JPWO2020027259A1 - Charge transport varnish - Google Patents

Abstract

For example, a charge-transporting varnish containing an aniline derivative having a repeating unit of metaphenylene in a molecule and an organic solvent as represented by the following formula has good charge-transporting property by low-temperature firing and is a thin film having a high refractive index. To provide an organic EL element having excellent characteristics when this thin film is applied to a hole injection layer or the like.

Description

The present invention relates to a charge transporting varnish.

In the organic electroluminescence (hereinafter referred to as organic EL) element, a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injection layer. In particular, the hole injection layer is responsible for transferring charges between the anode and the hole transport layer or the light emitting layer, and plays an important role in achieving low voltage drive and high brightness of the organic EL element.
The method for forming the hole injection layer is roughly divided 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 is flatter in a larger area. A thin film with high properties can be efficiently produced. Therefore, at present, the area of organic EL displays is being increased, and 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 provides a thin film that can be applied to various wet processes and can realize excellent EL device characteristics when applied to a hole injection layer of an organic EL device. We have been developing compounds with good solubility in materials and organic solvents used for them (see, for example, Patent Documents 1 to 3).
On the other hand, various incorporations have been made so far in order to improve the performance of organic EL elements, but efforts are being made to adjust the refractive index of the functional film used for the purpose of improving the light extraction efficiency. .. 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 (for example, 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.

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

The present invention has been made in view of such circumstances, and is excellent when a thin film having good charge transport property and a high refractive index is provided by low-temperature firing and the thin film is applied to a hole injection layer or the like. It is an object of the present invention to provide a charge transporting varnish capable of realizing an organic EL device having such characteristics.

As a result of diligent studies to achieve the above object, the present inventor obtained a charge-transporting varnish containing a predetermined aniline derivative having a repeating unit of metaphenylene in the molecule by low-temperature firing at 200 ° C. or lower. The present invention has been completed by finding that a thin film having good charge transportability and a high refractive index is provided, and an organic EL element having excellent characteristics when this thin film is applied to a hole injection layer or the like is provided.

〔式中、Ｐｈ¹は、それぞれ独立して、式（Ｐ１）または式（Ｐ２）で表される基を表すが、少なくとも１つは式（Ｐ１）で表される基であり、

（式中、Ｒ¹〜Ｒ⁴は、それぞれ独立して、水素原子、シアノ基、またはシアノ基で置換されていてもよい、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数６〜２０のアリール基もしくは炭素数２〜２０のヘテロアリール基を表す。）
Ａｒ⁰は、それぞれ独立して、式（Ｂ０）で表される基を表し、

（式中、Ａｒ^Bは、単結合またはＥ基以外の任意の置換基（ピリジン環を含むものを除く。以下同様。）で置換されていてもよいフェニレン基を表し、Ａｒ^Bが前記フェニレン基の場合、Ａｒ^Gまたはその他の芳香環と結合して形成される縮合環の一部であってもよく、
Ａｒ^Gは、それぞれ独立して、Ｅ基以外の任意の置換基で置換されていてもよい、炭素数６〜２０のアリール基または炭素数２〜２０のヘテロアリール基を表し、
Ｅは、単結合、−Ｃ(Ｒ^a)₂−、−ＮＲ^b−、−ＮＨ−、Ｎ、−Ｏ−または−Ｓ−を表し、
Ｒ^aは、それぞれ独立して、水素原子またはヘテロ原子を含んでいてもよい炭素数１〜２０の１価炭化水素基を表し、Ｒ^aが前記１価炭化水素基の場合、Ｒ^a同士が互いに結合して炭素原子とともに環を形成していてもよく、Ｒ^bは、ヘテロ原子を含んでいてもよい炭素数１〜２０の１価炭化水素基を表し、
Ａｒ^Bが、単結合の場合、Ｅは単結合、かつ、Ａｒ^GはＥ基以外の任意の置換基で置換されていてもよいナフチル基であり、
Ｅが、−Ｃ(Ｒ^a)₂−基の場合、Ａｒ^BおよびＡｒ^Gは、互いに結合して縮合環を形成しており、それ以外の場合、Ａｒ^BおよびＡｒ^Gは、互いに結合して縮合環を形成していてもよく、
ｎ^Gは、Ｅに結合するＡｒ^G基の数であり、ＥがＮの場合は２を、それ以外の場合は１を表し、Ａｒ^G基が２個存在する場合、それらが互いに結合して窒素原子とともに縮合環を形成していてもよい。）
ｋは、１以上の整数を表す。〕
２． 前記Ａｒ⁰が、それぞれ独立して、式（Ｂ１）〜（Ｂ１６）のいずれかで表される基である１の電荷輸送性ワニス、

