Arylamine compound and its use

Abstract

For example, arylamine compounds represented by formula (1) or (2) have good solubility in organic solvents and provide a varnish having good storage stability and a thin film having good optical properties, and an organic EL element having good properties can be achieved when this thin film is applied to a hole injection layer or the like. (R1 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-20 alkyl group, a C1-20 alkyl halide group, a C1-20 alkoxy group, or a C6-20 aryl group, R2 each independently represent an optionally substituted aryl group optionally containing a hetero atom, Ars each independently represent an optionally substituted arylene group optionally containing a hetero atom, and X represents an optionally substituted arylene group optionally containing a hetero atom.)

Description

Technical Field

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

Background Art

[0002] Organic electroluminescence (hereinafter referred to as organic EL) elements are expected to be put into practical use in fields such as displays and lighting, and various developments have been made for the purpose of low-voltage driving, high brightness, long life, etc. regarding materials and element structures. In this organic EL element, a plurality of functional thin films are used. Among them, the hole injection layer, which is one of them, is responsible for the transfer of charges between the anode and the hole transport layer or the light-emitting layer, and plays an important role in achieving low-voltage driving and high brightness of the organic EL element.

[0003] The method for fabricating this hole injection layer is roughly classified into a dry process typified by a vapor deposition method and a wet process typified by a spin coating method. Comparing these processes, the wet process can more efficiently produce a thin film with high flatness over a large area. Therefore, at present when the large area of organic EL displays is being promoted, a hole injection layer that can be formed by a wet process is desired.

[0004] In view of such circumstances, the present inventors have developed a charge transport material that can be applied to various wet processes and provides a thin film capable of realizing excellent EL element characteristics when applied to the hole injection layer of an organic EL element, and a compound having good solubility in an organic solvent used therefor (see Patent Documents 1 to 3).

[0005] On the other hand, various efforts have been made to improve the performance of organic EL elements. For the purpose of improving the light extraction efficiency, etc., efforts have been made to adjust the refractive index of the functional thin films used. Specifically, in consideration of the overall structure of the element and the refractive index of other adjacent members, attempts have been made to improve the efficiency of the element by using a hole injection layer or a hole transport layer having a relatively high or low refractive index (see Patent Documents 4 and 5). Thus, the refractive index is an important factor in the design of organic EL elements, and in materials for organic EL elements, the refractive index is also considered to be an important physical property value that should be taken into account.

[0006] In addition, the coloring of the charge transporting thin film used in the organic EL element deteriorates the color purity and color reproducibility of the organic EL element. Therefore, in recent years, the charge transporting thin film for the organic EL element is desired to have a high transmittance in the visible region and high transparency (see Patent Document 6).

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention has been made in view of such circumstances, and an object of the present invention is to provide an arylamine compound that has good solubility in an organic solvent, gives a thin film having good optical properties, and has good properties when this thin film is applied to a hole injection layer or the like, thereby realizing an organic EL element.

Means for Solving the Problems

[0009] As a result of intensive studies to achieve the above object, the present inventors have found that a compound having an aryl diamine skeleton at the center and at least one arylcarbazole bonded to each of the two amino groups via a spacer having a predetermined arylene skeleton has good solubility in an organic solvent, and a varnish obtained by dissolving this in an organic solvent gives a thin film having excellent optical properties, and when this thin film is applied to a hole injection layer or the like, an organic EL element having good properties can be obtained, and thus the present invention has been completed.

[0010] That is, the present invention relates to 1. An arylamine compound represented by any one of the following formulas (1) to (6) (however, excluding the compounds represented by the following formulas (P1) to (P4)). [Chemical formula] [In the formula, Ar c each independently represents a group represented by the formula (Q), X each independently represents an arylene group which may be substituted and may contain a heteroatom, Y each independently represents a phenylene group which may be substituted, g each independently represents an integer of 1 to 10. [Chemical formula] (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, and R 2 each independently represents an aryl group which may be substituted and may contain a heteroatom, and Ar s each independently represents an arylene group which may be substituted and may contain a heteroatom.) [Chemical formula] 2. The above-mentioned Ars is an arylamine compound of 1 represented by any of the following formulas (101) to (118),

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Advantages of the Invention

[0011] The arylamine compound of the present invention has good solubility in an organic solvent. By using a charge transporting varnish containing this arylamine compound, a charge transporting thin film with high transparency and 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 elements, particularly as a thin film for electronic devices in which a thin film is laminated by a wet process on the upper layer. By applying the charge transporting thin film of the present invention to a hole injection layer or the like of an organic EL element, an element having good characteristics can be manufactured.

Brief Description of Drawings

[0012]

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Mode for Carrying Out the Invention

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

[0014]

Chemical formula

[0015] In formulas (1) to (6), Ar cEach independently represents a group represented by the following formula (Q), X each independently represents an arylene group which may be substituted and may contain a hetero atom, Y each independently represents a phenylene group which may be substituted, and g each 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]

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[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 hetero atom, Ar s Each independently represents an arylene group which may be substituted and may contain a hetero atom.

[0018] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic. For example, 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, n-decyl groups; 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, bicyclodecyl groups, etc. can be mentioned.

[0019] The alkoxy group having 1 to 20 carbon atoms may be a linear, branched or cyclic alkyl group therein, 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, 3-ethylhexyloxy group and the like.

[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, 9-phenanthryl group and the like.

[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, 2-(perfluorohexyl)ethyl group and the like.

[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 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 its constituent atom, and may have a fused ring structure or a linked ring structure. Its carbon number 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 heteroatom 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, etc. 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 described above.

[0024] Specific examples of the alkenyl group 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, n-1-eicosenyl group, etc.

[0025] Specific examples of the alkynyl group 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-pentadecynyl, n-1-eicosenyl group, etc.

[0026] R 2 is preferably an aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom, more preferably a phenyl group which may be substituted or a naphthyl group which may be substituted, still more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. Hereinafter, specific examples of preferred groups for R 2 are given, but are not limited thereto.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[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 that may contain a heteroatom as its constituent atom, and may have a structure in which rings are condensed or a structure in which rings are linked. Its carbon number 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 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. 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 described above. In a preferred embodiment, Ar s is a group represented by any one of the following formulas (101) to (118).

[0035]

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[0036]

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[0037]

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[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, and V 1 each independently represents 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.), S, O, or SO2, and V 2 is NR 5 (R 5 represents the same meaning as described above.), represents S or O. R 3 ~R 5 Examples of the halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and halogenated alkyl group having 1 to 20 carbon atoms in R

[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. Note that from the viewpoint of reducing the attenuation coefficient of the obtained thin film, at least one R 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. Considering this point, 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 even more preferably a methyl group in both cases. 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 even more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0040] Also, when not all of the R 3 are electron-withdrawing groups, from the viewpoint of reducing the attenuation coefficient of the obtained thin film, V1 S, O, and SO2 are preferred. Note that when V 1 is S, O, or SO2, an electron-withdrawing group may be present in R 3 . Furthermore, when not all Rs 3 are electron-withdrawing groups, V is preferably S or O from the viewpoint of reducing the attenuation coefficient of the resulting thin film. Note that when V 2 is S or O, an electron-withdrawing group may be present in R 2 . 3

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

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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

[0050] Hereinafter, specific examples suitable as Ar s will be given, but the invention is not limited thereto.

[0051] [Chemical formula]

[0052] [Chemical formula]

[0053] [Chemical formula]

[0054] [Chemical formula]

[0055] [Chemical formula] (In the formula, R 4 and R 5 represent the same meaning as described above.)

[0056] [Chemical formula] (In the formula, R 4 and R 5 represent the same meaning as described above.)

[0057] [Chemical formula] (In the formula, R4 and R 5 represents the same meaning as described above.)

[0058]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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

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

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

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

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

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

[0071] [Chemical formula]

[0072] [Chemical formula] (In the formula, R 5 represents the same meaning as described above.)

[0073] [Chemical formula] (In the formula, R 5 represents the same meaning as described above.)

[0074] The arylene group in which X in the above formulas (1) and (2) may be substituted and which may contain a heteroatom is not particularly limited, and may have a structure in which rings are condensed or a structure in which rings are 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 in which X may be substituted and which 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, etc. 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 described above.

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

[0076] [Chemical formula]

[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, and W 1 each independently represents a single bond, C(R 7 )2 (wherein 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.), S, O, or SO2, and W 2 is C(R 7 )2 (wherein R 7 represents the same meaning as described 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, and W 3 is NR 8 (R 8 represents the same meaning as described above.), S or O. Examples of the halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and halogenated alkyl group having 1 to 20 carbon atoms in R 6 to R 8 are the same as those described above.

[0078] In particular, R 6 each independently is 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. From the viewpoint of reducing the attenuation coefficient of the obtained thin film, at least one R 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. Considering this point, a trifluoromethyl group is more preferable. R 7 each independently is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group in both cases. 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 even more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0079] Also, when all of the Rs 6 are not electron-withdrawing groups, W is preferably S, O, or SO2 from the viewpoint of reducing the attenuation coefficient of the resulting thin film. Incidentally, when W 1 is S, O, or SO2, an electron-withdrawing group may be present in R 1 . 6

[0080] Also, when all of the Rs 6 are not electron-withdrawing groups, W is preferably S, O, or SO2 from the viewpoint of reducing the attenuation coefficient of the resulting thin film. Incidentally, when W 2 is S, O, or SO2, an electron-withdrawing group may be present in R 2 . 6 Furthermore, when all of the Rs 6 are not electron-withdrawing groups, W is preferably S or O from the viewpoint of reducing the attenuation coefficient of the resulting thin film. Incidentally, when W 3 is S, O, or SO2, an electron-withdrawing group may be present in R 3 . 6

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

[0082]

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

[0084]

Chemical formula

[0085] In the 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 described 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 even more preferably a methyl group or a trifluoromethyl group.

