WO2020241730A1

WO2020241730A1 - Arylamine compound and use thereof

Info

Publication number: WO2020241730A1
Application number: PCT/JP2020/021058
Authority: WO
Inventors: 小島　圭介; 歳幸遠藤
Original assignee: 日産化学株式会社
Priority date: 2019-05-31
Filing date: 2020-05-28
Publication date: 2020-12-03
Also published as: CN113874352A; KR20220016122A; TW202108738A; JPWO2020241730A1

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, Ar^s 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

Arylamine compounds and their uses

The present invention relates to arylamine compounds and their use.

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 related to materials and element structures are expected for the purpose of low voltage drive, high brightness, long life, etc. Has been made.
A plurality of functional thin films are used in this organic EL element, and one of them, the hole injection layer, is responsible for the transfer of electric charge between the anode and the hole transport layer or the light emitting layer, and is low in the organic EL element. It plays an important role in achieving voltage drive and high brightness.

The method for producing the hole injection layer is roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. Comparing these processes, the wet process can efficiently produce a thin film with a large area and high flatness.
For this reason, as the area of organic EL displays is being increased, a hole injection layer that can be formed by a wet process is desired.

In view of these circumstances, the present inventors have a charge transporting property that gives a thin film that can be applied to various wet processes and can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element. We have been developing compounds with good solubility in materials and organic solvents used for them (see Patent Documents 1 to 3).

On the other hand, various efforts have been made to improve the performance of organic EL devices, but efforts have been made to adjust the refractive index of the functional thin film used for the purpose of improving the light extraction efficiency. There is. Specifically, by using a hole injection layer or a hole transport layer having a relatively high or low refractive index in consideration of the overall configuration of the device and the refractive index of other adjacent members, the efficiency of the device is high. Attempts have been made to achieve this (see Patent Documents 4 and 5).
As described above, the refractive index is an important factor in the design of the organic EL element, and in the material for the organic EL element, the refractive index is also considered to be an important physical property value to be considered.

Further, in recent years, the charge-transporting thin film for organic EL elements has been in the visible region because the coloring of the charge-transporting thin film used for the organic EL element reduces the color purity and color reproducibility of the organic EL element. It is desired to have high transparency and high transparency (see Patent Document 6).

International Publication No. 2008/129947 International Publication No. 2015/050253 International Publication No. 2017/217457 Special Table 2007-536718 Special Table 2017-501585 International Publication No. 2013/0426223

The present invention has been made in view of such circumstances, and when a thin film having good solubility in an organic solvent and good optical characteristics is provided and this thin film is applied to a hole injection layer or the like. It is an object of the present invention to provide an arylamine compound capable of realizing an organic EL device having good properties.

As a result of diligent studies to achieve the above object, the present inventors have at least arylcarbazole at the center via a spacer having an aryldiamine skeleton and a predetermined arylene skeleton at the two amino groups. The compounds bonded one by one have good solubility in an organic solvent, and the varnish obtained by dissolving this in an organic solvent gives a thin film having excellent optical properties, and this thin film is applied to a hole injection layer or the like. The present invention has been completed by finding that an organic EL element having good characteristics can be obtained in some cases.

That is, the present invention
1. 1. Arylamine compounds represented by any of the following formulas (1) to (6) (excluding compounds represented by the following formulas (P1) to (P4)),

Wherein, Ar ^c each independently represent a group represented by the formula (Q),
X represents an arylene group which may be independently substituted and may contain a heteroatom.
Y represents a phenylene group which may be substituted independently of each other.
g represents an integer of 1 to 10 independently of each other.

(In the formula, R ¹ is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents an alkoxy group of, or an aryl group having 6 to 20 carbon atoms, R ² represents an aryl group that may be independently substituted and may contain a hetero atom, and Ar ^s represents an aryl group. Represents an arylene group that may be independently substituted and may contain a heteroatom.)

2. 2. 1 arylamine compound, wherein Ar ^s is represented by any of the following formulas (101) to (118).

(In the formula, R ³ is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents an alkoxy group or an aryl group having 6 to 20 carbon atoms, where V ¹ is an independent C (R ⁴ ) ₂ (R ⁴ is an independent hydrogen atom and has 1 to 20 carbon atoms. It represents an alkyl group or an alkyl halide 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 SO ₂ , V ² stands for NR ⁵ (R ⁵ stands for the same meaning as above), S or O)
3. 3. 1 arylamine compound, wherein Ar ^s is represented by any of the following formulas (101A) to (118A).

(In the equation, R ³ , V ¹ and V ² have the same meanings as described above.)
4. Wherein Ar ^s is 3 arylamine compound represented by any one of the following formulas (101A-1) ~ (118A -3),

(In the formula, R ⁴ and R ⁵ have the same meanings as described above.)
5. X is an arylamine compound according to any one of 1 to 4 represented by any of the following formulas (201) to (207).

(In the formula, R ⁶ is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents an alkoxy group or an aryl group having 6 to 20 carbon atoms, W ¹ is an independent single bond, and C (R ⁷ ) ₂ (R ⁷ is an independent hydrogen atom and 1 carbon atom. Represents an alkyl group of ~ 20 or an alkyl halide group having 1 to 20 carbon atoms), S, O, or SO ₂ , where W ² is C (R ⁷ ) ₂ (R ⁷ is independent of each other). (Same as above), NR ⁸ (R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or SO _2. W ³ stands for NR ⁸ (R ⁸ stands for the same meaning as above), S or O.)
6. 5 arylamine compounds, wherein X is represented by any of the following formulas (201A) to (207A).

(In the formula, R ⁶ , W ¹ , W ² and W ³ have the same meanings as described above.)
7. 6 arylamine compounds represented by any of the following formulas (201A-1) to (207A-1), wherein X is

(In the formula, R ⁷ , R ⁸ and W ³ have the same meanings as described above.)
8. Wherein Ar ^c is one of arylamine compounds of 1-7 are the same group,
9. A charge-transporting varnish containing any of the arylamine compounds 1 to 8 and an organic solvent.
10. 9 charge-transporting varnishes containing dopant material,
11. Charge transport thin films made using 9 or 10 charge transport varnishes,
12. Provided is an electronic device including 11 charge transporting thin films.

The arylamine compound of the present invention has good solubility in an organic solvent, and by using a charge-transporting varnish containing this arylamine compound, a charge-transporting thin film having high transparency and high refractive index can be obtained. be able to.
This charge transporting thin film can be suitably used as a thin film for electronic devices such as organic EL devices, particularly as a thin film for electronic devices in which a thin film is laminated by a wet process on an upper layer, and the charge transporting property of the present invention can be used. By applying a thin film to a hole injection layer or the like of an organic EL device, an device having good characteristics can be manufactured.

FIG. 5 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 1-1. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-2. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-2. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-2. 3 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 1-3. 3 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 1-3. It is ¹ H-NMR spectrum figure of the compound obtained in the production example 1-4. It is ¹ H-NMR spectrum figure of the compound obtained in the production example 1-4. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-5. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-5. 6 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 1-6. 6 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 1-6. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-7. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-7. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-8. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-8. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-9. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 1-9. It is ¹ H-NMR spectrum figure of the compound obtained in the production example 2-1. It is ¹ H-NMR spectrum figure of the compound obtained in the production example 2-2. It is ¹ H-NMR spectrum figure of the compound obtained in the production example 2-2. 3 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 2-3. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 2-4. It is ¹ H-NMR spectrum figure of the compound obtained in Production Example 2-4. 3 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 2-5. 3 is a ¹ H-NMR spectrum diagram of the compound obtained in Production Example 2-5. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-1. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-2. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-3. It is a ¹ H-NMR spectrum of the compound obtained in Example 1-4. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-5. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-6. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-7. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-8. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-9. It is a ¹ H-NMR spectrum of the compound obtained in Example 1-10. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-11. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-12. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-12. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-13. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-13. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-14. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-15. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-16. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-17. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-17. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-18. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-19. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-20. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-21. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-22. It is ¹ H-NMR spectrum figure of the compound obtained in Example 1-23. It is ¹ H-NMR spectrum figure of the compound obtained in Comparative Example 1-1. It is ¹ H-NMR spectrum figure of the compound obtained in Comparative Example 1-2. 6 is a ¹ H-NMR spectrum diagram of the compound obtained in Comparative Example 1-3.

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 of the following formulas (1) to (6), and includes the compounds represented by the formulas (P1) to (P4) as described above. do not do.

In the formula (1) ~ (6), Ar c each independently represent a group represented by the following formula (Q), X is independently together may be substituted, a hetero atom Represents an arylene group which may contain, Y represents an independently and optionally substituted phenylene group, and g each independently represents an integer of 1 to 10, but preferably. Ar ^c each independently represent a group represented by the following formula (Q ') or (Q'').

In formulas (Q), (Q') and (Q ″), R ¹ independently has a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom. Represents an alkyl halide group of up to 20, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ² may be independently substituted and contains a heteroatom. It represents an aryl group which may be an aryl group, and Ar ^s represents an arylene group which may be independently substituted and may contain a heteroatom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl. , N-Pentyl, n-Hexyl, n-Heptyl, n-octyl, n-Nonyl, n-decyl group and other linear or branched alkyl groups having 1 to 20 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. , Cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl group and other cyclic alkyl groups having 3 to 20 carbon atoms.

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

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- Examples include phenyl, 9-phenyl group and the like.

The alkyl halide 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, and tri. Fluoromethyl, 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-Hexafluoropropane-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, 2- (perfluorohexyl) ethyl group and the like.

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, and an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. , All hydrogen atoms are even more preferred.

The aryl group which may be substituted with R ^{2 in} the above formulas (Q), (Q') and (Q ″) and may contain a hetero atom contains a hetero atom as a constituent atom thereof. It is also a good arylene group, 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, and more preferably 30 or less.
Specific examples of the substituent of the aryl group which may be substituted with R ² and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms. Examples thereof include an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkyl halide 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. Specific examples of the atom, the alkyl group having 1 to 20 carbon atoms, the alkyl halide 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 above. Can be mentioned.

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 and the like can be mentioned.

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, and 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-eicosynyl group and the like can be mentioned.

As R ² , an aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom is preferable, and a phenyl group which may be substituted and a naphthyl group which may be substituted may be used. More preferably, both are more preferably a phenyl group or a naphthyl group, and both are even more preferably a phenyl group.
Hereinafter, specific examples of groups suitable for R ² will be given, but the present invention is not limited thereto.

The arylene group which may be substituted with Ar ^{s in} the above formulas (Q), (Q') and (Q ″) and may contain a hetero atom contains a hetero atom as a constituent atom thereof. It is also a good arylene group, 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, and more preferably 30 or less.
Specific examples of the substituent of the arylene group which may be substituted with Ar ^s and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms. Examples thereof include an alkyl halide group having 1 to 20, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogen having 1 to 20 carbon atoms. Examples of the alkylated alkyl group, 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 one preferred embodiment, Ar ^s is a group represented by any one of the following formulas (101) to (118).

R ³ independently contains a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Alternatively, it represents an aryl group having 6 to 20 carbon atoms, where V ¹ is an independent C (R ⁴ ) ₂ (R ⁴ is an independent hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or (Represents an alkyl halide 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, It represents O or SO ₂ , where V ² is NR ⁵ (R ⁵ has the same meaning as above), S or O.
The halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkyl halide groups having 1 to 20 carbon atoms in R ³ to R ⁵ are described above. The same can be mentioned.