（式中、Ｒ⁵〜Ｒ²⁵、Ｒ²⁸〜Ｒ⁴⁹およびＲ⁵¹〜Ｒ¹⁹⁴は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、またはハロゲン原子、ニトロ基もしくはシアノ基で置換されていてもよい、ジフェニルアミノ基、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数６〜２０のアリール基もしくは炭素数２〜２０のヘテロアリール基を表し、Ｒ²⁶およびＲ²⁷は、それぞれ独立して、水素原子、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニル基、Ｚ²で置換されていてもよい炭素数６〜２０のアリール基もしくはＺ²で置換されていてもよい炭素数２〜２０のヘテロアリール基を表し、Ｒ⁵⁰は、水素原子、Ｚ¹で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルケニル基、Ｚ¹で置換されていてもよい炭素数２〜２０のアルキニル基、Ｚ²で置換されていてもよい炭素数６〜２０のアリール基もしくはＺ²で置換されていてもよい炭素数２〜２０のヘテロアリール基を表し、Ｚ¹は、ハロゲン原子、ニトロ基、シアノ基、ジフェニルアミノ基、Ｚ³で置換されていてもよい炭素数６〜２０のアリール基またはＺ³で置換されていてもよい炭素数２〜２０のヘテロアリール基を表し、Ｚ²は、ハロゲン原子、ニトロ基、シアノ基、ジフェニルアミノ基、Ｚ³で置換されていてもよい炭素数１〜２０のアルキル基、Ｚ³で置換されていてもよい炭素数２〜２０のアルケニル基またはＺ³で置換されていてもよい炭素数２〜２０のアルキニル基を表し、Ｚ³は、ハロゲン原子、ニトロ基、シアノ基またはジフェニルアミノ基を表し、Ａｒ⁴は、それぞれ独立して、ジ（炭素数６〜２０のアリール基）アミノ基で置換されていてもよい炭素数６〜２０のアリール基を表す。）
３． 前記式（１）で表されるアニリン誘導体が、式（１−１）〜（１−４）のいずれかで表される２の電荷輸送性ワニス、

（Ａｒ¹〜Ａｒ³は、それぞれ異なって前記式（Ｂ１）〜（Ｂ１６）のいずれかで表される基であり、各式のそれぞれにおいて、Ａｒ¹は、すべて同一の基を表し、Ａｒ²は、すべて同一の基を表し、Ａｒ³は、すべて同一の基を表す。）
４． 前記式（Ｐ１）で表される基の数（ｎ^m）と前記式（Ｐ２）で表される基の数（ｎ^p）が、０．５≦ｎ^m／（ｎ^m＋ｎ^p）を満たす１〜３のいずれかの電荷輸送性ワニス、
５． ドーパント物質を含む１〜４のいずれかの電荷輸送性ワニス、
６． 前記ドーパント物質が、アリールスルホン酸エステル化合物である５の電荷輸送性ワニス、
７． １〜６のいずれかの電荷輸送性用ワニスを用いて作製される電荷輸送性薄膜、
８． ７の電荷輸送性薄膜を備える電子素子、
９． ７の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子、
１０． 前記電荷輸送性薄膜が、正孔注入層または正孔輸送層である９の有機エレクトロルミネッセンス素子
を提供する。That is, the present invention
1. 1. A charge-transporting varnish containing an aniline derivative represented by the following formula (1) and an organic solvent.

[In the formula, Ph ¹ independently represents a group represented by the formula (P1) or the formula (P2), but at least one is a group represented by the formula (P1).

(In the formula, R ^{1 to} R ⁴ are each independently substituted with a hydrogen atom, a cyano group, or a cyano group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. , An alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.)
Ar ⁰ independently represents a group represented by the formula (B0).

(In the formula, Ar ^B represents a phenylene group which may be substituted with an arbitrary substituent other than a single bond or an E group (excluding those containing a pyridine ring. The same shall apply hereinafter), and Ar ^B is the phenylene group. In the case of, it may be a part of a fused ring formed by bonding with ^{Ar G or other aromatic rings.}
Ar ^G represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be independently substituted with any substituent other than the E group.
E represents a single bond, −C (R ^a ) ₂ −, −NR ^b −, −NH−, N, −O− or −S−.
R ^a independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom, and when R ^a is the monovalent hydrocarbon group, R ^a is used. It may be bonded to each other to form a ring with a carbon atom, and R ^b represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
When Ar ^B is a single bond, E is a single bond, and Ar ^G is a naphthyl group which may be substituted with an arbitrary substituent other than the E group.
When E is a −C ( ^Ra ) ₂ -group, Ar ^B and Ar ^G are bonded to each other to form a fused ring, otherwise Ar ^B and Ar ^G are bonded to each other. It may form a fused ring,
n ^{G is the number of Ar G} groups attached to E. If E is N, it represents 2, otherwise it represents 1, and ^{if there are two Ar G} groups, they are bound to each other. A fused ring may be formed together with the nitrogen atom. )
k represents an integer of 1 or more. ]
2. A charge-transporting varnish of 1 in which Ar ⁰ is a group represented by any of the formulas (B1) to (B16) independently.