[0086] Preferred X in the present invention includes, but is not limited to, those represented by the following formulas.

[0087]

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[0088]

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[0089]

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[0090] Examples of the optionally substituted phenylene group of 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, etc. Considering the balance of refractive index, transparency, and electrical properties, an optionally substituted 1,4-phenylene group or 1,3-phenylene group is preferred, and an unsubstituted 1,4-phenylene group or 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. Considering 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, 1 or 2 is still more preferred, and considering the availability of the starting compounds, 1 is most optimal.

[0092] In the present invention, Ar s is preferably a group represented by formula (107), more preferably a group represented by any of formulas (107A) to (107C), even more preferably a group represented by any of formulas (107A-1) to (107C-5), and still more 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 formulas (1) to (6), Ar c is 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 C2or a group represented by the formula (Q-3) (Ar C3 ) is.

[0094]

Chemical formula

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

[0096]

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[0097]

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[0098]

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[0099] The arylamine compound represented by the 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]

Chemical formula

[0101] Examples of the halogen atom include the same ones as described above. Examples of the pseudo halogen group include (fluoro)alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy, and nonafluorobutanesulfonyloxy groups; and aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy groups.

[0102] The charging ratio of the aryl diamine compound [I] and the aryl halide compound [II] is appropriately determined usually in the range of 1.2 to 0.6 equivalents of the aryl halide compound with respect to the total amount of substance of all NH groups of the aryl diamine compound [I] according to whether the compound to be synthesized is either of the arylamine compounds (1) and (2), and considering the reactivity and bulkiness of the raw material compounds, etc. When synthesizing the arylamine compound (1), it is preferable that the amount of the aryl halide compound is 1.0 equivalent or more.

[0103] Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; 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(P-t-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. Also, these catalysts may be used together with known appropriate ligands.

[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, 1,1'-bis(diphenylphosphino)ferrocene; tertiary phosphites such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite; 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, CPhos, etc., which are commercially available from Aldrich.

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

[0106] In addition, a base may be used in the above reaction. Examples of the base include simple alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxy potassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; hydrogenated alkali metals, hydroxylated alkali metals, alkoxy alkali metals, carbonate alkali metals, bicarbonate alkali metals; 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), lithium hexamethyldisilazane (LHMDS); and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine, and the like. When using a base, the amount used can be 0.1 to 5 equivalents, preferably 1 to 2 equivalents, relative to the aryl halide compound [II] used.

[0107] When all the starting compounds are solids or from the viewpoint of efficiently obtaining the target arylamine compound, each of the above reactions is carried out in a solvent. When using a solvent, the type thereof is not particularly limited 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-dimethoxyethane, 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.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), and the like. 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. In particular, about 0 to 200 °C is preferable, and 20 to 150 °C is more preferable. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the starting compounds, etc., but is usually about 30 minutes to 50 hours. After completion of the reaction, post-treatment is carried out according to a conventional method to obtain the target arylamine compound.

[0109] The arylamine compounds represented by the formulas (3) to (5) of the present invention (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] [Chemical formula] (In the formula, Y, R 1 , R 2 , Z, Ar s and g represent the same meanings as described above.)

[0111] The charging ratio of the aryldiamine compound [I'] to the aryl halide compound [II] is not particularly limited as long as the target product can be obtained. Usually, depending on which of the arylamine compounds (3) to (5) is to be synthesized, and considering the reactivity and bulkiness of the raw material compounds, etc., it is appropriately determined within the range of 1.2 equivalents or less of the aryl halide compound with respect to the total amount of substance of the NH groups of the aryldiamine compound [I']. When synthesizing the arylamine compound (3), it is preferably 1.0 equivalent or more of the aryl halide compound with respect to the total amount of substance of the NH groups of the aryldiamine compound [I']. When synthesizing the arylamine compound (4), it can be 2.0 equivalents or more of the aryl halide compound with respect to the amount of substance of the aryldiamine compound [I'], but 2.0 to 2.4 equivalents are preferred. When synthesizing the aryl halide amine compound (5), it can be 4.0 equivalents or more of the aryl compound with respect to the amount of substance of the aryldiamine compound [I'], but 4.0 to 4.8 equivalents are preferred. In addition, various conditions and preferred conditions of the coupling reaction regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compounds represented by the formula (1) or (2).

[0112] The arylamine compound represented by the 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] and an aryl halide compound [II] are reacted to obtain a dinitro compound [I”-2].

[0113]

Chemical formula

[0114] The charging ratio of the dinitro compound [I”-1] to the aryl halide compound [II] can be 1 equivalent or more of the aryl halide compound with respect to the total amount of substance of all NH groups of the dinitro compound, but about 1 to 1.2 equivalents is preferred. In addition, various reaction conditions and preferred conditions regarding catalysts, ligands, bases, solvents, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by formula (1) or (2).

[0115] Next, the nitro groups in the dinitro compound [I”-2] are reduced by hydrogenation to obtain an amine compound [I”-3]. The hydrogenation includes a hydrogenation reaction using Pd / C or the like and can be carried out by a known method.

[0116]

Chemical formula

[0117] Next, the amine compound [I”-3] and the aryl halide compound [II] can be reacted to obtain an arylamine compound (6).

[0118]

Chemical formula

[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 with respect to the amine compound, but about 2 to 2.4 equivalents is preferable. In addition, the various reaction conditions and preferred conditions regarding catalysts, ligands, bases, solvents, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by formula (1) or (2).

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

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

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

[0123] [Chemical formula]

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

[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, and D 3 represents an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms. 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 described above.

[0126] Examples of the alkandiyl 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-methylpentane-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, 2,5-dimethylhexane-2,5-diyl groups and the like.

[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, 9,10-phenanthrylene groups and the like.

[0128] The charging ratio of the arylcarbazole compound [III] to the diaryl halide compound [IV] can be 1.0 or more in terms of molar ratio with respect to 1 of the arylcarbazole compound [III], but about 1.0 to 1.2 is preferred.

[0129] When all the starting compounds are solids or from the viewpoint of efficiently obtaining the target halogenated arylamine compound, each of the above reactions is carried out in a solvent. When using a solvent, the type thereof 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, particularly, 1,4-dioxane, toluene, xylene, etc. are 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(P-t-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. In particular, it 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 starting compounds, etc., and is usually about 30 minutes to 50 hours. After completion of the reaction, post-treatment is carried out according to a conventional method to obtain the target arylamine halide compound.

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

[0133]

Chemical formula

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

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

[0136]

Chemical formula

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

[0138] Furthermore, as shown in the following scheme, the compound represented by formula [III'] can be obtained by reacting the compound represented by formula [III'-2] with an aryl halide compound (R 2 Z) and then treating it with a halogenating agent, or by treating the compound represented by formula [III'-2] with a halogenating agent and then reacting it with an aryl halide compound (R 2 Z). From the viewpoint of avoiding halogenation of the aryl group at the N-position of the carbazole skeleton and obtaining the target product more efficiently, the latter reaction is preferred.

[0139]

Chemical formula

[0140] As the halogenating agent used in the above reaction, known ones can be used, and the amount of the halogenating agent is about 1 to 1.5 moles per mole of the compound represented by formula [III'-1-1] or [III'-2] in terms of molar ratio. The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this kind of reaction. The above temperature is usually appropriately determined from the range of 0 to 140 °C, and the time is usually appropriately determined from 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 a raw material for the spacer backbone, can be obtained by reacting the compound represented by formula [VI'] with the compound represented by formula [VII] in the presence of a base, as shown in the following scheme.

[0142]

Chemical formula

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

[0144] The 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 a nitro group by hydrogenation, and the chain length (number of phenylene groups) can be extended by repeating the reactions of (A) and (B).

[0145]

Chem.

[0146]

Chem.

[0147] More specifically, for example, the amine compound included in the amine compound [I'] can be obtained by (A) a coupling reaction of m-phenylenediamine or 3-nitroaniline with 3-halogenonitrobenzene and (B) a reduction reaction of the nitro group by hydrogenation as shown in the following scheme. By repeating the reactions of (A) and (B), the chain length (number of m-phenylene) can be extended.

[0148]

Chem.

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

[0150] In this case, the charging ratio of the raw material compounds in each reaction is a molar ratio, and the raw material compound having a nitro group (raw material compound containing a halogen atom (pseudo-halogen group)) is added to the raw material compound having an amino group in the range of about 1 to 2.4, and is appropriately determined according to whether the number of added phenylene is 1 or 2.

[0151] In addition, examples of the palladium catalyst used in the coupling reaction include the same ones as described above. Also, in this case, a ligand can be used. As ligands, in addition to those exemplified above, commercially available from Aldrich, 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, CPhos and other biphenylphosphine compounds can be preferably used.