In particular, R ³ is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl halide group having 1 to 10 carbon atoms, respectively, and has a hydrogen atom and a carbon number of carbon atoms. Alkyl groups of 1 to 5 and fluoroalkyl groups having 1 to 5 carbon atoms are more preferable, and hydrogen atoms, methyl groups and trifluoromethyl groups are even more preferable. From the viewpoint of lowering the extinction coefficient of the obtained thin film, at least one R ³ may be 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. Preferably, in consideration of this point, a trifluoromethyl group is more preferable.
Independently, R ⁴ preferably has 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.
R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 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, and a naphthyl group, and a hydrogen atom. , Methyl group and phenyl group are even more preferable.

Also, if all R ³ is not an electron withdrawing group, the extinction coefficient of the thin film from the viewpoint of reducing the resulting, V ¹ is, S, O, SO ₂ are preferred. When V ¹ is S, O, SO ₂ , an electron-withdrawing group may be present in R ³ .
Furthermore, if all R ³ is not an electron withdrawing group, from the viewpoint of lowering the extinction coefficient of the thin film obtained, V ² is, S, O is preferred. When V ² is S or O, an electron-withdrawing group may be present in R ³ .

As Ar ^s , a group represented by any of the following formulas (101A) to (118A) is preferable.

(In the equation, R ³ , V ¹ and V ² have the same meaning as above.)

Hereinafter, specific examples suitable as Ar ^s will be given, but the present invention is not limited thereto.

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the equation, R ⁴ and R ⁵ have the same meaning as above.)

(In the formula, R ⁵ has the same meaning as above.)

(In the formula, R ⁵ has the same meaning as above.)

The arylene group which may be substituted with X in the above formulas (1) and (2) and may contain a hetero atom is not particularly limited, and even if the structure is a condensed ring, the ring is not particularly limited. May be a connected structure. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
Specific examples of the substituent of the arylene group which may be substituted with X and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom. Examples thereof include an alkyl group having 20 to 20, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogenation having 1 to 20 carbon atoms. Examples of the alkyl group, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms include the same as above.

In particular, considering the balance of refractive index, transparency and electrical characteristics, the arylene group which may be substituted with X in the above formulas (1) and (2) and may contain a heteroatom is the following formula ( A divalent group represented by any one of 201) to (207) is preferable.

In formulas (201) to (207), R ⁶ independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and an alkyl halide group having 1 to 20 carbon atoms. , Represents an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, W ¹ is an independent single bond, and C (R ⁷ ) ₂ (R ⁷ is an independent element. Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl halide group having 1 to 20 carbon atoms), S, O, or SO ₂ , where W ² is C (R ⁷ ) ₂ (R). ⁷ represents the same meaning as above), NR ⁸ (R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or. Represents SO ₂ , W ³ represents NR ⁸ (R ⁸ represents the same meaning as above), S or O. The halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkyl halide groups having 1 to 20 carbon atoms in R ⁶ to R ⁸ are described above. The same can be mentioned.

In particular, R ⁶ is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl halide group having 1 to 10 carbon atoms, respectively, and has a hydrogen atom and a carbon number of carbon atoms. Alkyl groups of 1 to 5 and fluoroalkyl groups having 1 to 5 carbon atoms are more preferable, and hydrogen atoms, methyl groups and trifluoromethyl groups are even more preferable. From the viewpoint of lowering the extinction 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 the point, a trifluoromethyl group is more preferable.
Independently, R ⁷ preferably has 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.
R ⁸ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 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, and a naphthyl group, and a hydrogen atom. , Methyl group and phenyl group are even more preferable.

Also, if all R ⁶ is not an electron withdrawing group, the extinction coefficient of the thin film from the viewpoint of reducing the obtained, W ¹ is, S, O, SO ₂ are preferred. When W ¹ is S, O, and SO ₂ , an electron-withdrawing group may be present in R ⁶ .

Also, if all R ⁶ is not an electron withdrawing group, the extinction coefficient of the thin film from the viewpoint of reducing the obtained, W ² is, S, O, SO ₂ are preferred. When W ² is S, O, SO ₂ , an electron-withdrawing group may be present in R ⁶ .
Furthermore, if all R ⁶ is not an electron withdrawing group, from the viewpoint of lowering the extinction coefficient of the resulting thin film, W ³ is, S, O is preferred. When W ³ is S, O, SO ₂ , an electron-withdrawing group may be present in R ⁶ .

Further, in the above formulas (201) to (207), the bonding position of the amino group and the spacer W ¹ on the aromatic ring is not particularly limited, but any of the following formulas (201A) to (207A). A divalent group represented by is preferable.

(In the formula, R ⁶ , W ¹ , W ² and W ³ have the same meanings as above.)

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

(In the formula, W ¹ , W ² and W ³ have the same meaning as above.)

In the formula (201A ') ~ (207A' ), R 6 ' are each independently 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 Represents an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Specific examples of the alkoxy group and the aryl group having 6 to 20 carbon atoms are the same as those described above.
Among these, R ^6'preferably an alkyl group having 1 to 10 carbon atoms and an alkyl halide group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms and a fluoroalkyl group having 1 to 5 carbon atoms. More preferably, a methyl group and a trifluoromethyl group are even more preferable.

Examples of X suitable in the present invention include those represented by the following formulas, but are not limited thereto.

(In the formula, R ⁷ , R ⁸ and W ³ have the same meaning as above.)

Examples of the phenylene group in which Y may be substituted in the above formulas (3) to (6) include a 1,4-phenylene group, which may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or the like. , 3-Phenylene group or 1,2-phenylene group, but may be substituted 1,4-phenylene group or 1,3-phenylene group in consideration of the balance of refractive index, transparency and electrical characteristics. Is preferable, and an unsubstituted 1,4-phenylene group or a 1,3-phenylene group is more preferable.

In the above formulas (3) to (6), g independently represents an integer of 1 to 10, but considering the solubility of the compound in an organic solvent and the transparency of the obtained thin film, 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 even more preferred, and 1 is optimal considering the availability of the starting compound.

In the present invention, Ar ^s is preferably a group represented by the formula (107), more preferably a group represented by any one of formulas (107A) ~ (107C), and even more preferably formula (107A-1) A group represented by any of (107C-5), more preferably a group represented by the formula (107B-1) or (107C-1).

In the present invention, from the viewpoint of ease of synthesis, it is preferable that ^Arc is the same group in each of the formulas (1) to (6).
In particular, Ar ^c is preferably a group (Ar ^C1) represented by the formula (Q-1), more preferably a group represented by the formula ^{(Q-2) (Ar C2} ) or formula (Q-3 ) Is a group (Ar ^C3 ).

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

(In the formula, X, Y, Ar ^C1 and g have the same meanings as above.)

(In the formula, X, Y, Ar ^C2 and g have the same meanings as above.)

(In the formula, X, Y, Ar ^C3 and g have the same meanings as above.)

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

(In the formula, Z represents a halogen atom or a pseudohalogen group, and X, R ¹ , R ² and Ar ^s have the same meanings as above.)

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

The charging ratio of the aryldiamine compound [I] to the halogenated aryl compound [II] depends on whether the compound to be synthesized is the arylamine compound (1) or (2), and the reaction of the raw material compound. Usually, the aryl halide compound is appropriately determined in the range of 1.2 to 0.6 equivalents with respect to the amount of all NH groups of the aryldiamine compound [I] in consideration of the properties and bulkiness. When synthesizing the arylamine compound (1), 1.0 equivalent or more of the aryl halide compound is preferable.

Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide and copper iodide; Pd (PPh ₃ ) ₄ (tetrax (triphenylphosphine) palladium), Pd (PPh ₃ ) ₂ Cl ₂ (Bis (triphenylphosphine) dichloropalladium), Pd (dba) ₂ (bis (dibenzylideneacetone) palladium), Pd ₂ (dba) ₃ (tris (dibenzylideneacetone) dipalladium), Pd (Pt-Bu) ₃ ) Examples thereof include palladium catalysts such as ₂ (bis (tri (t-butylphosphine)) palladium) and Pd (OAc) ₂ (palladium acetate). These catalysts may be used alone or in combination of two or more. These catalysts may also be used with suitable known ligands.

Examples of such ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl ( Phine) phosphine, di-t-butyl (4-dimethylaminophenyl) phosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphos) Tertiary phosphine such as fino) butane, 1,1'-bis (diphenylphosphine) ferrocene, tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, John Phos commercially available from Aldrich , CyjohnPhos, DavePhos, XPhos, SPhos , tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavePhos, 2'-Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me 3 (OMe) tBuXPhos , (2-Biphenyl) di-1-adamantylphosphine, RockPhos, CPhos and other biphenylphosphine compounds.

The amount of the catalyst used can be about 0.01 to 0.5 mol with respect to 1 mol of the aryl halide compound [II], but is preferably about 0.05 to 0.2 mol.
When a ligand is used, the amount used can be 0.1 to 5 equivalents with respect to the metal complex to be used, but 1 to 2 equivalents are preferable.

In addition, a base may be used in the above reaction. Examples of the base include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide. , Alkali metal alone such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, alkali metal hydride, alkali metal hydroxide, alkoxy alkali metal, alkali metal carbonate, alkali metal hydrogen carbonate; alkaline soil carbonate such as calcium carbonate Metals; n-butyl lithium, s-butyl lithium, t-butyl lithium, lithium diisopropylamide (LDA),

lithium

2,2,6,6-tetramethylpiperidin (LiTMP), hexamethyldisilazane lithium (LHMDS), etc. Organic lithium; Examples thereof include amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.
When a base is used, the amount used can be 0.1 to 5 equivalents with respect to the aryl halide compound [II] to be used, but 1 to 2 equivalents are preferable.

Each of the above reactions is carried out in a solvent when all the raw material compounds are solid or from the viewpoint of efficiently obtaining the target arylamine compound. When a solvent is used, the type 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.), and aromatics. Group hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesityrene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, etc.) P-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butylmethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methylethylketone, etc.) Methylisobutylketone, di-n-butylketone, cyclohexanone, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), urea Species (N, N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethylsulfoxide, sulfolane, etc.), nitriles (acetoyl, propionitrile, butyronitrile, etc.), etc., and these solvents alone It may be used, or two or more kinds may be mixed and used.

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is particularly preferably about 0 to 200 ° C., more preferably 20 to 150 ° C. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.
After completion of the reaction, post-treatment can be carried out according to a conventional method to obtain the desired arylamine compound.

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)) are aryl as shown in the following scheme. It can be produced by reacting a diamine compound [I'] with an aryl halide compound [II] in the presence of a catalyst.

(In the formula, Y, R ¹ , R ² , Z, Ar ^s and g have the same meanings as above.)

The charging ratio of the aryldiamine compound [I'] to the aryl halide compound [II] is not particularly limited as long as the desired product can be obtained, but usually the compounds to be synthesized are the arylamine compounds (3) to Depending on which of (5) is used, and in consideration of the reactivity and bulkiness of the raw material compound, the amount of the aryl halide compound is 1 with respect to the total amount of NH groups of the aryldiamine compound [I']. .2 Equivalent or less is appropriately determined, and when synthesizing the arylamine compound (3), 1.0 equivalent or more of the aryl halide compound is preferable with respect to the amount of all NH groups of the aryldiamine compound [I']. , In the case of synthesizing the arylamine compound (4), the amount of the aryldiamine compound [I'] can be 2.0 equivalents or more of the aryl halide compound, but 2.0 to 2.4 equivalents. Preferably, when synthesizing the arylamine halide compound (5), the amount of the aryl compound can be 4.0 equivalents or more with respect to the amount of the aryldiamine compound [I'], but 4.0 to 4.8 equivalents. Is preferable.
In addition, various conditions and suitable conditions of the coupling reaction regarding the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, etc. are described with respect to the arylamine compound represented by the formula (1) or (2). Is the same as.