(In the formula, R ^{5 to} R ²⁵ , R ^{28 to} R ^49, and R ^{51 to} R ¹⁹⁴ are independently hydrogen atoms, halogen atoms, nitro groups, cyano groups, or halogen atoms, nitro groups, or cyano groups. May be substituted, diphenylamino group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or 2 carbon atoms. Representing a heteroaryl group of ~ 20, R ²⁶ and R ²⁷ may be independently substituted with a hydrogen atom, Z ¹ or an alkyl group having 1 to 20 carbon atoms, even if substituted with ^{Z 1.} an alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group or Z ² in Z ¹ in optionally substituted alkynyl group having 2 to 20 carbon atoms, Z ² carbon atoms which may be substituted with 6-20 is represents a heteroaryl group having a carbon number of 2 to 20 even if, R ⁵⁰ is a hydrogen atom, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^1, optionally substituted by Z ¹ an alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group or Z ² in Z ¹ in optionally substituted alkynyl group having 2 to 20 carbon atoms, Z ² carbon atoms which may be substituted with 6-20 Represents a heteroaryl group having 2 to 20 carbon atoms which may be ^{substituted, and Z 1} is an aryl having 6 to 20 carbon atoms which may be substituted with a halogen atom, a nitro group, a cyano group, a diphenylamino group, or Z ^3. Represents a group or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 3, where Z 2} is a halogen atom, a nitro group, a cyano group, a diphenylamino group, or a carbon which may be substituted with ^{Z 3.} C 1 -C 20 alkyl group, an alkynyl group an alkenyl group or Z ³ may 2-20 carbon atoms substituted with a Z ³ good 2-20 carbon atoms which may be substituted by, Z ³ is Representing a halogen atom, a nitro group, a cyano group or a diphenylamino group, Ar ⁴ has 6 to 20 carbon atoms which may be independently substituted with a di (aryl group having 6 to 20 carbon atoms) amino group. Represents an aryl group.)
3. 3. The aniline derivative represented by the formula (1) is a charge-transporting varnish of 2 represented by any of the formulas (1-1) to (1-4).

(Ar ^{1 to} Ar ³ are different groups represented by any of the above formulas (B1) to (B16), and in each of the formulas, Ar ¹ all represent the same group, and Ar ² Represents all the same groups, and Ar ^{3 represents all the same groups.)}
4. ^{The number of groups (nm} ) represented by the formula (P1) and ^{the number of groups (n p} ) represented by the formula (P2) satisfy 0.5 ≦ ^nm / ( ^nm + n ^p ). Charge-transporting varnish, any of 1-3
5. A charge-transporting varnish, any of 1 to 4, containing a dopant material.
6. 5 charge-transporting varnishes in which the dopant substance is an aryl sulfonic acid ester compound,
7. A charge-transporting thin film prepared by using any of the charge-transporting varnishes 1 to 6.
8. Electronic device with 7 charge-transporting thin films,
9. Organic electroluminescence device with 7 charge-transporting thin films,
10. The charge-transporting thin film provides 9 organic electroluminescent devices that are hole-injecting layers or hole-transporting layers.

By using the charge transporting varnish of the present invention, a thin film having a high refractive index can be produced, and a thin film having excellent charge transporting property can be produced even when fired at a low temperature of 200 ° C. or lower.
The charge-transporting thin film obtained from the charge-transporting varnish of the present invention can be suitably used as a thin film for electronic devices such as organic EL devices, and can be used as a hole injection layer or a hole transport layer of an organic EL device. In particular, by using it as a hole injection layer, an organic EL device having excellent characteristics can be obtained.

Hereinafter, the present invention will be described in more detail.
The charge-transporting varnish of the present invention contains an aniline derivative represented by the following formula (1) and an organic solvent.

In the formula (1), Ph ¹ independently represents a group represented by the formula (P1) or the formula (P2), but as described later, at least one of ^{the (k + 1) Ph 1 groups is} , A group represented by the formula (P1).

Here, R ^{1 to} R ⁴ may be independently substituted with a hydrogen atom, a cyano group, or a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and the like. It represents an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.

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 groups 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.

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, and the like. 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, 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.

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.

Specific examples of the heteroaryl group having 2 to 20 carbon atoms include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isooxazolyl and 4-isooxazolyl. , 5-Isoxazolyl group and other oxygen-containing heteroaryl groups; 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl group and other sulfur-containing heteroaryl groups; 2-imidazolyl, 4 -Imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazyl, 3-pyrazil, 5-pyrazyl, 6-pyrazyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 6-pyrimidyl, 3-pyridadyl , 4-Pyridazil, 5-Pyridazil, 6-Pyridazil, 1,2,3-Triazine-4-yl, 1,2,3-Triazine-5-yl, 1,2,4-Triazine-3-yl, 1 , 2,4-Triazine-5-yl, 1,2,4-triazine-6-yl, 1,3,5-triazine-2-yl, 1,2,4,5-tetrazine-3-yl, 1 , 2,3,4-tetrazine-5-yl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 8-quinolinyl, 1-isoquinolinyl, 3-isoquinolinyl, 4 -Isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 8-isoquinolinyl, 2-quinoxanyl, 5-quinoxanyl, 6-quinoxanyl, 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl , 8-Kinazolinyl, 3-Synolinyl, 4-Synnolinyl, 5-Synolinyl, 6-Synnolinyl, 7-Synnolinyl, 8-Synnolinyl group and other nitrogen-containing heteroaryl groups and the like.

Among these, R ^{1 to} R ⁴ include an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a cyano group or a cyano group, and 6 to 20 carbon atoms which may be substituted with a cyano group. A heteroaryl group having 2 to 20 carbon atoms which may be substituted with an aryl group or a cyano group is preferable, and an alkyl group having 1 to 10 carbon atoms or a cyano which may be substituted with a hydrogen atom, a cyano group or a cyano group is preferable. A phenyl group which may be substituted with a group is more preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is the most suitable.