[0152] Examples of the base used in the coupling reaction include simple alkali metals such as lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; alkali metal hydrides, alkali metal hydroxides, alkoxyalkali metals, alkali metal carbonates, 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), lithium hexamethyldisilazane (LHMDS); and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine.

[0153] In addition, various conditions and preferred conditions of the coupling reaction regarding catalysts, solvents, reaction temperature and time, etc. are the same as those described for the arylamine compounds represented by formula (1) or (2). Also, the hydrogenation reaction using Pd / C can be carried out by a known method. When introducing a paraphenylene group or orthophenylene in place of the metaphenylene group, 4-halonitrobenzene or 2-halonitrobenzene may be used instead of 3-halonitrobenzene.

[0154] Hereinafter, specific examples of the arylamine compounds of the present invention are given, but the present invention is not limited thereto. 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, respectively. For example, the arylamine compounds of numbers 1 and 865 are the following compounds, respectively.

[0155]

Chemical formula

[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 arylamine compound of the present invention described above 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. However, this charge transporting varnish may contain a dopant substance for the purpose of improving its charge transporting ability or the like according to the use of the obtained thin film. Further, 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. However, it is preferable to use the arylamine compound of the present invention alone as a charge transporting material. In the present invention, charge transportability is synonymous with conductivity. The charge transport varnish may itself have charge transportability, or the solid film obtained therefrom may have charge transportability.

[0179] The dopant substance is not particularly limited as long as it is soluble in at least one solvent used in the varnish, and either an inorganic dopant substance or an organic dopant substance can be used. In addition, the inorganic and organic dopant substances may be used alone or in combination of two or more. Furthermore, the dopant substance is a substance whose function as a dopant substance begins to be expressed or improved for the first time by an external stimulus such as heating during firing, for example, when a part of the molecule is removed, for example, during the process of obtaining a charge transport thin film, which is a solid film, from the varnish. It may be an aryl sulfonate compound protected with a group that easily desorbs a sulfonic acid group.

[0180] In particular, in the present invention, as the inorganic dopant substance, heteropoly acid is preferable. Heteropoly acid is typically represented by the Keggin type represented by formula (H1) or the Dawson type represented by formula (H2), and has a structure in which a heteroatom is located at the center of the molecule. It is a polyacid formed by the condensation of an isopoly acid, which is an oxyacid such as vanadium (V), molybdenum (Mo), or tungsten (W), and an oxyacid of a different element. Examples of such oxyacids of different elements mainly include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).

[0181]

Chemical formula

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

[0183] The amount of the heteropoly acid used can be about 0.001 to 50.0, preferably about 0.01 to 20.0, more preferably about 0.1 to 10.0, in terms of mass ratio to the charge transport material 1.

[0184] On the other hand, as the organic dopant substance, a tetracyanoquinodimethane derivative or a benzoquinone derivative can be particularly used. Specific examples of the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 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, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and the like.

[0185]

Chemical formula

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

[0187] Specific examples of such halotetracyanoquinodimethane 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, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), and the like.

[0188] The usage amounts of the tetracyanoquinodimethane derivative and the benzoquinone derivative are preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and even more preferably 1 to 20 equivalents with respect to the charge transporting substance.

[0189] In addition, as the organic dopant substance, an electrically neutral onium borate salt composed of a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by the formulas (c1) to (c5) can also be used.

[0190]

Chemical formula

[0191]

Chemical formula

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

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

[0194] [Chemical formula]

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

[0196] Also, as the organic dopant substance, arylsulfonic acid compounds and arylsulfonic acid ester compounds can also be preferably 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, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 2,7-dinonyl-4,5-naphthalenedisulfonic acid, the 1,4-benzooxanedisulfonic acid compound described in International Publication No. 2005 / 000832, the arylsulfonic acid compound described in International Publication No. 2006 / 025342, the arylsulfonic acid compound described in International Publication No. 2009 / 096352, and the like.

[0198] Examples of the preferred arylsulfonic acid compound include the arylsulfonic acid compound represented by the formula (H4) or (H5).

[0199]

Chemical formula

[0200] A 1 represents O or S, with O being preferred. A 2 represents a naphthalene ring or an anthracene ring, with the naphthalene ring being preferred. A 3 represents a 2- to 4-valent perfluorobiphenyl group, p represents the number of bonding sites between A 1 and A 3 and is an integer satisfying 2 ≤ p ≤ 4, and A 3is a perfluorobiphenyldiyl group, preferably a perfluorobiphenyl-4,4'-diyl group, and p is preferably 2. q represents the number of sulfonic acid groups bonded to A 2 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, provided that at least 3 of A 4 ~A 8 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, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, and the like.

[0203] Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), perfluorobutenyl group, and the like. In addition, examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms are the same as those described above, and the fluorine atom is preferred as the halogen 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 8Among them, at least three are preferably fluorine atoms, and are 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 A 4 ~A 8 Among them, it is more preferable that at least three are fluorine atoms, and are 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, and A 4 、A 5 and A 8 are even more preferably fluorine atoms. Incidentally, the perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all hydrogen atoms of the alkenyl group are 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 the dopant substance is not particularly limited, but considering the solubility in the organic solvent when used together with the arylamine compound of the present invention, it is preferably 2000 or less, more preferably 1500 or less.

[0207] Hereinafter, specific examples of suitable arylsulfonic acid compounds are given, but the invention is not limited thereto.

[0208]

Chemical formula

[0209]

Chemical formula

[0210]

Chemical formula

[0211] The amount of the arylsulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, in terms of the molar ratio to the charge transporting material 1. As the arylsulfonic acid compound, a commercially available product may be used, or it can also be synthesized by known methods described in International Publication No. WO2006 / 025342, International Publication No. WO2009 / 096352, International Publication No. WO2015 / 111654, International Publication No. WO2015 / 053320, International Publication No. WO2015 / 115515, etc.

[0212] On the other hand, examples of the arylsulfonic acid ester compound include the arylsulfonic acid ester compound disclosed in International Publication No. WO2017 / 217455, the arylsulfonic acid ester compound disclosed in International Publication No. WO2017 / 217457, the arylsulfonic acid ester compound described in Japanese Patent Application No. 2017-243631 (International Publication No. WO2019 / 124412), etc. Specifically, those represented by any of the following formulas (H6) to (H8) are preferable.

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

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

[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, n-hexyl group, etc., and an alkyl group having 1 to 3 carbon atoms is 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, t-butyl group; aryl groups such as phenyl, naphthyl, phenanthryl group, etc.

[0216] In particular, R s1 ~R s4 Among them, 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 are preferably hydrogen atoms. In this case, as the linear alkyl group having 1 to 3 carbon atoms, a methyl group is preferred. Also, as R s5 a linear alkyl group having 2 to 4 carbon atoms or a phenyl group is preferred.

[0217] In formula (H7), A 14 is an m-valent hydrocarbon group having 6 to 20 carbon atoms containing one or more aromatic rings, which may be substituted, and this hydrocarbon group is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms containing one or more aromatic rings. Examples of such hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene, etc. Incidentally, in the above hydrocarbon group, some or all of the hydrogen atoms may be further substituted with substituents. Examples of such substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, nitro, cyano, hydroxy, amino, silanol, thiol, carboxy, sulfonic acid ester, phosphoric acid, phosphoric acid ester, ester, thioester, amide, organooxy, organoamino, organosilyl, organothio, acyl, sulfo, monovalent hydrocarbon group, and the like. Among these, A 14 is preferably a group derived from benzene, biphenyl or the like.

[0218] Also, A 15 is -O- or -S-, with -O- being preferred. A 16 is an (n + 1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is a group 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, pyrene and the like. Among them, A 16 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.

[0219] R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, and R s8 is a linear or branched monovalent aliphatic hydrocarbon group. However, the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more. The upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. Specific examples of the above 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, decyl groups; 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, hexenyl groups and the like. Among these, R s6 is preferably a hydrogen atom, and R s7 and R s8 are each independently preferably an alkyl group having 1 to 6 carbon atoms.

[0220] In formula (H8), R s9 to 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. 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, n-decyl groups and the like.

[0221] The halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as part or all of the hydrogen atoms of the above alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms. 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, 1,1,2,2,3,3,4,4,4-nonafluorobutyl groups and the like.

[0222] As the halogenated alkenyl group having 2 to 10 carbon atoms, as long as a part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms, it is not particularly limited. Specific examples thereof include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, perfluoro-3-butenyl group and the like.

[0223] Among these, R s9 is preferably 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, more preferably 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, and even more preferably a nitro group, a cyano group, a trifluoromethyl group, or a perfluoropropenyl group. R s10 ~R s13 is preferably a halogen atom, and more preferably a fluorine atom.

[0224] A 17 is -O-, -S- or -NH-, but -O- is preferred. A 18 is an (n + 1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is a group 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, pyrene and the like. Among these, A 18 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.

[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 the monovalent aliphatic hydrocarbon group 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, n-dodecyl groups; 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, hexenyl groups, etc. Among them, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 8 carbon atoms is even more preferred.

[0226] R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 is. 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 of R are the same as those described above. R s18 When R 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 of R include aryl groups such as phenyl, naphthyl, phenanthryl groups, etc., in addition to those other than the methyl group among the aforementioned monovalent aliphatic hydrocarbon groups. Among these, R s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group. In addition, examples of the substituent that the above monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, etc.