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, the dinitro compound [I "-1] is reacted with the aryl halide compound [II] to obtain the dinitro compound [I "-2].

(In the formula, R ¹ , R ² , Y, Z, Ar ^s and g have the same meanings as above.)

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 amount of substance of the total NH groups of the dinitro compound. About 1 to 1.2 equivalents are preferable.
In addition, the reaction conditions and suitable conditions regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2). Is.

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

(Wherein, Y, Ar ^c and g are the same as defined above.)

Next, the amine compound [I "-3] can be reacted with the aryl halide compound [II] to obtain the arylamine compound (6).

^{^{(Wherein, R 1, R 2, Y}} , Z, Ar c, Ar s and g are the same as defined above.)

The charging ratio of the amine compound [I "-3] and the aryl halide compound [II] can be 2 equivalents or more of the aryl halide compound with respect to the amine compound, but is about 2 to 2.4 equivalents. Is preferable.
In addition, the reaction conditions and suitable conditions regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2). Is.

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

(In the formula, R ¹ , R ² , Z and Ar ^s have the same meaning as above.)

Z ^B independently represents a group represented by the following formula (E1) or (E2).

Z'represents a halogen atom or a pseudohalogen group, and examples of the halogen atom and the pseudohalogen group include the same as above.
Here, Z and Z'may 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 Z. It is preferable that the reactivity of the atom (group) is higher than that of the atom (group). By providing such a difference in reactivity, the Z ^B group in the arylcarbazole compound [III] reacts preferentially with the Z'atom (group) over the Z atom (group), and is efficient. The desired aryl halide compound [II] can be obtained.

D ¹ and D ² independently represent 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 is an alcandiyl group or carbon having 1 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, which represent an arylene group having 6 to 20 carbon atoms, are the same as those described above.

The alcandiyl group having 1 to 20 carbon atoms includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, 2,2-dimethylpropane-1,3-diyl, and 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 group and the like.

As the arylene group having 6 to 20 carbon atoms, 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,2-anthrylene, 2,3-anthrylene, 1,2 -Phenantrylene, 3,4-phenanthrylene, 9,10-phenanthrylene group and the like can be mentioned.

The charging ratio of the arylcarbazole compound [III] to the dihalide aryl compound [IV] can be 1.0 or more with respect to the arylcarbazole compound [III] 1 in terms of molar ratio. However, it is preferably about 1.0 to 1.2.

Each of the above reactions is carried out in a solvent when all the raw material compounds are solid or from the viewpoint of efficiently obtaining the target arylamine halide compound. When a solvent is used, the type 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 methylisobutylketone and cyclohexanone; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned. These solvents can be used alone or in admixture of two or more. Of these, 1,4-dioxane, toluene, xylene and the like are particularly preferable.

Examples of the catalyst used in the above reaction are [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride (PdCl ₂ (dppf)) and tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). , Bis (triphenylphosphine) dichloropalladium (Pd (PPh ₃ ) ₂ Cl ₂ ), bis (benzilidenacetone) palladium (Pd (dba) ₂ ), tris (benzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ), Examples thereof include palladium catalysts such as bis (tri-t-butylphosphine) palladium (Pd (Pt-Bu ₃ ) ₂ ) and palladium (II) acetate (Pd (OAc) ₂ ).

The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is particularly preferably about 0 to 200 ° C., more preferably 20 to 150 ° C. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.
After completion of the reaction, post-treatment can be carried out according to a conventional method to obtain the desired arylamine halide compound.

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

(In the formula, Ar ^s , Z and Z'have the same meaning as above.)

As the halogenating agent, known ones can be used, and specific examples thereof include, but are not limited to, N-bromosuccinimide and the like. 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 type 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.

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

(In the formula, R ¹ , R ² , Z and Z ^B have the same meanings as above.)

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

Further, the compound represented by the formula [III'] is obtained after reacting the compound represented by the formula [III'-2] with an aryl halide compound (R ² Z) as shown in the following scheme. , be accomplished by treatment with a halogenating agent, the compound represented by the formula [III'-2], after treatment with a halogenating agent, can be obtained by reacting a halogenated aryl compound (R ² Z), The latter reaction is preferable from the viewpoint of avoiding halogenation of the N-position aryl group of the carbazole skeleton and obtaining the target product more efficiently.

(In the formula, R ¹ , R ² and Z have the same meanings as above.)

As the halogenating agent used in the above reaction, a known halogenating agent can be used, and the amount of the halogenating agent is represented by the formula [III'-1-1] or [III'-2] in terms of molar ratio. It is about 1 to 1.5 with respect to the compound 1 to be produced.
The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
The 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.

Further, the compound represented by the formula [VI] having two alkyl groups at the 9-position of the fluorene ring, which is a raw material of the spacer skeleton of Ar ^S , is prepared in the presence of a base as shown in the scheme below. It can be obtained by reacting a compound represented by the formula [VI'] with a compound represented by the formula [VII].

(Wherein, R ^3, Z and Z 'represent the same as defined above, R ^4' are each independently an alkyl group or a halogenated alkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Represents.)

The preparation of the compound represented by the formula [VI'] and the compound represented by the formula [VII] is represented by the formula [VII] with respect to the compound 1 represented by the formula [VI'] in terms of molar ratio. Compounds 1 to 1.5.
The bases that can be used in the above reaction are not particularly limited as long as they are the bases used in this type of reaction, and specific examples thereof include t-BuOK, t-BuONa, CsCO ₃ , K ₂ CO ₃ , and Na. ₂ CO ₃ , n-BuLi, t-BuLi, s-BuLi, NaOH, KOH, LiOH, etc., but t-BuOK, t-BuONa, n-BuLi, t-BuLi, s-BuLi, NaOH, KOH Is preferable.
The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
The temperature of the reaction is usually appropriately determined from the range of 0 to 140 ° C., and the time thereof is usually appropriately determined from the range of 0.1 to 100 hours.

The amine compounds that can be used as raw materials for the arylamine compounds of the present invention are (A) amine compounds [I'''] or [I''''] and aryl compounds [VIII], as shown in the following scheme. ] And (B) the reduction reaction of the nitro group by hydrogenation. By repeating the reactions (A) and (B), the chain length (phenylene number) is extended. I can go.

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

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

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

(In the formula, Z has the same meaning as above.)

Since it is possible to create even and odd phenylene numbers depending on whether the reaction above or below the above scheme is selected, it is synthetically difficult to protect one amino group with a protecting group. An amine compound [I'] having a desired number of phenylene can be freely produced without using a method.

In this case, the charging ratio of the raw material compounds in each reaction is 1 to 1 to the raw material compound having a nitro group (raw material compound containing a halogen atom (pseudohalogen group)) with respect to the raw material compound having an amino group. Within the range of about 2.4, it is appropriately determined depending on whether the number of phenylene to be added is 1 or 2.

Moreover, as the palladium catalyst used for the coupling reaction, the same thing as above can be mentioned. Also in this case, a ligand can be used. As the ligand, in addition to those exemplified above, JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDave, which are commercially available from Aldrich. -Biphenylphosphine compounds such as Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me ₃ (OMe) tBuXPhos, (2-Biphenyl) di-1-adamantylphosphine, RockPhos, CPhos can be preferably used. ..

Examples of the base used in the coupling reaction include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, and hydroxide. Alkali metal alone such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, alkali metal hydride, alkali metal hydroxide, alkoxy alkali metal, alkali metal carbonate, alkali metal hydrogen carbonate; calcium carbonate Alkali carbonate earth metals such as n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA),

lithium

2,2,6,6-tetramethylpiperidine (LiTMP), hexamethyldisilazane. Organic lithium such as lithium (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine and the like can be mentioned.

In addition, various conditions and suitable conditions of the coupling reaction regarding the catalyst, solvent, temperature and time of the reaction, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2).
Further, the hydrogenation reaction using Pd / C can be carried out by a known method.
When a paraphenylene group or orthophenylene is introduced instead of the metaphenylene group, 4-halonitrobenzene or 2-halonitrobenzene may be used instead of 3-halonitrobenzene.

Hereinafter, specific examples of the arylamine compound of the present invention will be given, but the present invention is not limited thereto.
In the table, H is a hydrogen atom, Ph is a phenyl group, Me is a methyl group, n-Hex is an n-hexyl group, p-Toly is a p-tolyl group, and 2-Thie is 2-thienyl. The groups, 1,3-Ph represents a 1,3-phenylene group, and 1,4-Ph represents a 1,4-phenylene group. For example, the arylamine compounds of Nos. 1 and 865 are the following compounds, respectively. ..

The above-mentioned arylamine compound of the present invention can be suitably used as a charge transporting substance. In this case, it can be used as a charge-transporting varnish containing the arylamine compound of the present invention and an organic solvent, and the charge-transporting varnish can be used to improve its charge-transporting ability depending on the use of the obtained thin film. It may contain a dopant substance for the purpose of. Further, the arylamine compound of the present invention can be used in combination with other conventionally known charge-transporting substances such as an aniline derivative and a thiophene derivative, but the arylamine compound of the present invention alone can be used as a charge-transporting substance. preferable.
In the present invention, charge transportability is synonymous with conductivity. The charge-transporting varnish may be one that has charge-transporting property by itself, and the solid film obtained thereby may have charge-transporting property.

The dopant substance is not particularly limited as long as it is soluble in at least one solvent used for the varnish, and either an inorganic dopant substance or an organic dopant substance can be used.
Further, the inorganic and organic dopant substances may be used alone or in combination of two or more.
Furthermore, the dopant substance first exhibits its function as a dopant substance in the process of obtaining a charge-transporting thin film which is a solid film from the varnish, for example, when a part of the molecule is removed by an external stimulus such as heating during firing. Alternatively, it may be a substance that improves, for example, an aryl sulfonic acid ester compound protected by a group in which a sulfonic acid group is easily eliminated.

In particular, in the present invention, a heteropolyacid is preferable as the inorganic dopant substance.
The heteropolyacid has a structure in which a hetero atom is located at the center of a molecule, which is typically represented by a Keggin type represented by the formula (H1) or a Dawson type chemical structure represented by the formula (H2). It is a polyacid formed by condensing isopolyacid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), and oxygen acid of a different element. Oxygen acids of such dissimilar elements mainly include oxygen acids of silicon (Si), phosphorus (P), and arsenic (As).

Specific examples of the heteropolyacid include phosphomolybdic acid, silicate molybdic acid, phosphotungstic acid, silicate tungstic acid, phosphotungstic acid, and the like, and these may be used alone or in combination of two or more. Good. These heteropolyacids are available as commercially available products, and can also be synthesized by a known method.
In particular, when one kind of heteropolyacid is used, the one kind of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most suitable. When two or more kinds of heteropolyacids are used, one of the two or more kinds of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.
In addition, in quantitative analysis such as elemental analysis, heteropolyacids have a large number of elements or a small number of elements from the structure represented by the general formula, but the heteropolyacid is obtained as a commercially available product or a known synthesis. As long as it is properly synthesized according to the method, it can be used in the present invention.
That is, for example, in general, phosphotungsten acid is represented by chemical formulas H ₃ (PW ₁₂ O ₄₀ ) and nH ₂ O, and phosphomolydic acid is represented by chemical formulas H ₃ (PMo ₁₂ O ₄₀ ) and nH ₂ O, respectively. , In quantitative analysis, even if the number of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product. Alternatively, it can be used in the present invention as long as it is appropriately synthesized according to a known synthesis method. In this case, the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthetic product or the commercially available product, but the form available as the commercially available product and the known synthesis. In a form that can be isolated by the method, it means the total mass in a state containing hydrated water and other impurities.

The amount of the heteropolyacid used can be about 0.001 to 50.0 with respect to the charge transporting substance 1 in terms of mass ratio, but is preferably about 0.01 to 20.0, more preferably 0. It is about 1 to 10.0.