That is, the optimum group represented by the formula (P1) is an unsubstituted metaphenylene group (benzene-1,3-diyl group), and the group represented by the formula (P2) is an unsubstituted paraphenylene. The group (benzene-1,4-diyl group) is optimal.

In the above formula (1), Ar ⁰ independently represents a group represented by the formula (B0).

In the formula, Ar ^B represents a phenylene group which may be substituted with an arbitrary substituent other than a single bond or an E group (excluding those containing a pyridine ring; the same shall apply hereinafter), and Ar ^B represents the phenylene group described above. In some cases, it may be part of a fused ring formed by bonding with ^{Ar G or other aromatic rings.}
Examples of the phenylene group in the phenylene group which may be substituted with an arbitrary substituent other than the E group include an orthophenylene group, a metaphenylene group and a paraphenylene group, but from the viewpoint of easiness of synthesizing an aniline derivative. , Metaphenylene group and paraphenylene group are preferable, and further, considering the solubility of the aniline derivative, the paraphenylene group is more preferable.

Ar ^G represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be independently substituted with any substituent other than the E group. Specific examples of these aryl groups and heteroaryl groups include, but are not limited to, those exemplified above.
Among them, Ar ^G is preferably an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 2 to 10 carbon atoms, which may be substituted with a substituent other than the E group, and is substituted with a substituent other than the E group. An aryl group having 6 to 10 carbon atoms which may be substituted is more preferable, and a phenyl group, a 1-naphthyl group and a 2-naphthyl group which may be substituted with a substituent other than the E group are even more preferable.

The substituent other than the E group substituted with Ar ^B and Ar ^G is not particularly limited as long as it does not contain a pyridine ring, but is a halogen atom, a nitro group, a cyano group, a diphenylamino group and a carbon number. An alkyl group of 1 to 20, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a diphenylamino group and an alkyl group substituted with these groups. , Alkenyl group, alkynyl group; alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, etc. substituted with an aryl group, etc. Can be mentioned. Specific examples of the alkyl group, alkenyl group, alkynyl group and aryl group include, but are not limited to, the same as those exemplified above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

E represents a single bond, -C (R ^a ) _2- , -NR ^b- , -NH-, N, -O- or -S-.
Here, R ^a independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom, and when R ^a is the above monovalent hydrocarbon group, R a. ^a may be bonded to each other to form a ring together with a carbon atom. R ^b represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain the hetero atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Examples thereof include an aryl group having 6 to 20 carbon atoms and a heteroaryl group having 2 to 20 carbon atoms, and specific examples thereof include those similar to those exemplified above. In addition, these groups may be further substituted with a substituent.
Such substituents include a halogen atom, a nitro group, a cyano group, a diphenylamino group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a carbon number of carbon atoms. Examples thereof include an aryl group of 6 to 20, a heteroaryl group having 2 to 20 carbon atoms, and those in which these groups are further substituted.

When Ar ^B is a single bond, E is also a single bond, and Ar ^G is a naphthyl group which may be substituted with an arbitrary substituent other than the E group. Examples of such a naphthyl group include a 1-naphthyl group and a 2-naphthyl group.
When E is a −C ( ^Ra ) ₂ -group, Ar ^B and Ar ^G are bonded to each other to form a fused ring, and in other cases, Ar ^B and Ar ^G are bonded to each other. May form a fused ring.

n ^{G is the number of Ar G} groups attached to E. If E is N, it represents 2, otherwise it represents 1, and ^{if there are two Ar G} groups, they are bound to each other. A fused ring may be formed together with the nitrogen atom.
Although k represents an integer of 1 or more, it is preferably 10 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, from the viewpoint of solubility of the aniline derivative.

As described above, the aniline derivative used in the present invention contains at least one metaphenylene structure in its straight chain, and at least one of the (k + 1) Ph ¹ groups in the formula (1) is the formula (1). Represents a group represented by P1).
^{Here, the number of groups (nm} ) represented by the formula (P1) in the formula (1) and ^{the number of groups (n p} ) represented by the formula (P2) ^{satisfy n m} + n ^p = k + 1. However, considering the balance between the solubility of the aniline derivative and the charge transportability and refractive index of the obtained charge transport thin film, ^nm and n ^p are preferably 0.5 ≦ ^nm / ( ^nm + n ^p ). , More preferably 0.6 ≤ ^nm / ( ^nm + n ^p ), even more preferably 0.8 ≤ ^nm / ( ^nm + n ^p ), and even more preferably 0.9 ≤ ^nm / (. n ^m + n ^p ) is satisfied, and most preferably 1 = ^nm / ( ^nm + n ^p ) is satisfied.

In a preferred embodiment of the present invention, Ar ⁰ in the formula (1) independently represents a group represented by any of the formulas (B1) to (B16), and in particular, the formula (B1'). A group represented by any of (B16'-5) is preferable.