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

[0228] [Chemical formula]

[0229] [Chemical formula]

[0230] [Chemical formula]

[0231] The usage amount of the aryl sulfonate compound is preferably about 0.01 to 20, more preferably about 0.05 to 10, in terms of the molar ratio to the charge transporting material 1. Commercially available products may be used for the aryl sulfonate compound, but it can also be synthesized by known methods described in International Publication No. 2017 / 217455, International Publication No. 2017 / 217457, International Publication No. 2019 / 124412, etc.

[0232] In the present invention, considering the production of a charge transporting thin film with excellent transparency and a high refractive index, it is preferable to use an aryl sulfonic acid compound or an aryl sulfonate compound as the dopant material. Considering obtaining a thin film with better solubility in the solvent and a smaller attenuation coefficient, it is more preferable to use an aryl sulfonate compound.

[0233] Furthermore, when the obtained thin film is used as the hole injection layer of an organic EL element, for the purpose of improving the injectability into the hole transport layer and improving the lifetime characteristics of the element, etc., the above charge transporting varnish may contain an organic silane compound. The content is usually about 1 to 30% by mass based on the total mass of the charge transporting material and the dopant material.

[0234] As the organic solvent used when preparing the charge transporting varnish of the present invention, a high-polarity solvent capable of dissolving the arylamine compound of the present invention well can be used. The arylamine compound of the present invention can be dissolved in a solvent regardless of the polarity of the solvent. Further, if necessary, a low-polarity solvent may be used in terms of having better process compatibility than the high-polarity solvent. In the present invention, the low-polarity solvent is defined as having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and the high-polarity solvent is defined as having a relative dielectric constant of 7 or more at a frequency of 100 kHz.

[0235] Examples of the low-polarity solvent include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based 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-based 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 and the like.

[0236] Examples of the high-polarity solvent include amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone-based 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 And the like.

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

[0238] The method for preparing the charge transporting varnish is not particularly limited. For example, there are methods of dissolving all of the solid components such as the charge transporting substance containing the arylamine compound of the present invention in an organic solvent at once, and methods of dissolving a part of the solid components in an organic solvent and then dissolving the remaining solid components.

[0239] In particular, when preparing the charge transporting varnish, from the viewpoint of reproducibly obtaining a thin film with higher flatness, it is desirable to filter using a filter on the submicrometer order or the like after dissolving the charge transporting substance, the dopant substance, etc. in an organic solvent.

[0240] The charge transport varnish described above can be easily used to manufacture a charge transport thin film, and thus can be suitably used in the manufacture of electronic devices, particularly organic EL devices. In this case, the charge transport thin film can be formed by applying the above-described charge transport varnish on a substrate and firing it. The method for applying the varnish is not particularly limited, and examples include dip coating, spin coating, transfer printing, roll coating, brush painting, inkjet printing, spray coating, slit coating, etc. It is preferable to adjust the viscosity and surface tension of the varnish according to the coating method.

[0241] Also, the firing atmosphere of the charge transport varnish after coating is not particularly limited. Not only in the air atmosphere, but also in an inert gas such as nitrogen or in a vacuum, a thin film having a uniform film-forming surface and high charge transport properties can be obtained. However, depending on the type of dopant substance used, firing the varnish in an air atmosphere may result in a thin film having higher charge transport properties being obtained with good reproducibility.

[0242] The firing temperature is appropriately set within a range of about 100 to 260°C in consideration of the use of the obtained thin film, the degree of charge transport properties to be imparted to the obtained thin film, the type and boiling point of the solvent, etc. When the obtained thin film is used as a hole injection layer of an organic EL device, about 140 to 250°C is preferable, and about 145 to 240°C is more preferable. However, when the arylamine compound of the present invention is used as a charge transport substance, a thin film having good charge transport properties can be formed even by low-temperature firing at 200°C or lower. Note that, for the purpose of expressing higher uniform film-forming properties or promoting the reaction on the substrate during firing, a temperature change in two or more steps may be provided. The heating can be performed using an appropriate device such as a hot plate or an oven.

[0243] The film thickness of the charge transport thin film is not particularly limited. However, when used as a hole injection layer, hole transport layer, or hole injection and transport layer of an organic EL element, a film thickness of 5 to 300 nm is preferable. As methods for changing the film thickness, there are methods such as changing the solid content concentration in the varnish or changing the amount of solution (varnish amount) on the substrate during coating.

[0244] The charge transport thin film of the present invention described above generally exhibits a refractive index (n) of 1.60 or more and an extinction coefficient (k) of 0.100 or less at the average value in the wavelength range of 400 to 800 nm. However, in some embodiments, it exhibits a refractive index of 1.65 or more, in 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 other embodiments, it exhibits an extinction coefficient of 0.010 or less.

[0245] When applying the above charge transport thin film to an organic EL element, a configuration can be adopted in which the above charge transport thin film is provided between a pair of electrodes constituting the organic EL element. Typical configurations of organic EL elements include the following (a) to (f), but are not limited thereto. 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, hole transport layer, or hole injection and transport layer may also have the function of an electron blocking layer or the like, and the electron injection layer, electron transport layer, or electron injection and transport layer may also have the function of a hole (positive hole) blocking layer or the like. 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 and transport layer / Cathode (c) Anode / Hole injection and transport layer / Light emitting layer / Electron transport layer / Electron injection layer / Cathode (d) Anode / Hole injection and transport layer / Light emitting layer / Electron injection and transport layer / Cathode (e) Anode / Hole injection layer / Hole transport layer / Light emitting layer / Cathode (f) Anode / Hole injection and 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-transporting 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-transporting material are provided between the light-emitting layer and the anode, the layer closer to the anode is the "hole injection layer", and the other layers are the "hole transport layers". In particular, for the hole injection (transport) layer, a thin film that is excellent not only in hole acceptance from the anode but also in hole injection into the hole transport (light-emitting) layer is used. The "electron injection layer", "electron transport layer", and "electron injection / transport layer" are layers formed between the light-emitting layer and the 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 closer to the cathode is the "electron injection layer", and the other layers are the "electron transport layers". The "light-emitting layer" is an organic layer having a light-emitting function, and when a doping system is adopted, it contains a host material and a dopant material. At this time, the host material mainly has the function of promoting the recombination of electrons and holes and confining excitons within the light-emitting layer, and the dopant material has the function of efficiently emitting the excitons obtained by recombination. In the case of a phosphorescent element, the host material mainly has the function of confining the excitons generated mainly by the dopant within the light-emitting layer.

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

[0248] When manufacturing an organic EL element using the charge-transporting varnish of the present invention, examples of the materials used and the manufacturing method include, but are not limited to, the following. An example of a method for manufacturing an OLED device having a hole injection layer composed of a thin film obtained from the above charge transporting varnish is as follows. Note that, within a range that does not adversely affect the electrodes, it is preferable to perform surface treatment such as cleaning with alcohol, pure water, etc., or UV ozone treatment, oxygen-plasma treatment, etc. in advance. On the anode substrate, a hole injection layer is formed using the above charge transporting varnish by the above method. 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 the hole transport layer and the light-emitting layer by vapor deposition in this method, these layers are formed by a wet process using a composition for forming a hole transport layer containing a hole transporting polymer and a composition for forming a light-emitting layer containing a light-emitting polymer. Note that, if necessary, an electron blocking layer may be provided between the light-emitting layer and the hole transport layer.

[0249] Examples of the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metals typified by aluminum, or metal anodes composed of these alloys, etc., and those subjected to a planarization treatment are preferable. Polythiophene derivatives and polyaniline derivatives having high charge transportability can also be used. Note that other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

[0250] Examples of the material 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), 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] Examples of the hole-transporting polymer 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)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-end-capped with polysilsesquioxane, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)], and the like.

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

[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 and transport layer provided between the anode and the light-emitting layer of an organic EL element. In addition, it can also be used as a charge-transporting thin film in electronic elements such as organic optoelectronic conversion elements, organic thin-film solar cells, organic perovskite optoelectronic conversion elements, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic optical detectors, organic light receivers, organic field quenching elements, light-emitting electro-chemical cells, quantum dot light-emitting diodes, quantum lasers, organic laser diodes, and organic plasmonic light-emitting elements.