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 benzoquinone derivatives include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone, 2,3-dichloro-5, and so on. 6-Dicyano-1,4-benzoquinone (DDQ) and the like can be mentioned.

In the formula, R ⁵⁰⁰ to R ⁵⁰³ each independently represent a hydrogen atom or a halogen atom, but at least one is a halogen atom, at least two are preferably halogen atoms, and at least three are halogen atoms. It is more preferable that all of them are halogen atoms.
Examples of the halogen atom include the same as above, but a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

Specific examples of such halotetracyanoquinodimethane include 2-fluoro-7,7,8,8-tetracyanoquinodimethane and 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-Tetra Examples thereof include chloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ).

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

The organic dopant substance is an electrically neutral onium composed of a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by the formulas (c1) to (c5). Borate salts can also be used.

(In the formula, Ar represents an aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent, respectively, and L. Represents an alkylene group having 1 to 20 carbon atoms, -NH-, an oxygen atom, a sulfur atom or -CN ⁺ -.)

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

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

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

Further, as the organic dopant substance, an aryl sulfonic acid compound or an aryl sulfonic acid ester compound can also be preferably used.

Specific examples of the aryl sulfonic acid compound include benzene sulfonic acid, tosylic acid, p-styrene sulfonic acid, 2-naphthalene sulfonic acid, 4-hydroxybenzene sulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzene sulfonic acid, and dihexyl benzene. Sulfonic acid, 2,5-dihexylbenzene sulfonic acid, dibutylnaphthalene sulfonic acid, 6,7-dibutyl-2-naphthalene sulfonic acid, dodecylnaphthalene sulfonic acid, 3-dodecyl-2-naphthalene sulfonic acid, hexylnaphthalene sulfonic acid, 4 -Hexyl-1-naphthalene sulfonic acid, 7-hexyl-1-naphthalene sulfonic acid, 6-hexyl-2-naphthalen sulfonic acid, octyl naphthalene sulfonic acid, 2-octyl-1-naphthalene sulfonic acid, dinonyl naphthalene sulfonic acid , 2,7-Dinonyl-4-naphthalene sulfonic acid, dinonyl naphthalenedisulfonic acid, 2,7-dinonyl-4,5-naphthalenedisulfonic acid, 1,4-benzodioxanedisulfonic acid described in International Publication No. 2005/000832. Examples thereof include compounds, aryl sulfonic acid compounds described in International Publication No. 2006/025342, and aryl sulfonic acid compounds described in International Publication No. 2009/09632.

Examples of preferable aryl sulfonic acid compounds include aryl sulfonic acid compounds represented by the formula (H4) or (H5).

A ¹ represents O or S, with O being preferred.
A ² represents a naphthalene ring or an anthracene ring, but a naphthalene ring is preferable.
A ³ represents a 2- to tetravalent perfluorobiphenyl group, p represents the number of bonds between A ¹ and A ^3, and is an integer satisfying 2 ≦ p ≦ 4, where A ³ is perfluorobiphenyldiyl. The group, preferably a perfluorobiphenyl-4,4'-diyl group, preferably has a p of 2.
q represents the number of sulfonic acid groups bonded to A ² , and is an integer satisfying 1 ≦ q ≦ 4, but 2 is optimal.

A ⁴ to A ⁸ are independently hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, or halogenation having 2 to 20 carbon atoms. Representing an alkenyl group, at least three of A ⁴ to A ⁸ are halogen atoms.

Alkyl halide groups having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, and 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, 2,2,3,3,4,5,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, etc. Be done.

Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), perfluorobutenyl group and the like.
Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same as above, but the halogen atom is preferably a fluorine atom.

Among these, A ⁴ to A ⁸ are hydrogen atoms, halogen atoms, cyano groups, alkyl groups having 1 to 10 carbon atoms, alkyl halide groups having 1 to 10 carbon atoms, or alkenyl halides having 2 to 10 carbon atoms. a group, and at least 3 of the a ⁴ ~ a ⁸ is preferably a fluorine atom, a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, having 1 to 5 carbon atoms More preferably, it is an alkyl fluoride group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least 3 of A ⁴ to A ⁸ are fluorine atoms, and hydrogen atom, fluorine atom, cyano group, and the like. It is even more preferable that it is a perfluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkenyl group having 1 to 5 carbon atoms, and that A ⁴ , A ⁵ and A ⁸ are fluorine atoms.
The perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkenyl group are substituted with fluorine atoms.

R represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1 ≦ r ≦ 4, but 2 to 4 is preferable, and 2 is optimal.

The molecular weight of the aryl sulfonic acid compound used as the dopant substance is not particularly limited, but is preferably 2000 or less, more preferably 2000 or less, considering the solubility in an organic solvent when used together with the arylamine compound of the present invention. It is 1500 or less.

Specific examples of suitable aryl sulfonic acid compounds will be given below, but the present invention is not limited to these.

The amount of the aryl sulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, with respect to the charge transporting substance 1 in terms of the amount of substance (molar) ratio. ..
Commercially available products may be used as the aryl sulfonic acid compound, but International Publication No. 2006/025342, International Publication No. 2009/096322, International Publication No. 2015/111654, International Publication No. 2015/0533320, International Publication No. 2015 It can also be synthesized by a known method described in / 115515 and the like.

On the other hand, examples of the aryl sulfonic acid ester compound include an aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217455, an aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017-243631 (Japanese Patent Application No. 2017-243631). Examples thereof include the aryl sulfonic acid ester compounds described in International Publication No. 2019/124412), and specifically, those represented by any of the following formulas (H6) to (H8) are preferable.

(In the formula, m is an integer satisfying 1 ≦ m ≦ 4, preferably 2. n is an integer satisfying 1 ≦ n ≦ 4, but 2 is preferable.)

In formula (H6), A ¹¹ is an m-valent group derived from perfluorobiphenyl.
A ¹² is —O— or —S—, but —O— is preferred.
A ¹³ is a (n + 1) -valent group derived from naphthalene or anthracene, but a group derived from naphthalene is preferable.
R ^s1 to R ^s4 are each independently a hydrogen atom or a linear or branched chain alkyl group having 1 to 6 carbon atoms, and R ^s5 is an optionally substituted alkyl group having 2 to 20 carbon atoms. It is a monovalent hydrocarbon group of.

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 and the like. , An alkyl group having 1 to 3 carbon atoms is preferable.
The monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl. Alkyl groups such as groups; aryl groups such as phenyl, naphthyl and phenanthryl groups can be mentioned.

In particular, among R ^s1 to R ^s4 , R ^s1 or R ^s3 is a linear alkyl group having 1 to 3 carbon atoms, and the rest is a hydrogen atom, or R ^s1 is a linear alkyl group having 1 to 3 carbon atoms. It is preferable that R ^s2 to R ^s4 are hydrogen atoms. In this case, the methyl group is preferable as the linear alkyl group having 1 to 3 carbon atoms.
Further, as R ^s5 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable.

In the 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 the hydrocarbon group may be one or more. It is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms containing an aromatic ring.
Examples of such a hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene and the like.
In the above-mentioned hydrocarbon group, a part or all of the hydrogen atom may be further substituted with a substituent, and examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a 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 so on.
Among these, as A ¹⁴ , a group derived from benzene, biphenyl or the like is preferable.

Further, A ¹⁵ is —O— or —S—, but —O— is preferable.
A ¹⁶ is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is (n + 1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms.
Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like.
Among them, as A ¹⁶ , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.

R ^s6 and R ^s7 are independently hydrogen atoms or linear or branched chain monovalent aliphatic hydrocarbon groups, and R ^s8 is a linear or branched chain monovalent aliphatic hydrocarbon. It is a 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 linear or branched monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, and the like. Alkyl groups having 1 to 20 carbon atoms such as 2-ethylhexyl and decyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a hexenyl group.
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.

In the formula (H8), R ^s9 to R ^s13 independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl halide group having 1 to 10 carbon atoms. Alternatively, it is an alkenyl halide group having 2 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl. Examples thereof include t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group and the like.

The alkyl halide group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom. Specific examples 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, 3,3,4,5,4-pentafluorobutyl, 2 , 2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4-nonafluorobutyl group and the like.

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

Among these, as R ^s9 , a nitro group, a cyano group, an alkyl halide group having 1 to 10 carbon atoms, and an alkenyl halide group having 2 to 10 carbon atoms are preferable, and a nitro group, a cyano group, and 1 to 4 carbon atoms are preferable. The alkyl halide group and the alkenyl halide group having 2 to 4 carbon atoms are more preferable, and the nitro group, the cyano group, the trifluoromethyl group and the perfluoropropenyl group are even more preferable.
As R ^s10 to R ^s13 , a halogen atom is preferable, and a fluorine atom is more preferable.

A ¹⁷ is -O-, -S- or -NH-, but -O- is preferable.
A ¹⁸ is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is (n + 1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms.
Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like.
Among these, as A ¹⁸ , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.

R ^s14 to R ^s17 are independently hydrogen atoms or linear or branched chain monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
Specific examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl and n. -Alkyl groups having 1 to 20 carbon atoms such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl Examples thereof include alkenyl groups having 2 to 20 carbon atoms such as -2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and hexenyl groups, but alkyl groups having 1 to 20 carbon atoms are preferable, and alkyl groups having 1 to 20 carbon atoms are preferable. An alkyl group of 10 is more preferable, and an alkyl group having 1 to 8 carbon atoms is even more preferable.

R ^s18 is a linear or branched chain monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR ^s19 . R ^s19 is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.
^Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms of R ^{s18 include} the same groups as described above.
When R ^s18 is a monovalent aliphatic hydrocarbon group, R ^s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferable.
^Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms of R ^s19 include those other than the methyl group among the above-mentioned monovalent aliphatic hydrocarbon groups, and aryl groups such as phenyl, naphthyl, and phenanthryl groups.
Among these, R ^s19 is preferably a linear alkyl group or a phenyl group having 2 to 4 carbon atoms.
Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.

Specific examples of suitable aryl sulfonic acid ester compounds include, but are not limited to, those shown below.

The amount of the aryl sulfonic acid ester compound used is preferably about 0.01 to 20, more preferably about 0.05 to 10 with respect to the charge transporting substance 1 in terms of the amount of substance (molar) ratio.
A commercially available product may be used as the aryl sulfonic acid ester compound, but it may also be synthesized by a known method described in International Publication No. 2017/217455, International Publication No. 2017/217457, International Publication No. 2019/124412 and the like. it can.

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

Further, when the obtained thin film is used as the hole injection layer of the organic EL device, the charge transport varnish is an organic silane compound for the purpose of improving the injection property into the hole transport layer and improving the life characteristics of the device. May include. Its content is usually about 1 to 30% by mass with respect to the total mass of the charge transporting substance and the dopant substance.

As the organic solvent used when preparing the charge transporting varnish of the present invention, a highly polar solvent capable of satisfactorily dissolving the arylamine compound of the present invention 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 because it is superior in process compatibility to a high-polarity solvent. In the present invention, a low-polarity solvent is defined as a solvent having a relative permittivity of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as a solvent having a relative permittivity of 7 or more at a frequency of 100 kHz.

Examples of low polar solvents include, for example.
Chlorine-based solvents such as chloroform and chlorobenzene;
Aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene;
Aliphatic alcohol solvents such as 1-octanol, 1-nonanol, 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;
Esters 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, diethylene glycol monobutyl ether acetate, etc. Examples include a solvent.