Here, R ^{5 to} R ²⁵ , R ^{28 to} R ^49, and R ^{51 to} R ¹⁹⁴ are independently substituted with hydrogen atom, halogen atom, nitro group, cyano group, or halogen atom, nitro group, or cyano group, respectively. Diphenylamino group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or 2 to 2 carbon atoms. represents 20 heteroaryl group, R ²⁶ and R ²⁷ each, independently, a hydrogen atom, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^1, which may be substituted with Z ¹ alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group or Z ² in Z ¹ in optionally substituted alkynyl group having a carbon number of 2 to 20, Z ² carbon atoms which may be substituted with 6-20 represents an heteroaryl group having 2 to 20 carbon atoms may have, R ⁵⁰ is a hydrogen atom, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^1, which may be substituted with Z ¹ alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group or Z ² in Z ¹ in optionally substituted alkynyl group having a carbon number of 2 to 20, Z ² carbon atoms which may be substituted with 6-20 Represents a heteroaryl group having 2 to 20 carbon atoms which may be ^{substituted, and Z 1} is an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, a nitro group, a cyano group, a diphenylamino group, or Z ^3. Alternatively, it represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ^{3 , and Z 2} has a halogen atom, a nitro group, a cyano group, a diphenylamino group, or a carbon number which may be substituted with ^{Z 3.} 20 alkyl group, an alkenyl group, or Z ³ in which may be substituted alkynyl group having 2 to 20 carbon atoms in a good 2 to 20 carbon atoms optionally substituted by Z ^3, Z ³ is halogen Represents an atom, nitro group, cyano group or diphenylamino group, these halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, 6 to 20 carbon atoms. Specific examples of the aryl group and the heteroaryl group having 2 to 20 carbon atoms include those similar to those described above.

In particular, R ^{5 to} R ²⁵ , R ^{28 to} R ⁴⁹ and R ^{51 to} R ¹⁹⁴ are substituted with a hydrogen atom, a fluorine atom, a cyano group, a diphenylamino group which may be substituted with a fluorine atom, and a fluorine atom. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a fluorine atom, and a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a fluorine atom are preferable. , A hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and a phenyl group which may be substituted with a fluorine atom are more preferable. A group and a trifluoromethyl group are more preferable, and a hydrogen atom is most suitable.
The R ²⁶ and R ^27, an aryl group are carbon atoms and optionally 6-14 substituted by Z ^2, a heteroaryl group Z ² carbon atoms which may be substituted with 2 to 14 preferably in Z ² more preferably an aryl group which may having 6 to 14 carbon atoms optionally substituted, a phenyl group optionally substituted by Z ^2, may be substituted with Z ² 1-naphthyl group, substituted by Z ² A 2-naphthyl group which may be used is even more preferable.
The R ^50, a hydrogen atom, preferably an aryl group having 6 to 20 carbon atoms optionally substituted by Z ^2, and more aryl group hydrogen atom, Z ² carbon atoms which may be substituted with 6-14 preferably, hydrogen atom, a phenyl group which may be substituted with Z ^2, Z ² with optionally substituted 1-naphthyl group, Z ² and still more preferably, also be 2-naphthyl group optionally substituted by.

Further, Ar ⁴ independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di (aryl group having 6 to 20 carbon atoms) amino group.
Specific examples of the aryl group having 6 to 20 carbon atoms include the same groups as those described above, and specific examples of the di (aryl group having 6 to 20 carbon atoms) amino group include diphenylamino and 1 Examples thereof include −naphthylphenylamino, di (1-naphthyl) amino, 1-naphthyl-2-naphthylamino, di (2-naphthyl) amino group and the like.
Ar ⁴ includes phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4- Phenantryl group, 9-phenanthryl group, p- (diphenylamino) phenyl group, p- (1-naphthylphenylamino) phenyl group, p- (di (1-naphthyl) amino) phenyl group, p- (1-naphthyl-) A 2-naphthylamino) phenyl group and a p- (di (2-naphthyl) amino) phenyl group are preferable, and a p- (diphenylamino) phenyl group is more preferable.

Hereinafter, ^{specific examples of groups suitable as Ar 0} will be given, but the present invention is not limited thereto.

（式中、ＤＰＡは、ジフェニルアミノ基を表す。）

(In the formula, DPA represents a diphenylamino group.)

（式中、Ｒ⁵⁰は、上記と同じ意味を表す。）

(In the formula, R ⁵⁰ has the same meaning as above.)

In the present invention, ^{specific examples of groups suitable for R 50} include, but are not limited to, the following groups.

In the present invention, the alkyl group, alkenyl group and alkynyl group have preferably 10 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms.
The aryl group and the heteroaryl group have preferably 14 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably 6 or less carbon atoms.

In the present invention, considering the ease of synthesis, the aniline derivative represented by the formula (1) is preferably the aniline derivative represented by any of the formulas (1-1) to (1-4).

（Ａｒ¹〜Ａｒ³は、それぞれ異なって上記式（Ｂ１）〜（Ｂ１６）のいずれかで表される基であり、各式のそれぞれにおいて、Ａｒ¹は、すべて同一の基を表し、Ａｒ²は、すべて同一の基を表し、Ａｒ³は、すべて同一の基を表す。）

(Ar ^{1 to} Ar ³ are different groups represented by any of the above formulas (B1) to (B16), and in each of the formulas, Ar ¹ all represent the same group, and Ar ² Represents all the same groups, and Ar ^{3 represents all the same groups.)}

The aniline derivative represented by the formula (1) used in the present invention can be produced by reacting an amine compound represented by the formula (4) with an aryl compound represented by the formula (5) in the presence of a catalyst. ..