Examples

[0257] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The devices and reagents used are as follows. [Device] (1) MALDI-TOF-MS: manufactured by Bruker, autoflex III smartbeam (2) 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd. (3) Substrate cleaning: Substrate cleaning apparatus (vacuum plasma method) manufactured by Choshu Sangyo Co., Ltd. (4) Coating of varnish: Spin coater MS-A100 manufactured by Mikasa Co., Ltd. (5) Film thickness measurement: Fine shape measuring instrument Surf Coater ET-4000 manufactured by Kosaka Laboratory Ltd. (6) Fabrication of elements: Multifunctional vapor deposition apparatus system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd. (7) Measurement of current density and luminance of elements: Multichannel IVL measuring apparatus manufactured by HCS Co., Ltd. (8) Measurement of the lifetime of EL elements (measurement of luminance half-life): Organic EL luminance lifetime evaluation system PEL-105S manufactured by HCS Co., Ltd. (9) Measurement of refractive index (n) and extinction coefficient (k): Multi-incidence angle spectroscopic ellipsometer VASE manufactured by J.A. Woollam Japan

[0258] [Reagent] RuPhos manufactured by Aldrich t-BuXPhos manufactured by Aldrich t-Bu3PHBF4 manufactured by Fujifilm Wako Pure Chemical Corporation Copper(I) iodide manufactured by Fujifilm Wako Pure Chemical Corporation Ethylenediamine manufactured by Fujifilm Wako Pure Chemical Corporation Pd(DBA)2 manufactured by Tokyo Chemical Industry Co., Ltd. Pd(ОAc)2 manufactured by Tokyo Chemical Industry Co., Ltd. Pd[P(C6H5)3)]4 manufactured by 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, manufactured by Tokyo Chemical Industry Co., Ltd. Bis(pinacolato)diboron, manufactured by Tokyo Chemical Industry Co., Ltd. 3,3’,5,5’-Tetramethylbenzidine, manufactured by 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, manufactured by Tokyo Chemical Industry Co., Ltd. Benzyltriethylammonium chloride, manufactured by Tokyo Chemical Industry Co., Ltd. 3-Nitroaniline, manufactured by Tokyo Chemical Industry Co., Ltd. 1-Bromo-3-nitrobenzene, manufactured by Tokyo Chemical Industry Co., Ltd. Hydrogen chloride (approx. 1 mol / L ethyl acetate solution), manufactured by Tokyo Chemical Industry Co., Ltd. 4,4’-Diaminodiphenylamine, manufactured by 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, manufactured by Kanto Chemical Co., Inc. 2,2’-Bis(trifluoromethyl)benzidine, manufactured by Kanto Chemical Co., Inc. Bis(4-aminophenyl)sulfone, manufactured by Kanto Chemical Co., Inc. 1,4-Bis(4-amino-2-trifluoromethylphenoxy)benzene, manufactured by Kanto Chemical Co., Inc. Silica gel N60, manufactured by Kanto Chemical Co., Inc. Dimethyl sulfoxide, manufactured by Junsei Chemical Co., Ltd. Iodomethane, manufactured by Junsei Chemical Co., Ltd. Potassium carbonate, manufactured by Junsei Chemical Co., Ltd. Potassium acetate, manufactured by Tokyo Chemical Industry Co., Ltd. Toluene, manufactured by Junsei Chemical Co., Ltd. Tetrahydrofuran, manufactured by Junsei Chemical Co., Ltd. Ethyl acetate, manufactured by Junsei Chemical Co., Ltd. Methanol, manufactured by Junsei Chemical Co., Ltd. Hexane, manufactured by Junsei Chemical Co., Ltd. m-Tolidine, manufactured by Wakayama Seika Kogyo Co., Ltd. N,N'-Bis(4-aminophenyl)terephthalamide, manufactured by Wakayama Seika Kogyo Co., Ltd. Pd / C CGS-10DR [H2O]=54.40%, manufactured by N.E. Chemcat Corporation 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] [Chemical Formula]

[0260] Into a 100 mL reaction flask, 30 mmol (11.1 g) of 2-bromo-7-iodofluorene and 3 mmol (683.3 mg) of benzyltriethylammonium chloride were weighed, and then 60 mL of dimethyl sulfoxide was added. The mixture was stirred for 10 minutes while purging with nitrogen. Then, 14 g of a separately prepared 50 mass% aqueous solution of sodium hydroxide was added, and the mixture was stirred for 10 minutes. After that, 72.5 mmol (10.3 g) of iodomethane was added dropwise, and the mixture was stirred overnight at room temperature. During the process, a small amount of the solution in the flask was sampled, and the reaction was monitored using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At that time, no prominent peak corresponding to the by-product was confirmed. The obtained reaction mixture was added to 800 mL of a mixed solvent of methanol and water (3 / 1 (v / v)), and the precipitated solid was filtered off with a membrane filter. Finally, the recovered 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. The 1 1H-NMR spectrum (measurement solvent: deuterated DMSO) of the obtained compound is shown in Figure 1.

[0261] [Production Example 1-2] [Chemical Formula]

[0262] To a 200 mL two-necked flask, 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 were added. After stirring at room temperature for 5 minutes under a nitrogen stream, 30 mmol (1.82 g) of ethylenediamine was added thereto, and the mixture was stirred overnight under heating under reflux. After cooling the obtained reaction mixture to room temperature, the insoluble matter was removed by filtration through celite, the obtained 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. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figures 2 to 4.

[0263] [Production Example 1-3] [Chemical Formula]

[0264] Reaction and purification were carried out in the same manner as in Production Example 1-2, except that 88 mmol (20.6 g) of 4-iodoanisole was used instead of 44 mmol of 4-iodotoluene and the usage equivalents of other reagents were doubled, to obtain 11.1 g (78.7%) of 3-bromo-9-(4-methoxyphenyl)carbazole. The 1 1H-NMR spectrum of the obtained compound is shown in Figures 5 and 6.

[0265] [Production Example 1-4] [Chemical formula]

[0266] Into a 200 mL two-necked flask, 60 mmol (14.76 g) of 3-bromocarbazole, 4.5 mmol (0.86 g) of copper(I) iodide, 63 mmol (8.71 g) of potassium carbonate, and 61.5 mmol (16.2 g) of 18-crown-6 were added. After purging the inside of the flask with nitrogen, 100 mL of N,N-dimethylacetamide was added thereto, and the mixture was stirred at room temperature for 10 minutes. Then, the temperature was raised to 160 °C, and after stirring for 2 hours, 63 mmol (13.23 g) of 2-iodothiophene was added, and the mixture was further stirred for 70 hours. After cooling the reaction mixture to room temperature, the insoluble matter was removed by filtration through celite, and the obtained filtrate was concentrated. The concentrate was purified by column chromatography (developing solvent: n-hexane / ethyl acetate = 100 / 0 → 95 / 5) to obtain 5.80 g (29.5%) of 3-bromo-9-(thiophen-2-yl)carbazole. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in FIGS. 7 and 8.

[0267] [Production Example 1-5] [Chemical formula]

[0268] Reaction and purification were carried out in the same manner as in Production Examples 1-4, except that 60 mmol (14.76 g) of 2-bromocarbazole was used instead of 3-bromocarbazole, to obtain 7.36 g (37.2%) of 2-bromo-9-(thiophen-2-yl)carbazole. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in FIGS. 9 and 10.

[0269] [Production Example 1-6] [Chemical formula]

[0270] Into a 100 mL reaction flask, 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 were added. After nitrogen substitution while stirring at room temperature for 10 minutes, the temperature was raised to 90 °C and further stirred overnight. The reaction mixture was mixed with 75 mL of water and 75 mL of methylene chloride for extraction, and the organic layer was recovered. The recovered organic layer was dried over magnesium sulfate, and magnesium sulfate was removed by filtration. 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 pinacol ester. The 1 ¹H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in FIGS. 11 and 12.

[0271] [Production Example 1-7] [Chemical Formula]

[0272] Reaction and purification were carried out in the same manner as in Production Example 1-6, except that 10 mmol (3.522 g) of 3-bromo-9-(p-methoxyphenyl)carbazole was used instead of 5 mmol of 3-bromo-9-(p-tolyl)carbazole, and the usage equivalents of other reagents were doubled, to obtain 1.53 g (38.3%) of 9-(p-methoxyphenyl)carbazole-3-boronic acid pinacol ester. The 1 ¹H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in FIGS. 13 and 14.

[0273] [Production Example 1-8] [Chemical Formula]

[0274] Instead of 5 mmol of 3-bromo-9-(p-tolyl)carbazole, 15 mmol (4.92 g) of 3-bromo-9-(thiophen-2-yl)carbazole was used, and the reaction and purification were carried out in the same manner as in Production Example 1-6 except that the use equivalent of other reagents was tripled, to obtain 2.53 g (44.9%) of 9-(thiophen-2-yl)carbazole-3-boronic acid pinacol ester. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in FIGS. 15 and 16.

[0275] [Production Example 1-9] [Chemical formula]

[0276] Instead of 3-bromo-9-(p-tolyl)carbazole, 5 mmol (1.64 g) of 2-bromo-9-(thiophen-2-yl)carbazole was used, and 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 pinacol ester. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in FIGS. 17 and 18.

[0277] [Production Example 2-1] [Chemical formula]

[0278] Into a 100 mL reaction flask, add 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 0.15 mmol (173.5 mg) of Pd[P(C6H5)3]4. Stir at room temperature for 10 minutes while purging with nitrogen, and then stir at 60 °C for 5 hours. During the process, a small amount of the solution in the flask was sampled, and the reaction was monitored using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At that time, no prominent peak corresponding to the by-product was confirmed. Add the obtained reaction mixture to 400 mL of a mixed solvent of methanol and water (3 / 1 (v / v)), filter off the precipitated solid through a membrane filter, and dry the filtered solid under reduced pressure at 60 °C. Furthermore, dissolve the dried solid in 20 mL of tetrahydrofuran, add the obtained solution to 200 mL of n-hexane, filter off the precipitated solid through a membrane filter, and dry the filtered solid under reduced pressure at 60 °C. Finally, dissolve the dried solid in 20 mL of tetrahydrofuran, add the obtained solution to 200 mL of a mixed solvent of methanol and water (3 / 1 (v / v)), and filter off the precipitated solid through a membrane filter. The obtained 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. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 19.