Further, as a highly polar solvent, for example,
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone;
Ketone solvents such as ethyl methyl ketone, isophorone, cyclohexanone;
Cyan-based 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;
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. Monohydric alcohol solvent;
Examples thereof include sulfoxide-based solvents such as dimethyl sulfoxide.

The viscosity of the charge-transporting varnish is appropriately determined depending on the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa · s at 25 ° C. In the present invention, the solid content means a component other than the solvent contained in the charge transporting varnish of the present invention.
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, and the like, but is usually 0.1 to 20.0 mass. It is about%, preferably about 0.5 to 10.0% by mass, and more preferably about 1.0 to 5.0% by mass in consideration of improving the coatability of the varnish.

The method for preparing the charge-transporting varnish is not particularly limited, but for example, a method of dissolving all solids such as a charge-transporting substance containing the arylamine compound of the present invention in an organic solvent at once, or a solid. Examples thereof include a method in which a part of the charge is dissolved in an organic solvent and then the remaining solid content is dissolved.

In particular, when preparing a charge-transporting varnish, from the viewpoint of obtaining a thin film with higher flatness with good reproducibility, after dissolving a charge-transporting substance, a dopant substance, etc. in an organic solvent, a submicrometer-order filter or the like is used. It is desirable to use and filter.

Since the charge transporting varnish described above can easily produce a charge transporting thin film by using the varnish, it can be suitably used when manufacturing an electronic device, particularly an organic EL device.
In this case, the charge-transporting thin film can be formed by applying the above-mentioned charge-transporting varnish on a substrate and firing it.
The varnish coating method is not particularly limited, and examples thereof include a dip method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an inkjet method, a spray method, and a slit coating method. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.

Further, the firing atmosphere of the charge-transporting varnish after coating is not particularly limited, and a thin film having a uniform film-forming surface and high charge-transporting property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum can be obtained. Although it can be obtained, depending on the type of dopant substance used, a thin film having higher charge transportability may be obtained with good reproducibility by firing the varnish in an air atmosphere.

The firing temperature is appropriately set within the range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability applied to the obtained thin film, the type of solvent, the boiling point, etc., and the obtained thin film is obtained. When used as a hole injection layer for an organic EL element, it is preferably about 140 to 250 ° C., more preferably about 145 to 240 ° C., but when the arylamine compound of the present invention is used as a charge transporting substance, it is as low as 200 ° C. or less. Even by firing, a thin film having good charge transportability can be formed.
At the time of firing, a temperature change of two or more steps may be applied for the purpose of exhibiting higher uniform film forming property or allowing the reaction to proceed on the substrate, and heating may be performed by, for example, a hot plate or the like. It may be carried out using an appropriate device such as an oven.

The film thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 300 nm when used as a hole injection layer, a hole transport layer, or a hole transport layer of an organic EL element. As a method of changing the film thickness, there are methods such as changing the solid content concentration in the varnish and changing the amount of solution (varnish amount) on the substrate at the time of coating.

The charge-transporting thin film of the present invention described above usually exhibits a refractive index (n) of 1.60 or more and an extinction coefficient (k) of 0.100 or less with an average value in the wavelength region of 400 to 800 nm. In some embodiments, it exhibits a refractive index of 1.65 or higher, in other embodiments it exhibits a refractive index of 1.70 or higher, and in some embodiments it has an extinction coefficient of 0.050 or lower. Shows an extinction coefficient of 0.010 or less.

When the above-mentioned charge-transporting thin film is applied to an organic EL element, the above-mentioned charge-transporting thin film can be provided between a pair of electrodes constituting the organic EL element.
Typical configurations of the organic EL element include, but are not limited to, the following (a) to (f). In the following configuration, if necessary, an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode. Further, the hole injection layer, the hole transport layer or the hole injection transport layer may also have a function as an electron block layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer is a hole (hole). It may also have a function as a block layer or the like. Further, if necessary, an arbitrary functional layer can be provided between the layers.
(A) Electron / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / Cathode (c) anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (d) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (e) anode / positive Hole injection layer / hole transport layer / light emitting layer / cathode (f) anode / hole injection transport layer / light emitting layer / cathode

The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. When it has a function and only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a "hole injection transport layer", and between the light emitting layer and the anode, When two or more layers of the hole transporting material are provided, the layer close to the anode is the “hole injection layer” and the other layers are the “hole transport layer”. In particular, as the hole injection (transport) layer, a thin film having excellent not only hole acceptability from the anode but also hole injection property into the hole transport (emission) layer is used.
The "electron injection layer", "electron transport layer" and "electron transport layer" are layers formed between the light emitting layer and the cathode and have a function of transporting electrons from the cathode to the light emitting layer. When only one layer of electron transporting material is provided between the light emitting layer and the cathode, it is an "electron injection transporting layer", and a layer of electron transporting material is provided between the light emitting layer and the cathode. When two or more layers are provided, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layer".
The "light emitting layer" is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is adopted. At this time, the host material mainly has a function of promoting the recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. Has a function. In the case of a phosphorescent device, the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.

The charge-transporting thin film produced from the charge-transporting varnish of the present invention is a functional layer 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 the organic EL element. However, as described above, it is usually suitable as a hole injection layer on which an upper layer is formed by a coating method.

Examples of materials and methods for producing an organic EL device using the charge-transporting varnish of the present invention include, but are not limited to, the following.
An example of a method for manufacturing an OLED device having a hole injection layer made of a thin film obtained from the charge transporting varnish is as follows. It is preferable that the electrode is preliminarily subjected to surface treatment such as cleaning with alcohol, pure water or the like, UV ozone treatment, oxygen-plasma treatment or the like within a range that does not adversely affect the electrode.
A hole injection layer is formed on the anode substrate by the above method using the above charge transporting varnish. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer / hole block layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited. Alternatively, instead of forming the hole transport layer and the light emitting layer by vapor deposition in the method, a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light emitting layer containing a light emitting polymer are used. These layers are formed by a wet process using. If necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.

Examples of the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metals typified by aluminum, and metal anodes composed of alloys thereof. Those that have been flattened are preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
Examples of other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, 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 -Triarylamines such as -naphthyl (phenyl) amino] triphenylamine (1-TNATA), 5,5 "-bis- {4- [bis (4-methylphenyl) amino] phenyl} -2,2': Examples thereof include oligothiophenes such as 5', 2 "-turthiophene (BMA-3T).

Examples of the material forming the light emitting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, and (2-hydroxyphenyl) benzo. Low molecular weight luminescent materials such as thiazole metal complexes and silol derivatives; poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3-alkyl Examples thereof include, but are not limited to, a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) and polyvinylcarbazole.
When the light emitting layer is formed by vapor deposition, it may be co-deposited with a light emitting dopant, and the light emitting dopant is a metal complex such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ). , A naphthacene derivative such as rubrene, a quinacridone derivative, a condensed polycyclic aromatic ring such as perylene, and the like, but are not limited thereto.

Examples of the material for forming the electron transport layer / whole block layer include, but are not limited to, an oxydiazole derivative, a triazole derivative, a phenanthroline derivative, a phenylquinoxaline derivative, a benzimidazole derivative, and a pyrimidine derivative.

Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li ₂ O), magnesium oxide (Mg O), and alumina (Al ₂ O ₃ ), lithium fluoride (LiF), and sodium fluoride (NaF). Examples include, but are not limited to, metal fluorides such as.
Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
Examples of the material for forming the electron block layer include, but are not limited to, tris (phenylpyrazole) iridium and the like.

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] -endcapped with polysilsis quinoxane, poly [(9,9-) Didioctylfluorenyl-2,7-diyl) -co- (4,4'-(N- (p-butylphenyl)) diphenylamine)] and the like can be mentioned.

Examples of the luminescent polymer include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), and poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene) (MEH-). Examples thereof include polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

The charge-transporting thin film obtained from the charge-transporting varnish of the present invention serves as a functional layer 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 the organic EL element. Although it can be used, other organic photoelectric conversion elements, organic thin film solar cells, organic perovskite photoelectric conversion elements, organic integrated circuits, organic field effect transistors, organic thin films, organic light emitting transistors, organic optical testers, organic photoreceivers, organic It can also be used as a charge transporting thin film in electronic devices such as electric field extinguishing devices, light emitting electronic chemical batteries, quantum dot light emitting diodes, quantum lasers, organic laser diodes and organic Plasmon light emitting devices.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The equipment and reagents used are as follows.
[apparatus]
(1) MALDI-TOF-MS: manufactured by Bruker, autoflex III smart beam
(2) ^{1 1} H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.
(3) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Sangyo Co., Ltd. (decompression plasma method)
(4) Application of varnish: Spin coater MS-A100 manufactured by Mikasa Co., Ltd.
(5) Film thickness measurement: Kosaka Laboratory Co., Ltd. Fine shape measuring machine Surfcoder ET-4000
(6) Manufacture of element: Multi-function vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
(7) Measurement of element current density and brightness: Multi-channel IVL measuring device manufactured by EHC Co., Ltd. (8) Life measurement of EL element (brightness half-life measurement): Organic EL brightness life manufactured by EHC Co., Ltd. Evaluation system PEL-105S
(9) Measurement of refractive index (n) and extinction coefficient (k): Multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woolam Japan

[reagent]
RuPhos Aldrich t-BuXPhos Aldrich t-Bu ₃ PHBF ₄ Fujifilm Wako Chemical Co., Ltd. Copper Iodide (I) Fujifilm Wako Chemical Co., Ltd. Toluene Diamine Fujifilm Wako Chemical Co., Ltd. Pd (DBA) ) ₂ Pd (ОAc) manufactured by Tokyo Kasei Kogyo Co., Ltd. ₂ Pd [P (C ₆ H ₅ ) ₃ )] manufactured by Tokyo Kasei Kogyo Co., Ltd. ₄ Pd (dppf) Cl ₂ manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Bromo-9-Phenylcarbazole manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Bromocarbazole manufactured by Tokyo Kasei Kogyo Co., Ltd. 4-Iodotoluene manufactured by Tokyo Kasei Kogyo Co., Ltd. 4-iodoanisol Tokyo Kasei Kogyo Co., Ltd. ) 18-Crown-6 Tokyo Kasei Kogyo Co., Ltd. Bis (Pinacolat) Diboron Tokyo Kasei Kogyo Co., Ltd. 3,3', 5,5'-Tetramethylbenzidine Tokyo Kasei Kogyo Co., Ltd. Lithium Hexamethyldi Shirajide (LHMDS) 1.3 mol / L tetrahydrofuran solution 2-Bromo-7-iodofluorene manufactured by Tokyo Kasei Kogyo Co., Ltd. benzyltriethylammonium chloride manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Nitroaniline manufactured by Tokyo Kasei Kogyo Co., Ltd. Tokyo 1-Bromo-3-nitrobenzene manufactured by Kasei Kogyo Co., Ltd. Hydrogen chloride (approx. 1 mL / L ethyl acetate solution) manufactured by Tokyo Kasei Kogyo Co., Ltd. 4,4'-diaminodiphenylamine manufactured by Tokyo Kasei Kogyo Co., Ltd. Tokyo Kasei Kogyo Co., Ltd. ) T-BuONa Tokyo Kasei Kogyo Co., Ltd. (9-Phenyl-9H-carbazole-3-yl) boronic acid Tokyo Kasei Kogyo Co., Ltd. 1,4-dioxane Kanto Chemical Co., Ltd. 2,2'- Bis (Trifluoromethyl) benzidine Kanto Chemical Co., Ltd. Bis (4-aminophenyl) Sulfone Kanto Chemical Co., Ltd. 1,4-Bis (4-amino-2-trifluoromethylphenoxy) benzene Kanto Chemical Co., Ltd. Silica Silica N60 dimethylsulfoxide manufactured by Kanto Chemical Co., Ltd. Iodomethane manufactured by Genuine Chemical Co., Ltd. Potassium carbonate manufactured by Genuine Chemical Co., Ltd. Potassium acetate manufactured by Genuine Chemical Co., Ltd. Toluene manufactured by Tokyo Kasei Kogyo Co., Ltd. Ethyl acetate manufactured by Chemical Co., Ltd. Methanol manufactured by Genuine Chemical Co., Ltd. Hexene manufactured by Genuine Chemical Co., Ltd. m-trizine manufactured by Genuine Chemical Co., Ltd. N, N'-bis (4-aminophenyl) terephthalamide manufactured by Wakayama Seika Kogyo Co., Ltd. Wakayama Seika Kogyo Co., Ltd. Pd / C CGS-10DR [H2O] = 54. 40% N. E. Chemcat 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole Beijing aglaia technology development co., Ltd

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

Weigh 30 mmol (11.1 g) of 2-bromo-7-iodofluorene and 3 mmol (683.3 mg) of benzyltriethylammonium chloride into a 100 mL reaction flask, add 60 mL of dimethyl sulfoxide, and stir for 10 minutes while substituting with nitrogen. did.
After adding 14 g of a separately prepared 50 mass% sodium hydroxide aqueous solution and stirring for 10 minutes, 72.5 mmol (10.3 g) of iodomethane was added dropwise thereto, and the mixture was stirred overnight at room temperature. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous 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 by 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 H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.