（式中、Ｘは、ハロゲン原子または擬ハロゲン基を表し、Ａｒ⁰、Ｐｈ¹およびｋは、上記と同じ意味を表す。）

(In the formula, X represents a halogen atom or a pseudohalogen group, and Ar ⁰ , Ph ¹ and k 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 amine compound represented by the formula (4) to the aryl compound represented by the formula (5) can be equal to or more than the equivalent amount of the aryl compound with respect to the amount of substance of the total NH groups of the amine compound. However, about 1 to 1.2 equivalents are 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 (P-t-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, and di-t-butyl ( Phosphine) phosphine, di-t-butyl (4-dimethylaminophenyl) phosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) Examples thereof include tertiary phosphine such as fino) butane and 1,1'-bis (diphenylphosphine) ferrocene, and tertiary phosphine such as trimethylphosphine, triethylphosphine and triphenylphosphine.

The amount of the catalyst used can be about 0.1 to 0.2 mol with respect to 1 mol of the aryl compound represented by the formula (5), but about 0.15 mol is preferable.
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.

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 desired aniline derivative. 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 (dimethylsulfoxylene, sulfolane, etc.), nitriles (acetoyl, propionitrile, butyronitrile, etc.), etc., and these solvents are used 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.
After completion of the reaction, post-treatment can be carried out according to a conventional method to obtain the desired aniline derivative.

The aniline derivative represented by the above formula (1-1) can also be produced by the following method.
First, the dinitro compound represented by the formula (1-1-4) is reacted with the aryl compound represented by the formula (6) to obtain the dinitro compound represented by the formula (1-1-3). ..

（式中、Ａｒ¹、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ar ¹ , Ph ¹ , X and k have the same meaning as above.)

The charging ratio of the dinitro compound represented by the formula (1-1-4) to the aryl compound represented by the formula (6) is such that the aryl compound is equivalent or more with respect to the amount of substance of the total NH groups of the dinitro compound. However, about 1 to 1.2 equivalents are preferable.
In addition, various conditions of the coupling reaction regarding the amount of catalyst for the aryl compound, the solvent, the reaction temperature, etc. are the same as the above conditions described for the method for producing the aniline derivative represented by the formula (1).

Next, the nitro group in the dinitro compound represented by the formula (1-1-3) is reduced by hydrogenation to obtain an amine compound represented by the formula (1-1-2). Hydrogenation includes a hydrogenation reaction using Pd / C or the like, and can be carried out by a known method.

（式中、Ａｒ¹、Ｐｈ¹およびｋは、上記と同じ意味を表す。）

(In the formula, Ar ¹ , Ph ¹ and k have the same meaning as above.)

Next, the amine compound represented by the formula (1-1-2) is reacted with the aryl compound represented by the formula (7) to obtain the amine compound represented by the formula (1-1-1). The obtained amine compound represented by the formula (1-1-1) is reacted with the aryl compound represented by the formula (8) to obtain an aniline derivative represented by the formula (1-1). Obtainable.

（式中、Ａｒ¹、Ａｒ²、Ａｒ³、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ph ¹ , X and k have the same meanings as above.)

The charging ratio of the amine compound represented by the formula (1-1-2) to the aryl compound represented by the formula (7) or the amine compound represented by the formula (1-1-1) and the formula (8). ) Can be 2 equivalents or more of the aryl compound with respect to the amine compound, but it is preferably about 2 to 2.4 equivalents.
In addition, various conditions of the coupling reaction regarding the amount of catalyst for the aryl compound, the solvent, the reaction temperature, etc. are the same as the above conditions described for the method for producing the aniline derivative represented by the formula (1).

The aniline derivative represented by the formula (1-2) can also be produced by the following method.
An aniline derivative represented by the formula (1-2) is obtained by reacting the amine compound represented by the formula (1-1-1) obtained by the above method with the aryl compound represented by the formula (6). Can be obtained.

（式中、Ａｒ¹、Ａｒ²、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ar ¹ , Ar ² , Ph ¹ , X and k have the same meaning as above.)

The conditions of the coupling reaction regarding the charging ratio of the amine compound and the aryl compound, the amount of catalyst for the aryl compound, the solvent, the reaction temperature, etc. are the same as the above conditions described for the method for producing the aniline derivative represented by the formula (1). Is.

The aniline derivative represented by the formula (1-3) can also be produced by the following method.
An aniline derivative represented by the formula (1-3) is obtained by reacting the amine compound represented by the formula (1-1-2) obtained by the above method with the aryl compound represented by the formula (7). Can be obtained.

（式中、Ａｒ¹、Ａｒ²、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ar ¹ , Ar ² , Ph ¹ , X and k have the same meaning as above.)

The charging ratio of the amine compound represented by the formula (1-1-2) to the aryl compound represented by the formula (7) is such that the aryl compound is equivalent or more with respect to the amount of substance of the total NH groups of the amine compound. However, about 1 to 1.2 equivalents are preferable.
In addition, various conditions of the coupling reaction regarding the amount of catalyst for the aryl compound, the solvent, the reaction temperature, etc. are the same as the above conditions described for the method for producing the aniline derivative represented by the formula (1).