[0279] [Production Example 2-2] [Chemical formula]

[0280] Into a 100 mL reaction flask, add 2.5 mmol (0.958 g) of 9-(p-tolyl)carbazole-3-boronic acid pinacol ester, 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 0.075 mmol (86.7 mg) of Pd[P(C6H5)3]. After stirring at room temperature for 10 minutes while purging with nitrogen, stir at 60 °C overnight. After cooling the obtained reaction mixture to room temperature, the aqueous layer was removed. The obtained organic layer was added dropwise to a mixed solvent of methanol and water (3 / 1 (v / v)), and the precipitated solid was filtered off with a membrane filter. The filtered solid was dried under reduced pressure at 60 °C. 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 filtered off with 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. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figures 20 and 21.

[0281] [Production Example 2-3] [Chemical formula]

[0282] Reaction and purification were carried out in the same manner as in Production Example 2-2, except that 15 mmol (5.99 g) of 9-(p-methoxyphenyl)carbazole-3-boronic acid pinacol ester was used instead of 9-(p-tolyl)carbazole-3-boronic acid pinacol ester, and the use equivalents of the other reagents were increased by 6 times. 5.80 g (70.4%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-methoxyphenyl)-9H-carbazole was obtained. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 22.

[0283] [Production Example 2-4]

Chemical formula

[0284] Instead of 9-(p-tolyl)carbazole-3-boronic acid pinacol ester, 5 mmol (1.79 g) of 9-(thiophen-2-yl)carbazole-3-boronic acid pinacol ester was used, and the reaction and purification were carried out in the same manner as in Production Example 2-2 except that the use equivalent of other reagents was doubled, 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. The 1 1H-NMR spectrum of the obtained compound is shown in FIGS. 23 and 24 (measurement solvent: deuterated THF).

[0285] [Production Example 2-5]

Chemical formula

[0286] Instead of 9-(p-tolyl)carbazole-3-boronic acid pinacol ester, 5 mmol (1.88 g) of 9-(thiophen-2-yl)carbazole-2-boronic acid pinacol ester was used, and the reaction and purification were carried out in the same manner as in Production Example 2-2 except that the use equivalent of other reagents was doubled, 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. The 1 1H-NMR spectrum of the obtained compound is shown in FIGS. 25 and 26 (measurement solvent: deuterated THF).

[0287] [Production Example 3]

Chemical formula

[0288] A 1000 mL reaction flask equipped with a reflux column was charged with 5 mmol (2.88 g) of Pd(DBA)₂, 10 mmol (4.25 g) of t-BuXPhos, 300 mmol (41.46 g) of potassium carbonate, 100 mmol (13.82 g) of 3-nitroaniline, 110 mmol (22.22 g) of 1-bromo-3-nitrobenzene, and 1000 mL of toluene. After purging the inside of the flask with nitrogen, the mixture was stirred overnight in an 80 °C bath. During the process, a small amount of the solution in the flask was sampled, and the reaction was monitored using liquid chromatography. As the area of the peak attributable to the raw materials decreased, the area of the peak attributable to the target product increased. At that time, no prominent peak corresponding to by-products was confirmed. The reaction solution was cooled to room temperature and filtered through a filter filled with 200 g of silica gel N60. The obtained filtrate was concentrated until it weighed 100 g, and the concentrate was added dropwise to 1000 mL of toluene. 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] [Chemical Formula]

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

[0291] [Example 1-1] [Chemical formula]

[0292] Into a 30 mL reaction flask equipped with a reflux column, 0.1 mmol (57.6 mg) of Pd(DBA)₂, 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, and the system was purged with nitrogen. Then, 10 mL of dioxane was added, and the mixture was stirred at room temperature for 5 minutes. Next, 1.69 mL (equivalent to 2.2 mmol of LHMDS) of a 1.3 mol / L tetrahydrofuran solution of LHMDS was added, and the mixture was stirred at room temperature for 5 minutes. After that, the mixture was heated and stirred in a bath at 110 °C for 8 hours (internal temperature 92 °C). During this process, a small amount of the solution in the flask was sampled, and the reaction was monitored using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At that time, no prominent peak corresponding to the by-product was confirmed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was placed in a separatory funnel together with 50 mL of a saturated aqueous ammonium chloride solution and 50 mL of a mixed solvent of ethyl acetate and tetrahydrofuran (2 / 1 (v / v)) for extraction. The organic layer was left in the separatory funnel, and the aqueous layer was recovered. 50 mL of saturated brine was added to the separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were each recovered. Then, all the recovered aqueous layers were combined and placed in a separatory funnel, and 20 mL of ethyl acetate was added thereto for extraction. The organic layer was recovered, and all the recovered organic layers were combined and dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and the solvent was distilled off from the resulting filtrate using a rotary evaporator. The resulting residue was dissolved in 3 mL of toluene, and column chromatography (developing solvent: n-hexane / methylene chloride = 60 / 40 → 0 / 100) was performed using the resulting solution, and the fraction containing the target product was collected. Finally, the solvent was removed from the collected fraction, and after drying under reduced pressure at 70 °C, 0.56 g (>99%) of arylamine compound C2d was obtained. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 27.

[0293] [Example 1-2] [Chemical formula]

[0294] The operation was carried out in the same manner as in Example 1-1 except that 0.5 mmol (123.2 mg) of N,N'-bis(4-aminophenyl)terephthalamide was used instead of 3,3',5,5'-tetramethylbenzidine, and 0.43 g (70.9%) of arylamine compound D2d was obtained. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 28.

[0295] [Example 1-3] [Chemical formula]

[0296] The operation was carried out in the same manner as in Example 1-1 except that 0.5 mmol (160.12 mg) of 2,2'-bis(trifluoromethyl)benzidine was used instead of 3,3',5,5'-tetramethylbenzidine, and 0.46 g (44.8%) of arylamine compound A3d was obtained. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 29.

[0297] [Example 1-4] [Chemical formula]

[0298] The operation was carried out in the same manner as in Example 1-1 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 arylamine compound E3d. The 1 1H-NMR spectrum (measurement solvent: CDCl3) of the obtained compound is shown in Fig. 30.

[0299] [Example 1-5] [Chemical formula]

[0300] The operation was carried out in the same manner as in Example 1-4 except that 2.1 mmol (1.375 mg) of 3-(7-bromo-9,9-dihexyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole was used instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole to obtain 0.71 g (55.8%) of arylamine compound E3i. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 31.

[0301] [Example 1-6] [Chemical formula]

[0302] The operation was carried out in the same manner as in Example 1-1 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 arylamine compound F3d. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 32.

[0303] [Example 1-7]

Chemical formula

[0304] The operation was carried out in the same manner as in Examples 1-3, 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, to obtain 0.32 g (40.3%) of arylamine compound A3b. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 33.

[0305] [Example 1-8]

Chemical formula

[0306] The operation was carried out in the same manner as in Examples 1-3, 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, to obtain 0.57 g (60.2%) of arylamine compound A3c. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 34.

[0307] [Example 1-9]

Chemical formula

[0308] The operation was carried out in the same manner as in Example 1-1, 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 arylamine compound G3d. The 1The 1H-NMR spectrum (measurement solvent: deuterated THF) is shown in Fig. 35.

[0309] [Example 1-10] [Chemical formula]

[0310] Into a 200 mL reaction flask equipped with a reflux column, 2 mmol (0.45 g) of Pd(OAc)2, 4 mmol (1.16 g) of t-Bu3PHBF4, 40 mmol (3.84 g) of t-BuONa, 4 mmol (797.0 mg) of 4,4'-diaminodiphenylamine, and 20.6 mmol (10.61 g) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole were weighed, and the inside of the flask was purged with nitrogen. Then, 50 mL of toluene was added thereto, and the mixture was stirred overnight in a bath at 110 °C. During the process, a small amount of the solution in the flask was sampled, and the reaction was monitored using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At that time, no prominent peak corresponding to the by-product was confirmed. The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and column chromatography was performed using the solution obtained by diluting the resulting concentrate with 10 mL of toluene (developing solvent: n-hexane / methylene chloride = 70 / 30 (v / v) → 55 / 45 (v / v)). The fraction of the target product was collected, the collected fraction was concentrated, and column chromatography was performed again under the same conditions using the solution obtained by diluting the resulting concentrate with 10 mL of toluene, and the fraction of the target product was collected. The collected fraction was concentrated, the concentrate was dissolved in 30 mL of tetrahydrofuran, the resulting solution was dropped into a mixed solvent of ethyl acetate and methanol (1 / 1 (v / v)), and the precipitated solid was collected by a membrane filter. The obtained solid was dried to obtain 2.67 g (28.2%) of the arylamine compound H3d. The 1 The 1H-NMR spectrum (measurement solvent: deuterated THF) is shown in Fig. 36.

[0311] [Example 1-11] [Chem.]