[Manufacturing Example 1-2]

In a 200 mL two-necked flask, 20 mmоl (4.93 g) of 3-bromocarbazole, 44 mmоl (9.61 g) of 4-iodotoluene, 16 mmоl (3.05 g) of copper (I) iodide, and 50 mmоl (16.3 g) of cesium carbonate. ), 100 mL of toluene was added, and the mixture was stirred at room temperature for 5 minutes under a nitrogen stream, 30 mmоl (1.82 g) of ethylenediamine was added thereto, and the mixture was stirred overnight under heating and reflux.
After cooling the resulting reaction mixture to room temperature, the insoluble material is removed by filtration through Celite, the obtained filtrate is concentrated, and the concentrate is purified by column chromatography to purify 3-bromo-9- (4-tolyl) carbazole. 2.84 g (42.2%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 2 to 4.

[Manufacturing Example 1-3]

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 equivalents used for other reagents were doubled. , 3-Bromo-9- (4-methoxyphenyl) carbazole 11.1 g (78.7%) was obtained. The ¹ H-NMR spectra of the obtained compound are shown in FIGS. 5 and 6.

[Manufacturing Example 1-4]

In a 200 mL two-necked flask, 3-bromocarbazole 60 mmоl (14.76 g), copper (I) iodide 4.5 mmоl (0.86 g), potassium carbonate 63 mmоl (8.71 g), 18-crown-6 61. After adding 5 mmоl (16.2 g) and replacing 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 the mixture was stirred for 2 hours, 63 mmоl (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 material is removed by Celite filtration, the obtained filtrate is concentrated, and the concentrate is column chromatographed (developing solvent: n-hexane / ethyl acetate = 100/0 → 95/5). To obtain 5.80 g (29.5%) of 3-bromo-9- (thiophene-2-yl) carbazole. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 7 and 8.

[Manufacturing Example 1-5]

The reaction and purification were carried out in the same manner as in Production Example 1-4 except that 60 mmоl (14.76 g) of 2-bromocarbazole was used instead of 3-bromocarbazole, and 2-bromo-9- (thiophene-2-) was used. Il) Carbazole 7.36 g (37.2%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 9 and 10.

[Manufacturing Example 1-6]

In a 100 mL reaction flask, 5-bromo-9- (p-tolyl) carbazole 5 mmоl (1.68 g), bis (pinacolat) diboron 5.05 mmоl (1.28 g), potassium acetate 15 mmоl (1.47 g), Pd ( dppf) Cl ₂ 0.15 mmоl (0.125 g) and 50 mL of N, N-dimethylformamide were added, nitrogen was replaced with stirring at room temperature for 10 minutes, the temperature was raised to 90 ° C., and the mixture was further stirred overnight.
The reaction mixture, 75 mL of water, and 75 mL of methylene chloride were mixed and extracted, 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 pinacolate. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 11 and 12.

[Manufacturing Example 1-7]

Except for using 3-bromo-9- (p-methoxyphenyl) carbazole 10 mmоl (3.522 g) instead of 3-bromo-9- (p-tolyl) carbazole 5 mmоl and doubling the amount of other reagents used. Was reacted and purified in the same manner as in Production Example 1-6 to obtain 1.53 g (38.3%) of 9- (p-methoxyphenyl) carbazole-3-boronic acid pinacolalate. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 13 and 14.

[Manufacturing Example 1-8]

3-Bromo-9- (thiophene-2-yl) carbazole 15 mmоl (4.92 g) was used in place of 3-bromo-9- (p-tolyl) carbazole 5 mmоl, and the equivalents of other reagents used were tripled. The reaction and purification were carried out in the same manner as in Production Example 1-6 except that 2.53 g (44.9%) of 9- (thiophene-2-yl) carbazole-3-boronic acid pinacolate was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 15 and 16.

[Manufacturing Example 1-9]

The same method as in Production Example 1-6 except that 5 mmol (1.64 g) of 2-bromo-9- (thiophene-2-yl) carbazole was used instead of 3-bromo-9- (p-tolyl) carbazole. The reaction and purification were carried out in 1.26 g (67.2%) of 9- (thiophene-2-yl) carbazole-2-boronic acid pinacolate. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 17 and 18.

[Manufacturing Example 2-1]

In a 100 mL reaction flask, 5 mmol (1.44 g) of (9-phenyl-9H-carbazole-3-yl) boronic acid, 5.25 mmol (2) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene. .95 g), 15 mmol (600 mg) of sodium hydroxide, 75 mL of mixed solvent of tetrahydrofuran and water (2/1 (v / v)) and Pd [P (C ₆ H ₅ ) ₃ )] ₄ 0.15 mmol (173.5 mg) ) Was added, and the mixture was stirred at room temperature for 10 minutes while substituting with nitrogen, and then stirred at 60 ° C. for 5 hours. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The obtained reaction mixture was added to 400 mL of a mixed solvent of methanol and water (3/1 (v / v)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
Further, 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 by a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
Finally, the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of a mixed solvent of methanol and water (3/1 (v / v)), and the precipitated solid was filtered off by a membrane filter. The obtained solid was dried under reduced pressure at 60 ° C. to 1.28 g (49.8%) of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole. Got The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Manufacturing Example 2-2]

In a 100 mL reaction flask, 2.5 mmоl (0.958 g) of 9- (p-tolyl) carbazole-3-boronic acid pinacolaate, 2.63 mmоl of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene ( 1.05 g), 7.5 mmol (300 mg) of sodium hydroxide, 37.5 mL of mixed solvent of tetrahydrofuran and water (2/1 (v / v)) and Pd [P (C ₆ H ₅ ) ₃ )] ₄₀ . 075 mmol (86.7 mg) was added, and the mixture was stirred at room temperature for 10 minutes while substituting with nitrogen, and then stirred 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)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
Further, 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 by a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C. 3- (7-Bromo-9,9-dimethyl-9H-fluorene-2-yl) -9- (p-tolyl) -9H-carbazole 1.10 g (83.3%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 20 and 21.

[Manufacturing Example 2-3]

Instead of 9- (p-tolyl) carbazole-3-boronic acid pinacolalate, use 15 mmol (5.99 g) of 9- (p-methoxyphenyl) carbazole-3-boronic acid pinacolaate, and use 6 equivalents of other reagents. The reaction and purification were carried out in the same manner as in Production Example 2-2 except for doubling, and 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9- (p-methoxy) was carried out. To obtain 5.80 g (70.4%) of phenyl) -9H-carbazole. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Manufacturing Example 2-4]

Instead of 9- (p-tolyl) carbazole-3-boronic acid pinacolalate, use 9- (thiophene-2-yl) carbazole-3-boronic acid pinacolate 5 mmоl (1.79 g), and use equivalent amounts of other reagents. The reaction and purification were carried out in the same manner as in Production Example 2-2 except that the amount was doubled, and 3- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -9- (thiophene-). 2-Il) -9H-carbazole 1.86 g (76.8%) was obtained. The ¹ H-NMR spectrum of the obtained compound is shown in FIGS. 23 and 24 (measurement solvent: heavy THF).

[Manufacturing Example 2-5]

Instead of 9- (p-tolyl) carbazole-3-boronic acid pinacolaate, use 9- (thiophene-2-yl) carbazole-2-boronic acid pinacolate 5 mmоl (1.88 g), and use equivalent amounts of other reagents. The reaction and purification were carried out in the same manner as in Production Example 2-2 except that the amount was doubled, and 2- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -9- (thiophene-) was carried out. 2-Il) -9H-carbazole 2.0 g (77.7%) was obtained. The ¹ H-NMR spectrum of the obtained compound is shown in FIGS. 25 and 26 (measurement solvent: heavy THF).

[Manufacturing Example 3]

Reaction flask 1000mL fitted with a reflux _{column, Pd (DBA) 2 5mmol (} 2.88g), t-BuXPhos10mmol (4.25g), potassium carbonate 300mmol (41.46g), 3- nitroaniline 100 mmol (13.82 g ), 110 mmol (22.22 g) of 1-bromo-3-nitrobenzene and 1000 mL of toluene were added to replace the inside of the flask with nitrogen, and then the mixture was stirred overnight in a bath at 80 ° C. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The reaction mixture was cooled to room temperature, filtered through a filter filled with 200 g of silica gel N60, the obtained filtrate was concentrated to a weight of 100 g, the concentrate was added dropwise to 1000 mL of toluene, and the resulting solid was filtered off. .. The obtained solid was dried to obtain 24.1 g of bis (3-nitrophenyl) amine (yield 93.1%).

[Manufacturing Example 4]

In a 300 mL reaction flask equipped with a reflux column, weigh 77.15 mmоl (20 g) of bis (3-nitrophenyl) amine and Pd / C CGS-10DR [H2O] = 54.40% 2 g, and replace the inside of the flask with hydrogen. did. After adding 200 mL of tetrahydrofuran to it, the mixture was stirred at 50 ° C. overnight. The mixture was cooled to room temperature, filtered through a filter filled with 200 g of Celite, and the solvent was distilled off from the filtrate under reduced pressure. After collecting a small amount of the residue and confirming the formation of 3,3'-diaminodiphenylamine by ¹ H-NMR, 100 g of tetrahydrofuran was added to the residue, and the obtained solution was cooled to 0 ° C. in an ice bath and heated to a temperature. After confirming that was stable, 50 mL of a hydrogen chloride solution (about 1 mL / 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 salt.

[Example 1-1]

Pd (DBA) ₂ 0.1 mmol (57.6 mg), RuPhos 0.15 mmol (70.0 mg), 3,3', 5,5'-tetramethylbenzidine 0.5 mmol in a 30 mL reaction flask equipped with a reflux column. Weigh in (120.2 mg), 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 2.1 mmol (1080.4 mg), and pour through the system. Nitrogen substituted.
10 mL of dioxane is added thereto, and the mixture is stirred at room temperature for 5 minutes, then 1.69 mL of LHMDS 1.3 mol / L tetrahydrofuran solution (equivalent to 2.2 mmol of LHMDS) is added, and the mixture is stirred at room temperature for 5 minutes and then in a bath at 110 ° C. for 8 hours. The mixture was heated and stirred (internal temperature 92 ° C.). On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture is placed in a separatory funnel together with 50 mL of a saturated aqueous solution of ammonium chloride 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 liquid funnel, and the aqueous layer was recovered. 50 mL of saturated saline was placed in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered, respectively. Then, all the recovered aqueous layers are put together in a separating funnel, 20 mL of ethyl acetate is put therein and extraction is performed, the organic layer is recovered, all the recovered organic layers are put together, and this is dried with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate by a rotary evaporator. Column chromatography (developing solvent: n-hexane / methylene chloride = 60/40 → 0/100) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the desired product was separated. I took it.
Finally, the solvent was removed from the fraction, and the mixture was dried under reduced pressure at 70 ° C. to obtain 0.56 g (> 99%) of the arylamine compound C2d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 27.