The aniline derivative represented by the formula (1-4) can also be produced by the following method.
An aniline derivative represented by the formula (1-4) can be obtained by reacting the amine compound represented by the formula (4) with the aryl compound represented by the formula (6).

（式中、Ａｒ¹、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ar ¹ , Ph ¹ , X and k have the same meaning as above.)

The conditions of the coupling reaction regarding the charging ratio of the amine compound and the aryl compound, the amount of catalyst for the aryl compound, the solvent, the reaction temperature, etc. are the same as the above conditions described for the method for producing the aniline derivative represented by the formula (1). Is.

The amine compound that can be used as a raw material for the aniline derivative used in the present invention is an amine represented by the formula (A) (1-1-4) or the formula (1-1-5) as shown in the following scheme. It can be obtained by the coupling reaction between the compound and the aryl compound represented by the formula (9) and the reduction reaction of the nitro group by hydrogenation (B), and by repeating these (A) and (B), The chain length (m- or p-phenylene number) can be extended.

（式中、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ph ¹ , X and k have the same meanings as above.)

（式中、Ｐｈ¹、Ｘおよびｋは、上記と同じ意味を表す。）

(In the formula, Ph ¹ , X and k have the same meanings as above.)

To give a more specific example, one compound of the amine compound included in the formula (4) is (A) m-phenylenediamine or 3-nitroaniline and 3-halo, as shown in the following scheme. It can be obtained by a coupling reaction with nitrobenzene and (B) a reduction reaction of nitro groups by hydrogenation, and by repeating these reactions (A) and (B), the chain length (m-phenylene number) is extended. Can be done.

（式中、Ｘは、上記と同じ意味を表す。）

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

Since it is possible to make the phenylene number even or odd 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 represented by the formula (4) having a desired number of phenylene can be freely produced without using a method.

In this case, the charging ratio of the amine compound or m-phenylenediamine represented by the formula (1-1-4) to the aryl compound or 3-halonitrobenzene represented by the formula (9) is the substance amount ratio. The aryl compound or 3-halonitrobenzene represented by the formula (9) is preferably about 2 to 2.4 with respect to the amine compound represented by the formula (1-1-4) or m-phenylenediamine 1.
The charging ratio of the amine compound or 3-nitroaniline represented by the formula (1-1-5) to the aryl compound or 3-halonitrobenzene represented by the formula (9) is a substance amount ratio. The aryl compound or 3-halonitrobenzene represented by the formula (9) is preferably about 1 to 1.2 with respect to the amine compound represented by (1-1-5) or 3-nitroaniline 1.

Examples of the palladium catalyst used in the coupling reaction include the same ones as described above. Also in this case, a ligand can be used. As 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. -Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me ₃ (OMe) tBuXPhos, (2-Biphenyl) di-1-adamantylphosphine, RockPhos, CPhos and other biphenylphosphine compounds 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 metals 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.

Other conditions of the coupling reaction regarding the solvent, reaction temperature, etc. are the same as the above conditions described for the method for producing the aniline derivative represented by the formula (1).
Further, the hydrogenation reaction using Pd / C can be carried out by a known method.
When a paraphenylene group is introduced instead of the metaphenylene group, 4-halonitrobenzene may be used instead of 3-halonitrobenzene.

The charge-transporting varnish of the present invention contains the charge-transporting substance composed of the above-mentioned aniline derivative and an organic solvent, and a dopant substance is used for the purpose of improving the charge-transporting ability depending on the use of the obtained thin film. It may be included.

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.
Further, the dopant substance functions as a dopant substance for the first time in the process of obtaining a charge-transporting thin film which is a solid film from a varnish, for example, when a part of the molecule is removed by an external stimulus such as heating at the time of firing. It may be a substance that becomes expressed or improved, 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 an isopolyacid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), with an 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. In addition, these heteropolyacids are available as commercial 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 phosphotung acid or phosphomolybdic acid, and phosphotung acid is most suitable. When two or more kinds of heteropolyacids are used, one of the two or more kinds of heteropolyacids is preferably phosphotung acid or phosphomolybdic acid, and more preferably phosphotung 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 those obtained as commercial products or known synthetics. 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 phosphomolybdic 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 heteropolymetalate used can be about 0.001 to 50.0 with respect to the charge-transporting substance 1 composed of the aniline derivative represented by the formula (1) in terms of mass ratio, but is preferably 0. It is about 01 to 20.0, more preferably about 0.1 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), halotetracyanoquinodimethane represented by the formula (H3), and the like.
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. More preferably, all are halogen atoms.
Examples of the halogen atom include the same ones as described 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, still more preferably, with respect to the aniline derivative represented by the formula (1). Is 1 to 20 equivalents.

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-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, Dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 2,7-dinonyl-4,5-naphthalenedisulfonic acid, International Publication No. 2005/000832, 1,4 -Benzodioxane disulfonic acid compounds, aryl sulfonic acid compounds described in International Publication No. 2006/025342, aryl sulfonic acid compounds described in International Publication No. 2009/096322, and the like can be mentioned.