[0312] Into a 30 mL reaction flask equipped with a reflux column, 2.5 mmol (0.56 g) of Pd(OAc)₂, 5 mmol (1.45 g) of t-Bu₃PHBF₄, 25 mmol (2.40 g) of t-BuONa, 2.5 mmol (80.4 mg) of 3,3'-diaminodiphenylamine dihydrochloride, and 12.6 mmol (6.49 g) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole were weighed in, and the inside of the flask was purged with nitrogen. Then, 50 mL of toluene was added thereto, and the mixture was stirred overnight in a bath at 110 °C. During the process, a small amount of the solution in the flask was sampled, and the reaction was monitored using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target product increased. At that time, no prominent peak corresponding to the by-product was confirmed. The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and column chromatography was performed using the solution obtained by diluting the resulting concentrate with 5 mL of toluene (developing solvent: n-hexane / methylene chloride = 70 / 30 (v / v) → 55 / 45 (v / v)), the fractions of the target product were collected, the collected fractions were concentrated, and column chromatography was performed again under the same conditions using the solution obtained by diluting the resulting concentrate with 5 mL of toluene, and the fractions of the target product were collected. The collected fractions were concentrated, the concentrate was dissolved in 30 mL of tetrahydrofuran, the resulting solution was dropped into a mixed solvent of ethyl acetate and methanol (1 / 1 (v / v)), and the precipitated solid was collected by a membrane filter. The obtained solid was dried to obtain 2.34 g (39.5%) of arylamine compound I3d. The 1 ¹H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 37.

[0313] [Example 1-12] [Chem.]

[0314] Into 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)₂, 0.8 mmol (232.1 mg) of t-Bu₃PHBF₄, and 4 mmol (384.4 mg) of t-BuONa were added. After nitrogen substitution, 8 mL of toluene was added, and the mixture was stirred for 10 minutes and then stirred overnight under heating under reflux conditions. After cooling the reaction mixture to room temperature, the aqueous layer was removed from the cooled reaction mixture, and the obtained 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, the obtained solid was dissolved in tetrahydrofuran, and this solution was added dropwise to n-hexane. The obtained solid was collected by filtration and dried under reduced pressure to obtain 210 mg (21.5%) of arylamine compound I3e. The 1 ¹H-NMR spectra (measurement solvent: deuterated THF) of the obtained compound are shown in FIGS. 38 and 39.

[0315] [Example 1-13] [Chemical formula]

[0316] The operation was carried out in the same manner as in Example 1-12 except that 2.02 mmol (1051.4 mg) of 2-(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-(p-tolyl)-9H-carbazole to obtain 157.0 mg (16.4%) of arylamine compound I3h. The 1 ¹H-NMR spectra (measurement solvent: deuterated THF) of the obtained compound are shown in FIGS. 40 and 41.

[0317] [Example 1-14] [Chemical formula]

[0318] Except for using 2.1 mmol (1109.8 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, the operation was carried out in the same manner as in Examples 1-3 to obtain 323.8 mg (38.3%) of arylamine compound A3e. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 42.

[0319] [Examples 1-15] [Chemical formula]

[0320] Except for using 2.1 mmol (1143.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-methoxyphenyl)-9H-carbazole instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, the operation was carried out in the same manner as in Examples 1-3 to obtain 552.6 mg (50.8%) of arylamine compound A3f. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 43.

[0321] [Examples 1-16] [Chemical formula]

[0322] Instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, 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, and the operation was carried out in the same manner as in Example 1-3 to obtain 3 g (499.9 mg, 48.1%) of arylamine compound A. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 44.

[0323] [Example 1-17] [Chemical formula]

[0324] Instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, 2.1 mmol (1093.0 mg) of 2-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was used, and the operation was carried out in the same manner as in Example 1-3 to obtain 3 h (664.9 mg, 64.0%) of arylamine compound A. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figs. 45 and 46.

[0325] [Example 1-18] [Chemical formula]

[0326] To 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)2, 0.4 mmol (166 mg) of t-Bu3PHBF4, and 4 mmol (385 mg) of t-BuONa were added, and after nitrogen substitution, 10 mL of toluene was added. The mixture was stirred at room temperature for 5 minutes and then stirred at 100 °C for 6 hours. After cooling the reaction mixture to room temperature, the cooled reaction mixture was filtered through a membrane filter, activated carbon was added to the resulting filtrate, and the mixture was stirred for 1 hour. The activated carbon was removed by filtration, the resulting 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. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 47.

[0327] [Example 1-19] [Chemical formula]

[0328] The procedure was carried out in the same manner as in Example 1-18 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. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 48.

[0329] [Example 1-20] [Chemical formula]

[0330] The procedure was carried out in the same manner as in Example 1-18 except that 2.1 mmol (1080.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluorene-2-yl)-9-phenyl-9H-carbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole to obtain 535 mg (51.9%) of arylamine compound B3d. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Figure 49.

[0331] [Example 1-21] [Chemical formula]

[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, 0.1 mmol (57.5 mg) of Pd(DBA)₂, 0.2 mmol (84 mg) of t-Bu₃PHBF₄, and 2 mmol (193 mg) of t-BuONa were added. After purging with nitrogen, 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 cooling the reaction mixture to room temperature, the cooled reaction mixture was filtered through a membrane filter, activated carbon was added to the obtained filtrate, and the mixture was stirred for 1 hour. The activated carbon was removed by filtration, 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. The 1 ¹H-NMR spectrum (measurement solvent: deuterated DMSO) of the obtained compound is shown in Figure 50.

[0333] [Example 1-22] [Chemical formula]

[0334] The operation was carried out in the same manner as in Example 1-21 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. The 1 ¹H-NMR spectrum (measurement solvent: deuterated DMSO) of the obtained compound is shown in Figure 51.

[0335] [Example 1-23] [Chemical formula]

[0336] Except for using 2.1 mmol (1080.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole instead of 3-(4-bromophenyl)-9-phenylcarbazole, the operation was carried out in the same manner as in Example 1-21 to obtain 114.0 mg (19.1%) of arylamine compound B2d. The 1 1H-NMR spectrum (measurement solvent: deuterated DMSO) of the obtained compound is shown in Fig. 52.

[0337] [Comparative Example 1-1] [Chemical formula]

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

[0339] [Comparative Example 1-2] [Chemical formula]

[0340] Except for using 2.1 mmol (677 mg) of 3-bromo-N-phenylcarbazole instead of 3-(4-bromophenyl)-9-phenylcarbazole, the operation was carried out in the same manner as in Example 1-18 to obtain 236.2 mg (36.6%) of arylamine compound B3a. The 1 1H-NMR spectrum (measurement solvent: deuterated THF) of the obtained compound is shown in Fig. 54.

[0341] [Comparative Example 1-3] [Chemical formula]

[0342] The operation was carried out in the same manner as in Example 1-21 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. The 1 1H-NMR spectrum (measurement solvent: deuterated DMSO) of the obtained compound is shown in Fig. 55.

[0343] [2] Preparation of varnish for hole injection layer [Comparative Example 2-1] To chloroform (10 g), arylamine compound A3a (0.025 g) and aryl sulfonate A (0.025 g) represented by the following formula were added, and the resulting solution stirred and dissolved at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish A3a-1.

[0344] [Chemical formula]

[0345] [Example 2-1] To chloroform (10 g), arylamine compound A3b (0.028 g) and aryl sulfonate A (0.022 g) were added, and the resulting solution stirred and dissolved at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish A3b-1.

[0346] [Example 2-2] To chloroform (10 g), arylamine compound A3c (0.030 g) and aryl sulfonate A (0.020 g) were added, and the resulting solution stirred and dissolved at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish A3c-1.

[0347] [Example 2-3] To chloroform (10 g), arylamine compound A3d (0.031 g) and aryl sulfonate A (0.019 g) were added, and the resulting solution stirred and dissolved at room temperature 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] To chloroform (10 g), arylamine compound A3e (0.031 g) and aryl sulfonate A (0.019 g) were added, and the resulting solution stirred and dissolved at room temperature 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] To chloroform (10 g), arylamine compound A3f (0.032 g) and aryl sulfonate A (0.018 g) were added, and the resulting solution stirred and dissolved at room temperature 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] To chloroform (10 g), arylamine compound A3g (0.031 g) and aryl sulfonate A (0.019 g) were added, and the resulting solution stirred and dissolved at room temperature 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] To chloroform (10 g), arylamine compound A3h (0.031 g) and aryl sulfonate A (0.019 g) were added, and the resulting solution stirred and dissolved at room temperature 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] To chloroform (10 g), arylamine compound B3a (0.026 g) and aryl sulfonate A (0.024 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature 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] To chloroform (10 g), arylamine compound B3b (0.029 g) and aryl sulfonate A (0.021 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transporting varnish B3b-1.

[0354] [Example 2-9] To chloroform (10 g), arylamine compound B3c (0.030 g) and aryl sulfonate A (0.020 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature 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] To chloroform (10 g), arylamine compound B3d (0.031 g) and aryl sulfonate A (0.019 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature 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] To chloroform (10 g), arylamine compound B2a (0.020 g) and aryl sulfonate A (0.030 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature 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] To chloroform (10 g), arylamine compound B2b (0.022 g) and aryl sulfonate A (0.028 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish B2b-1.

[0358] [Example 2-12] To chloroform (10 g), arylamine compound B2c (0.024 g) and aryl sulfonate A (0.026 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish B2c-1.

[0359] [Example 2-13] To chloroform (10 g), arylamine compound B2d (0.025 g) and aryl sulfonate A (0.025 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish B2d-1.