[Example 1-2]

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. The operation was carried out in the same manner to obtain 0.43 g (70.9%) of the arylamine compound D2d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-3]

Same 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. The procedure was carried out to obtain 0.46 g (44.8%) of arylamine compound A3d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-4]

The procedure was the same 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. This was carried out to obtain 0.35 g (35.3%) of the arylamine compound E3d. The ¹ H-NMR spectrum (measurement solvent: CDCl ₃ ) of the obtained compound is shown in FIG.

[Example 1-5]

3- (7-Bromo-9,9-dihexyl-9H-fluorene-2) instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole -Il) -9-Phenyl-9H-carbazole 2.1 mmol (1.375 mg) was used, but the procedure was the same as in Example 1-4, and 0.71 g (55.8) of the arylamine compound E3i was used. %) Was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-6]

Examples 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. The same procedure as in 1-1 was carried out to obtain 0.35 g (32.4%) of arylamine compound F3d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-7]

3- (4-Bromophenyl) -9-phenyl-9H-carbazole instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 2. The procedure was the same as in Example 1-3 except that 1 mmol (836.4 mg) was used to obtain 0.32 g (40.3%) of the arylamine compound A3b. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 33.

[Example 1-8]

3- (4'-Bromo- [1,1'-biphenyl] -4 instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole -Il) -9-Phenyl-9H-carbazole 2.1 mmol (996.2 mg) was used, but the procedure was the same as in Example 1-3, and the arylamine compound A3c was 0.57 g (60.2 mg). %) Was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-9]

The arylamine compound was operated in the same manner as in Example 1-1 except that 0.5 mmol (106.1 mg) of m-trizine was used instead of 3,3', 5,5'-tetramethylbenzidine. 0.17 g (17.5%) of G3d was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-10]

Reaction flask fitted with a reflux column _{200mL, Pd (ОAc) 2 2mmol} (0.45g), t-Bu 3 PHBF 4 4mmol (1.16g), t-BuONa40mmol (3.84g), 4,4'- Weigh 4 mmol (797.0 mg) of diaminodiphenylamine and 20.6 mmol (10.61 g) of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole. The inside of the flask was replaced with nitrogen. Toluene (50 mL) was added thereto, and the mixture was stirred overnight in a bath at 110 ° C. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous 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 the obtained concentrate was diluted with 10 mL of toluene and column chromatography was performed using the obtained solution (developing solvent: n-hexane / methylene chloride = 70/30 (v / v) → 55/45 (v / v)), collect the fractions of interest, concentrate the collected fractions, dilute the resulting concentrate with 10 mL of toluene and use the resulting solution for column chromatography again under the same conditions. And collected the fractions of the target object. The collected fractions are concentrated, the concentrate is dissolved in 30 mL of tetrahydrofuran, the obtained solution is added dropwise to a mixed solvent of ethyl acetate and methanol (1/1 (v / v)), and the precipitated solid is recovered by a membrane filter. did. The obtained solid was dried to obtain 2.67 g (28.2%) of the arylamine compound H3d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-11]

Reaction flask fitted with a reflux column _{30mL, Pd (ОAc) 2 2.5mmol} (0.56g), t-Bu 3 PHBF 4 5mmol (1.45g), t-BuONa25mmol (2.40g), 3,3 '-Diaminodiphenylamine dihydrochloride 2.5 mmol (80.4 mg), 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 12.6 mmol (6) .49 g) was weighed and the inside of the flask was replaced with nitrogen. Toluene (50 mL) was added thereto, and the mixture was stirred overnight in a bath at 110 ° C. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous 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 the obtained concentrate was diluted with 5 mL of toluene and column chromatography was performed using the obtained solution (developing solvent: n-hexane / methylene chloride = 70/30 (v / v) → 55/45 (v / v)), collect the fractions of interest, concentrate the collected fractions, dilute the resulting concentrate with 5 mL of toluene and use the resulting solution for column chromatography again under the same conditions. And collected the fractions of the target object. The collected fractions are concentrated, the concentrate is dissolved in 30 mL of tetrahydrofuran, the obtained solution is added dropwise to a mixed solvent of ethyl acetate and methanol (1/1 (v / v)), and the precipitated solid is recovered by a membrane filter. did. The obtained solid was dried to obtain 2.34 g (39.5%) of arylamine compound I3d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 37.

[Example 1-12]

In a 50 mL flask, 0.4 mmоl (108.9 mg) of 3,3'-diaminodiphenylamine dihydrochloride, 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9- (p) -Trill) -9H-carbazole 2.02 mmоl (1067.5 mg), Pd (ОAc) ₂ 0.4 mmоl (89.8 mg), t-Bu ₃ PHBF ₄ 0.8 mmоl (232.1 mg), t-BuONa ₄ mmоl (384) After adding (0.4 mg) and replacing with nitrogen, 8 mL of toluene was added, and the mixture was stirred for 10 minutes, and then stirred overnight under heating and 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. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 38 and 39.

[Example 1-13]

2- (7-bromo-9,9-dimethyl-9H) instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9- (p-tolyl) -9H-carbazole -Fluorene-2-yl) -9- (thiophene-2-yl) -9H-carbazole 2.02 mmоl (1051.4 mg) was used, but the same procedure as in Example 1-12 was carried out to create an aryl. Amine compound I3h 157.0 mg (16.4%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 40 and 41.

[Example 1-14]

3- (7-Bromo-9,9-dimethyl-9H-fluorene-2) instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole -Il) -9- (p-tolyl) -9H-carbazole 2.1 mmol (1109.8 mg) was used, but the procedure was the same as in Example 1-3, and the arylamine compound A3e 323.8 mg. (38.3%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-15]

3- (7-Bromo-9,9-dimethyl-9H-fluorene-2) instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole -Il) -9- (p-methoxyphenyl) -9H-carbazole 2.1 mmol (1143.4 mg) was used, and the same procedure as in Example 1-3 was carried out to carry out the same procedure as in Example 1-3 to carry out the same procedure as for the arylamine compound A3f 552. 6 mg (50.8%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 43.

[Example 1-16]

3- (7-Bromo-9,9-dimethyl-9H-fluorene-2) instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole -Il) -9- (thiophene-2-yl) -9H-carbazole 2.1 mmol (1093.0 mg) was used. 9.9 mg (48.1%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-17]

2- (7-Bromo-9,9-dimethyl-9H-fluorene-2) instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole The arylamine compound A3h 664 was operated in the same manner as in Example 1-3 except that 2.1 mmol (1093.0 mg) of -9H-carbazole was used. 9.9 mg (64.0%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 45 and 46.

[Example 1-18]

Octafluorobiphenyl-4,4'-diamine 0.5 mmоl (164 mg), 3- (4-bromophenyl) -9-phenylcarbazole 2.1 mmol (836 mg), Pd (ОAc) _{20 in a} 50 mL reaction flask. After adding 2 mmоl (45 mg), t-Bu ₃ PHBF ₄ 0.4 mmоl (166 mg) and t-BuONa ₄ mmоl (385 mg) for nitrogen substitution, add 10 mL of toluene, stir at room temperature for 5 minutes, and then stir at 100 ° C. for 6 hours. Stirred.
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. 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)), and the arylamine compound B3b 311.8 mg. (44.6%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 47.

[Example 1-19]

3- (4'-Bromo- [1,1'-biphenyl] -4-yl) -9-phenyl-9H-carbazole 2.1 mmol (996) instead of 3- (4-bromophenyl) -9-phenylcarbazole The procedure was the same as in Example 1-18 except that .2 mg) was used to obtain 391 mg (41.1%) of arylamine compound B3c. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-20]

Instead of 3- (4-bromophenyl) -9-phenylcarbazole, 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 2.1 mmol (1080) The procedure was the same as in Example 1-18 except that 0.4 mg) was used to obtain 535 mg (51.9%) of arylamine compound B3d. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-21]

Octafluorobiphenyl-4,4'-diamine 0.5 mmоl (164 mg), 3- (4-bromophenyl) -9-phenylcarbazole 2.1 mmol (836 mg), Pd (DBA) _{20 in a} 50 mL reaction flask. After adding 1 mmоl (57.5 mg), t-Bu ₃ PHBF ₄ 0.2 mmоl (84 mg) and t-BuONa 2 mmоl (193 mg) for nitrogen substitution, add 10 mL of toluene, stir at room temperature for 5 minutes, and then at 100 ° C. The mixture was stirred 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. 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)), and the arylamine compound B2b 419.0 mg. (87.0%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.

[Example 1-22]

3- (4'-Bromo- [1,1'-biphenyl] -4-yl) -9-phenyl-9H-carbazole 2.1 mmol (996) instead of 3- (4-bromophenyl) -9-phenylcarbazole The procedure was the same as in Example 1-21 except that .2 mg) was used to obtain 72.9 mg (13.1%) of arylamine compound B2c. The ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.

[Example 1-23]

Instead of 3- (4-bromophenyl) -9-phenylcarbazole, 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 2.1 mmol (1080) The operation was carried out in the same manner as in Example 1-21 except that 0.4 mg) was used to obtain 114.0 mg (19.1%) of the arylamine compound B2d. The ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.

[Comparative Example 1-1]

Instead of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole, use 2.1 mmol (676.6 mg) of 3-bromo-N-phenylcarbazole. Arylamine compound A3a 0.45 g (70.0%) was obtained by the same procedure as in Example 1-3 except that it was used. The ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG. 53.

[Comparative Example 1-2]

The procedure was the same as in Example 1-18, except that 2.1 mmol (677 mg) of 3-bromo-N-phenylcarbazole was used instead of 3- (4-bromophenyl) -9-phenylcarbazole. Arylamine compound B3a 236.2 mg (36.6%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 54.

[Comparative Example 1-3]

The procedure was the same 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. Arylamine compound B2a 272.3 mg (67.2%) was obtained. The ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG. 55.

[2] Preparation of varnish for hole injection layer [Comparative Example 2-1]
A solution obtained by adding an arylamine compound A3a (0.025 g) and an aryl sulfonic acid ester A (0.025 g) represented by the following formula to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared. A charge-transporting varnish A3a-1 was obtained by filtering with a syringe filter having a pore size of 0.2 μm.

[Example 2-1]
A solution obtained by adding arylamine compound A3b (0.028 g) and aryl sulfonic acid ester A (0.022 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared having a pore size of 0.2 μm. The mixture was filtered through a syringe filter to obtain a charge-transporting varnish A3b-1.

[Example 2-2]
The solution obtained by adding arylamine compound A3c (0.030 g) and aryl sulfonic acid ester A (0.020 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3c-1.

[Example 2-3]
The solution obtained by adding arylamine compound A3d (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3d-1.

[Example 2-4]
The solution obtained by adding arylamine compound A3e (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3e-1.

[Example 2-5]
The solution obtained by adding arylamine compound A3f (0.032 g) and aryl sulfonic acid ester A (0.018 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. The mixture was filtered through a filter to obtain a charge-transporting varnish A3f-1.

