1 minute in the atmosphere, and then baked at 200° C. for 15 minutes to form a 50 nm thin film on the ITO substrate. The ITO substrate used was the same as that used in Comparative Example 6-1. Next, the ITO substrate on which the thin film was formed was placed in a deposition device (vacuum degree 1.0×10 -5 A 30 nm film of α-NPD was formed at 0.2 nm / sec using a 1000 sieve vacuum chamber (Pa). Next, a 10 nm film of an electron block material HTEB-01 manufactured by Kanto Chemical Co., Ltd. was formed. Next, an emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and an emitting layer dopant material Ir(ppy)3 were co-deposited. The deposition rate of the co-deposition was controlled so that the concentration of Ir(ppy)3 was 6%, and a 40 nm film was laminated. Next, thin films of Alq3, lithium fluoride, and aluminum were laminated in order to obtain an organic EL device. At this time, the deposition rate was 0.2 nm / sec for Alq3 and aluminum, and 0.02 nm / sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively. In order to prevent deterioration of characteristics due to the influence of oxygen, water, etc. in the air, the organic EL element was sealed with a sealing substrate before evaluating its characteristics. Sealing was performed as follows. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, the organic EL element was placed between the sealing substrates, and the sealing substrates were bonded together with an adhesive (MORESCO Moisture Cut WB90US(P) manufactured by MORESCO Corporation). At this time, a moisture scavenger (HD-071010W-40 manufactured by DYNIC Co., Ltd.) was placed inside the sealing substrate together with the organic EL element. The bonded sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation dose: 6,000 mJ / cm2). 2 ), and then annealed at 80°C for 1 hour to harden the adhesive.

[0381] [Examples 8-1 to 8-12] Organic EL elements were prepared in the same manner as in Comparative Example 8-1, except that charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1, B2d-1, H3d-1, or I3d-1 were used instead of charge-transporting varnish A3a-1.

[0382] The resulting organic EL device had a brightness of 5,000 cd / m 2 The driving voltage, current density, current efficiency, luminous efficiency, external luminescence quantum yield (EQE), and LT90 (initial luminance 5,000cd / m 2 The time required for a 10% decrease in the concentration of 1,000 mg / kg of 10% ethanol was measured. The results are shown in Table 26.

[0383] [Table 26]

[0384] As shown in Table 26, compared with the organic EL element of Comparative Example 8-1, all of the organic EL elements of the present invention exhibited driving voltages comparable to or lower than that, and had half-lives comparable to or longer than that.

Claims

1. An arylamine compound represented by the following formula (3): 【Chemistry 1】 [In the formula, Ar c are the same group and represent a group represented by formula (Q), 【Chemistry 2】 [In the formula, R 1 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 2 each independently represents an aryl group which may be substituted and may contain a heteroatom; Ar s represents an arylene group represented by any one of the following formulas (101A-1), (101B-1), (101C-1), (105A-1), (107A-1), (107A-2), (107A-3), (107A-4) and (107A-5), 【Chemistry 3】 (In the formula, R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. X represents any one of groups represented by the following formulas (201A-1) to (208A-1): 【Chemistry 4】 【Chemistry 5】 [In the formula, R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; R 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; W 3 is N.R. 8 (R 8 has the same meaning as above. ), represents S or O. Y represents a phenylene group; Each g independently represents an integer of 1 to 10.

2. The R 1 The arylamine compound according to claim 1, wherein is a hydrogen atom.

3. The R 2 The arylamine compound according to claim 1 or 2, wherein is an aryl group having 6 to 10 carbon atoms.

4. The R 2 The arylamine compound according to claim 1 or 2, wherein the arylamine compound is represented by any one of the following formulas: 【Chemistry 6】

5. A charge-transporting varnish comprising the arylamine compound according to any one of claims 1 to 4 and an organic solvent.

6. 6. The charge transport varnish of claim 5 which contains a dopant material.

7. A charge transporting thin film produced by using the charge transporting varnish of claim 5 or 6.

8. An electronic device comprising the charge transporting thin film according to claim 7.

9. 9. The electronic device according to claim 8, wherein the charge transporting thin film is a hole injection layer.

10. 10. The electronic device according to claim 9, which is an organic EL device.

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