[0360] [Example 2-14] To chloroform (10 g), arylamine compound H3d (0.033 g) and aryl sulfonate A (0.017 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish H3d-1.

[0361] [Example 2-15] To chloroform (10 g), arylamine compound I3d (0.033 g) and aryl sulfonate A (0.017 g) were added, and the resulting solution obtained by stirring and dissolving at room temperature was filtered through a syringe filter with a pore size of 0.2 μm to obtain charge transport varnish I3d-1.

[0362] [3] Preparation of varnish for hole transport layer [Comparative Example 3-1] A solution obtained by adding arylamine compound A3a (0.040 g) to chloroform (10 g) and stirring at room temperature until dissolved was filtered through a syringe filter with a pore size of 0.2 μm to obtain 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 compounds A3b, A3c, A3d, A3e, A3f, A3g, A3h, B3d, B2d, H3d, or I3d were used respectively instead of arylamine compound A3a.

[0364] [4] Fabrication of thin films and evaluation of film physical properties [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 at 120 °C for 1 minute under air baking. Next, the dried quartz substrate was baked at 200 °C for 15 minutes in an air atmosphere to form a uniform 50-nm thin film on the quartz substrate. Using the obtained quartz substrate with the film, the visible region average refractive index (n) and visible region average extinction coefficient (k) at wavelengths of 400 to 800 nm were measured. The results are shown in Table 23.

[0365]

Table 23

[0366] As shown in Table 23, it can be seen that the thin film obtained from the charge transporting varnish of the present invention has a refractive index equal to or higher than that of the thin film obtained from the charge transporting varnish of Comparative Example 4-1 and an extinction coefficient 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 property evaluation of hole-only devices (HODs) [Comparative Example 5-1] As the ITO substrate, a 25 mm × 25 mm × 0.7 t 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 by an O2 plasma cleaning device (150 W, 30 seconds) before use. Subsequently, 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, dried for 1 minute, and then fired 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 fired at 130 °C for 10 minutes in an air atmosphere to form a hole transport layer (film thickness: 40 nm). On this, an 80-nm aluminum thin film was formed at 0.2 nm / second using a vapor deposition apparatus (vacuum degree: 1.0 × 10 -5 Pa) to obtain a hole-only device (HOD). 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 International Publication No. 2013 / 084664 and 0.271 g of an arylsulfonic acid represented by formula (4) synthesized according to the method described in International Publication No. 2006 / 025342 were dissolved in 6.7 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere. To the obtained solution, 10 g of cyclohexanol and 3.3 g of propylene glycol were sequentially added and stirred to obtain a composition for forming a hole injection layer (the same applies hereinafter).

[0368] [Chemical formula]

[0369] [Examples 5-1 to 5-11] HODs were fabricated in the same manner as in Example 5-1, except that the 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 used instead of the charge-transporting varnish A3a-2, respectively.

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

[0371] [Table 24]

[0372] As shown in Table 24, it can be seen that the thin films prepared from the charge transporting varnish of the present invention exhibit better charge transport properties than the thin films prepared from the charge transporting varnish of the Comparative Example. This improvement in charge transport properties is considered to be associated with an increase in the effective conjugation length of the conductive sites in the arylamine compound of the present invention.

[0373] [6] Fabrication of single layer devices (SLD) and HOD and evaluation of the relative intensity of the current density of HOD with respect to the current density of SLD [Comparative Example 6-1] As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate on which indium tin oxide (ITO) was patterned with a film thickness of 150 nm on the surface was used, and impurities on the surface were removed by an O2 plasma cleaning apparatus (150 W, 30 seconds) before use. The charge transporting varnish A3a-1 was applied onto the ITO substrate by spin coating, dried at 120 °C for 1 minute under the atmosphere, and then fired at 200 °C for 15 minutes to form a hole injection layer (film thickness: 50 nm) on the ITO substrate. On this, an aluminum thin film with a thickness of 80 nm was formed at 0.2 nm / second using a vapor deposition apparatus (vacuum degree 1.0 × 10 -5 Pa) to obtain a single layer device (SLD).

[0374] [Examples 6-1 to 6-12, Comparative Example 6-2] Except that the 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 respectively instead of the charge transporting varnish A3a-1, SLDs were fabricated in the same manner as in Comparative Example 6-1.

[0375] [Comparative Example 7-1] The charge transport varnish A3a-1 was applied to an ITO substrate using a spin coater, dried in air at 120°C for 1 minute, and then fired at 200°C for 15 minutes to form a 50-nm thin film on the ITO substrate. As the ITO substrate, the same ITO substrate as in Comparative Example 6-1 was used. On top of that, thin films of α-NPD and aluminum were sequentially deposited using a vapor deposition apparatus (vacuum degree: 2.0×10 -5 Pa) to obtain HOD. The vapor deposition was performed under the condition of a vapor deposition rate of 0.2 nm / second. The film thicknesses of the α-NPD and aluminum thin films were 30 nm and 80 nm, respectively.

[0376] [Examples 7-1 to 7-12, Comparative Example 7-2] Except that the charge transport 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 the charge transport varnish A3a-1, HOD was produced in the same manner as in Comparative Example 7-1.

[0377] The current densities 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 4V were measured. The results are shown in Table 25. Also shown is the relative intensity of the current density of HOD with respect to the current density of SLD calculated using these measured values. Note that a high relative intensity indicates that efficient hole supply to the hole transport layer has been achieved.

[0378] [Table 25]

[0379] As shown in Table 25, it was found that the device using the hole injection layer made from the charge transport varnish of the present invention had a higher relative intensity of the current density of HOD with respect to the current density of SLD compared to the devices made in the comparative examples.

[0380] [7] Fabrication and Characterization of Organic EL Devices [Comparative Example 8-1] The charge transporting varnish A3a-1 was applied onto an ITO substrate using a spin coater, then dried at 120 °C for 1 minute in air, and then baked at 200 °C for 15 minutes to form a 50-nm thin film on the ITO substrate. Note that the same ITO substrate as in Comparative Example 6-1 was used as the ITO substrate. Next, for the ITO substrate on which the thin film was formed, α-NPD was deposited at a rate of 0.2 nm / sec to a thickness of 30 nm using a vapor deposition apparatus (vacuum degree: 1.0×10 -5 Pa). Next, 10 nm of the electron blocking material HTEB-01 manufactured by Kanto Chemical Co., Inc. was deposited. Next, the light-emitting layer host material NS60 and the light-emitting layer dopant material Ir(ppy)3 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. were co-evaporated. The co-evaporation was controlled such that the concentration of Ir(ppy)3 was 6%, and 40 nm was laminated. Next, thin films of Alq3, lithium fluoride, and aluminum were sequentially laminated to obtain an organic EL device. At this time, the deposition rates were 0.2 nm / sec for Alq3 and aluminum, and 0.02 nm / sec for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively. Note that in order to prevent characteristic degradation due to the influence of oxygen, water, etc. in the air, the organic EL device was sealed with a sealing substrate and then its characteristics were evaluated. The sealing was performed according to the following procedure. 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 device was placed between the sealing substrates, and the sealing substrates were bonded together with an adhesive (manufactured by MORESCO CORPORATION, MORESCO MOISTURE CUT WB90US(P)). At this time, a water-trapping agent (HD-071010W-40 manufactured by Dainic Co., Ltd.) was placed in the sealing substrate together with the organic EL device. The bonded sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation dose: 6,000 mJ / cm 2 ) and then annealed at 80 °C for 1 hour to cure the adhesive.

[0381] [Examples 8-1 to 8-12] Instead of the charge transport varnish A3a-1, an organic EL element was fabricated in the same manner as Comparative Example 8-1, except that the charge transport 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 respectively.

[0382] The driving voltage, current density, current efficiency, luminous efficiency, external quantum efficiency of luminescence (EQE), and LT90 (the time required for a 10% decrease in the initial luminance of 5,000 cd / m 2 were measured when the obtained organic EL element was caused to emit light at a luminance of 5,000 cd / m 2 . 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 equal to or lower than those of the comparative example and had half-lives equal to or longer than those of the comparative example.

Claims

1. An arylamine compound represented by the following formula (1) (however, compounds represented by the following formulas (P1) to (P4) are excluded). 【Chemical Formula 1】 [In the formula, Ar c is the same group and represents a group represented by formula (Q), 【Chemical Formula 2】 [In the formula, R 1 represents a hydrogen atom, and R 2 represents an aryl group represented by any of the following formulas, 【Chemical Formula 3】 Ar s represents an arylene group represented by any of the following formulas (101A-1), (101B-1), (101C-1), (105A-1) and (107A-1), 【Chemical Formula 4】 (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.) ] X represents a group represented by any of the following formulas (201A-1) to (208A-1). ] 【Chemical Formula 5】 【Chemical Formula 6】 【Chemical Formula 7】

2. A charge-transporting varnish containing the arylamine compound according to Claim 1 and an organic solvent.

3. The charge-transporting varnish according to Claim 2 containing a dopant substance.

4. A charge-transporting thin film produced using the charge-transporting varnish according to Claim 2 or 3.

5. An electronic device provided with the charge-transporting thin film according to Claim 4.

6. The electronic device according to Claim 5, wherein the charge-transporting thin film is a hole injection layer. Claim 7 The electronic device according to claim 6, which is an organic EL device.

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