[Example 2-6]
The solution obtained by adding 3 g (0.031 g) of the arylamine compound A (0.031 g) and the aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3g-1.

[Example 2-7]
The solution obtained by adding arylamine compound A3h (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. The mixture was filtered through a filter to obtain a charge-transporting varnish A3h-1.

[Comparative Example 2-2]
The solution obtained by adding arylamine compound B3a (0.026 g) and aryl sulfonic acid ester A (0.024 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3a-1.

[Example 2-8]
The solution obtained by adding arylamine compound B3b (0.029 g) and aryl sulfonic acid ester A (0.021 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3b-1.

[Example 2-9]
The solution obtained by adding arylamine compound B3c (0.030 g) and aryl sulfonic acid ester A (0.020 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3c-1.

[Example 2-10]
The solution obtained by adding arylamine compound B3d (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3d-1.

[Comparative Example 2-3]
The solution obtained by adding arylamine compound B2a (0.020 g) and aryl sulfonic acid ester A (0.030 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2a-1.

[Example 2-11]
The solution obtained by adding arylamine compound B2b (0.022 g) and aryl sulfonic acid ester A (0.028 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2b-1.

[Example 2-12]
The solution obtained by adding arylamine compound B2c (0.024 g) and aryl sulfonic acid ester A (0.026 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2c-1.

[Example 2-13]
The solution obtained by adding arylamine compound B2d (0.025 g) and aryl sulfonic acid ester A (0.025 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2d-1.

[Example 2-14]
The solution obtained by adding arylamine compound H3d (0.033 g) and aryl sulfonic acid ester A (0.017 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish H3d-1.

[Example 2-15]
The solution obtained by adding arylamine compound I3d (0.033 g) and aryl sulfonic acid ester A (0.017 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish I3d-1.

[3] Preparation of varnish for hole transport layer [Comparative Example 3-1]
The solution obtained by adding arylamine compound A3a (0.040 g) to chloroform (10 g) and stirring at room temperature to dissolve it is filtered through a syringe filter having a pore size of 0.2 μm to carry charge-transporting varnish A3a-2. Got

[Examples 3-1 to 3-11]
In the same manner as in Comparative Example 3-1 except that the arylamine compounds A3b, A3c, A3d, A3e, A3f, A3g, A3h, B3d, B2d, H3d, or I3d were used instead of the arylamine compound A3a. Obtains 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. It was.

[4] Production of thin film and evaluation of film physical properties [Comparative Example 4-1 and Examples 4-1 to 4-3]
The 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 atmospheric firing. Next, the dried quartz substrate was calcined at 200 ° C. for 15 minutes in an air atmosphere to form a uniform thin film of 50 nm on the quartz substrate.
Using the obtained quartz substrate with a film, the visible region average refractive index (n) and the visible region average extinction coefficient (k) at a wavelength of 400 to 800 nm were measured. The results are shown in Table 23.

As shown in Table 23, the thin film obtained from the charge-transporting varnish of the present invention has the same or higher refractive index than the thin film obtained from the charge-transporting varnish of Comparative Example 4-1 and is equivalent. Or it can be seen that it has a low extinction coefficient.

[5] Fabrication and characterization of hole-only devices (HOD) [Comparative Example 5-1]
As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and before use, an O ₂ plasma cleaning device (150 W, 30 seconds) is used. Impurities on the surface were removed. Subsequently, the composition for forming a hole injection layer obtained by the method described later is 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. , A hole injection layer (film thickness: 30 nm) was formed.
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). Formed.
A hole-only element (HOD) was obtained by forming an aluminum thin film of 80 nm at 0.2 nm / sec using a vapor deposition apparatus (vacuum degree 1.0 × 10 ^-5 Pa).
The composition for forming a hole injection layer was prepared by the following procedure. 0.137 g of the aniline derivative represented by the formula (3) synthesized according to the method described in WO2013 / 084664 and the aryl represented by the formula (4) synthesized according to the method described in WO 2006/025432. 0.271 g of sulfonic acid was 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).

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

The current density at a drive voltage of 4 V was measured for each HOD produced in the above Examples and Comparative Examples. The results are shown in Table 24.

As shown in Table 24, it can be seen that the thin film prepared from the charge transporting varnish of the present invention exhibits better charge transporting property than the thin film prepared from the charge transporting varnish of the comparative example. This improvement in charge transportability is considered to be associated with an increase in the effective conjugation length of the conductive site in the arylamine compound of the present invention.

[6] Fabrication of single-layer device (SLD) and HOD and evaluation of relative strength of HOD current density with respect to SLD current density [Comparative Example 6-1]
As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and before use, an O ₂ plasma cleaning device (150 W, 30 seconds) is used. Impurities on the surface were removed.
Charge-transporting varnish A3a-1 is applied onto an ITO substrate by spin coating, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes, and a hole injection layer (film thickness:: 50 nm) was formed.
On this, an aluminum thin film of 80 nm was formed at 0.2 nm / sec using a vapor deposition apparatus (vacuum degree 1.0 × 10 ^-5 Pa) to obtain a single-layer device (SLD).

[Examples 6-1 to 6-12, Comparative Example 6-2]
Instead of the charge-transporting varnish A3a-1, the charge-transporting varnish 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, but SLD was prepared in the same manner as in Comparative Example 6-1.

[Comparative Example 7-1]
The charge-transporting varnish A3a-1 is applied to an ITO substrate using a spin coater, dried in the 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. Formed. As the ITO substrate, the same ITO substrate as in Comparative Example 6-1 was used.
A thin film of α-NPD and aluminum was sequentially laminated on it using a thin film deposition apparatus (vacuum degree 2.0 × 10 ^-5 Pa) to obtain HOD. The vapor deposition was carried out under the condition of a vapor deposition rate of 0.2 nm / sec. The film thicknesses of the α-NPD and aluminum thin films were 30 nm and 80 nm, respectively.

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

Voltages of SLDs prepared in Examples 6-1 to 6-12 and Comparative Examples 6-1 to 6-2, and HODs prepared in Examples 7-1 to 7-12 and Comparative Examples 7-1 to 7-2. The current density when driven at 4 V was measured. The results are shown in Table 25. In addition, the relative intensity of the HOD current density with respect to the SLD current density calculated using these measured values is also shown. The high relative strength indicates that the hole supply to the hole transport layer is efficiently realized.

As shown in Table 25, the device using the hole injection layer made from the charge-transporting varnish of the present invention has a higher relative strength of the HOD current density with respect to the SLD current density than the device made in the comparative example. I understand.

[7] Fabrication and characterization of organic EL devices [Comparative Example 8-1]
The charge-transporting varnish A3a-1 is applied to an ITO substrate using a spin coater, dried in the 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. Formed. As the ITO substrate, the same ITO substrate as in Comparative Example 6-1 was used.
Next, on the ITO substrate on which the thin film was formed, α-NPD was deposited at 0.2 nm / sec at 30 nm using a thin film deposition apparatus (vacuum degree 1.0 × 10 ^-5 Pa). Next, a 10 nm film was formed on the electronic block material HTEB-01 manufactured by Kanto Chemical Co., Inc. Next, the light emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and the light emitting layer dopant material Ir (ppy) ₃ were co-deposited. For co-evaporation, the vapor deposition rate was controlled so that the concentration of Ir (ppy) ₃ was 6%, and 40 nm was laminated. Next, thin films of Alq ₃ , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL device. At this time, the vapor deposition rate was 0.2 nm / sec for Alq ₃ and aluminum, and 0.02 nm / sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
In order to prevent the deterioration of the characteristics due to the influence of oxygen, water, etc. in the air, the organic EL element was sealed with a sealing substrate and then the characteristics were evaluated. Sealing was performed by 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, an organic EL element is placed between the sealing substrates, and the sealing substrate is an adhesive (Matsumura Oil Research Corp., Moresco Moisture Cut WB90US (P)). It was pasted together. At this time, a water catching agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed in the sealing substrate together with the organic EL element. The bonded substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm ² ) and then annealed at 80 ° C. for 1 hour to cure the adhesive.

[Examples 8-1 to 8-12]
Instead of the charge-transporting varnish A3a-1, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-, respectively. An organic EL device was produced in the same manner as in Comparative Example 8-1 except that 1, B2d-1, H3d-1, or I3d-1 was used.

Drive voltage, current density, current efficiency, luminous efficiency, external emission quantum yield (EQE) and LT90 (initial brightness 5,000 cd / m) when the obtained organic EL element is made to emit light at a brightness of 5,000 cd / m ^2. ^The time required for a 10% reduction in ² ) was measured. The results are shown in Table 26.

As shown in Table 26, as compared with the organic EL element of Comparative Example 8-1, all the organic EL elements of the present invention show the same or less drive voltage and have the same or more half-life. Had had.

Claims

Arylamine compounds represented by any of the following formulas (1) to (6) (however, compounds represented by the following formulas (P1) to (P4) are excluded).

Wherein, Ar c each independently represent a group represented by the formula (Q),
X represents an arylene group which may be independently substituted and may contain a heteroatom.
Y represents a phenylene group which may be substituted independently of each other.
g represents an integer of 1 to 10 independently of each other.

(In the formula, R 1 is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. alkoxy group or an aryl group having a carbon number of 6 ~ 20, R 2, each independently, together with optionally substituted, represents an aryl group which may contain a hetero atom, Ar s is Represents an arylene group that may be substituted independently and may contain a heteroatom.)]
Wherein Ar s is an arylamine compound of claim 1, wherein represented by any one of the following formulas (101) to (118).

(In the formula, R 3 is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents an alkoxy group or an aryl group having 6 to 20 carbon atoms, where V 1 is an independent C (R 4 ) 2 (R 4 is an independent hydrogen atom and has 1 to 20 carbon atoms. It represents an alkyl group or an alkyl halide 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 SO 2 , V 2 stands for NR 5 (R 5 stands for the same meaning as above), S or O)
Wherein Ar s is represented by the following formula (101A) ~ arylamine compound of claim 1, wherein represented by any one of (118A).

(In the equation, R 3 , V 1 and V 2 have the same meanings as described above.)
Wherein Ar s is represented by the following formula (101A-1) ~ (118A -3) arylamine compound of claim 3, wherein represented by any one of the.

(In the formula, R 4 and R 5 have the same meanings as described above.)
The arylamine compound according to any one of claims 1 to 4, wherein X is represented by any of the following formulas (201) to (207).

(In the formula, R 6 is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents an alkoxy group or an aryl group having 6 to 20 carbon atoms, W 1 is an independent single bond, and C (R 7 ) 2 (R 7 is an independent hydrogen atom and 1 carbon atom. Represents an alkyl group of ~ 20 or an alkyl halide group having 1 to 20 carbon atoms), S, O, or SO 2 , where W 2 is C (R 7 ) 2 (R 7 is independent of each other). (Same as above), NR 8 (R 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or SO 2. W 3 stands for NR 8 (R 8 stands for the same meaning as above), S or O.)
The arylamine compound according to claim 5, wherein X is represented by any of the following formulas (201A) to (207A).

(In the formula, R 6 , W 1 , W 2 and W 3 have the same meanings as described above.)
The arylamine compound according to claim 6, wherein X is represented by any of the following formulas (201A-1) to (207A-1).

(In the formula, R 7 , R 8 and W 3 have the same meanings as described above.)
Wherein Ar c is an arylamine compound as claimed in any one of claims 1 to 7 of the same group.
A charge-transporting varnish containing the arylamine compound according to any one of claims 1 to 8 and an organic solvent.
The charge transporting varnish according to claim 9, which contains a dopant substance.
A charge-transporting thin film produced by using the charge-transporting varnish of claim 9 or 10.
An electronic device including the charge transporting thin film according to claim 11.