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 a perfluorobiphenyl diyl. 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 of 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 a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or an alkenyl halide having 2 to 10 carbon atoms. a group, and at least 3 of the a ⁴ to a ⁸ is preferably fluorine is atomic, hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, 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 the perfluoroalkyl group has 1 to 5 carbon atoms or the perfluoroalkenyl group having 1 to 5 carbon atoms, and 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 above-mentioned aniline derivative used in the present invention. Is 1500 or less.

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

The amount of the aryl sulfonic acid compound used is preferably about 0.01 to 20.0, more preferably 0.4 to the amount of the aniline derivative 1 represented by the formula (1) in terms of the amount of substance (molar). It is about 5.0.
A commercially available product may be used as the aryl sulfonic acid compound, but it can also be synthesized by a known method described in International Publication No. 2006/025342, International Publication No. 2009/09632, and the like.

On the other hand, examples of the aryl sulfonic acid ester compound include the aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217455, the aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017-243631. The above-mentioned aryl sulfonic acid ester compounds and the like can be mentioned, and specifically, those represented by any of the following formulas (H6) to (H8) are preferable.

（式中、ｍは、１≦ｍ≦４を満たす整数であるが、２が好ましい。ｎは、１≦ｎ≦４を満たす整数であるが、２が好ましい。）

(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 independently hydrogen atoms or linear or branched alkyl groups having 1 to 6 carbon atoms, and R ^s5 has 2 to 20 carbon atoms which may be substituted. 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. , Alkyl groups having 1 to 3 carbon atoms are 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 and 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 hydrocarbon compounds 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. Group, cyano group, hydroxy group, amino group, silanol group, thiol group, carboxy group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, ester group, thioester group, amide group, monovalent hydrocarbon group, organo Examples thereof include an oxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group and a sulfo group.
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 this 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 monovalent aliphatic hydrocarbon groups, and R ^s8 is a linear or branched 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 a halogenated alkenyl group having 2 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl 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 , 2,3,3,4,5,4-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 the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms. 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. Alkyl halide groups and alkenyl halide groups having 2 to 4 carbon atoms are more preferable, and nitro groups, cyano groups, trifluoromethyl groups and perfluoropropenyl groups 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 this 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 the above-mentioned monovalent aliphatic hydrocarbon groups other than the methyl group, 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.

In the present invention, in consideration of obtaining a thin film having high charge transportability with good reproducibility, availability of a dopant substance, and the like, the dopant substance includes an aryl sulfonic acid compound, an aryl sulfonic acid ester compound, an onium borate salt, and a halotetra. It is preferable to use at least one of cyanoquinodimethane and a benzoquinone derivative, and it is more preferable to use an aryl sulfonic acid ester compound in consideration of obtaining a thin film having a high refractive index.

In the present invention, the amount of the dopant substance in the varnish is preferably about 0.01 to 20, more preferably about 0.05 to 15 with respect to the aniline derivative 1 represented by the formula (1) in terms of molar ratio. be.

In addition to the above-mentioned charge-transporting substance composed of the aniline derivative, other known charge-transporting substances can also be used for the charge-transporting varnish of the present invention.

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 be contained, and the content thereof is usually about 1 to 30% by mass with respect to the total mass of the charge transporting substance and the dopant substance.

The organic solvent used in preparing the charge-transporting varnish of the present invention is not particularly limited as long as it can dissolve the charge-transporting substance and the dopant substance, and either a high-polarity solvent or a low-polarity solvent is used. be able to. 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. If necessary, a plurality of high-polarity solvents and low-polarity solvents can be mixed.
In particular, when the aniline derivative which is a charge transporting substance has a primary or secondary arylamine structure in its skeleton, at least one highly polar solvent is used to obtain the aniline derivative which is a charge transporting substance. When the skeleton does not have a primary or secondary arylamine structure, at least one low-polarity solvent can be used to obtain a charge-transporting varnish having excellent uniformity with good reproducibility.

Examples of low polar solvents include, for example.
Chlorine-based solvents such as chloroform and chlorobenzene;
Aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetraline, cyclohexylbenzenes and decylbenzenes;
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.

Further, the varnish is provided with a high-viscosity organic solvent having a viscosity of 10 to 200 mPa · s at 25 ° C., particularly 35 to 150 mPa · s, and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure). By containing at least one kind, the viscosity of the varnish can be easily adjusted, and as a result, the varnish can be adjusted according to the coating method to be used, which gives a thin film having high flatness with good reproducibility.
Examples of the high-viscosity organic solvent include cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and 1,3-butanediol. Examples thereof include, but are not limited to, 2,3-butanediol, 1,4-butanediol, propylene glycol, and hexylene glycol. These solvents may be used alone or in combination of two or more.
The addition ratio of the high-viscosity organic solvent to the entire solvent used for the varnish is preferably within the range in which the solid does not precipitate, and the addition ratio is preferably 5 to 80% by mass as long as the solid does not precipitate.

Further, for the purpose of improving the wettability with respect to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., the other solvent is added in an amount of 1 to 90% by mass, preferably 1 to 90% by mass, based on the total amount of the solvent used for the varnish. It can also be mixed at a ratio of 1 to 50% by mass.
Examples of such a solvent include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and diethylene glycol. Examples thereof include, but are not limited to, monoethyl ether, diacetone alcohol, γ-butylollactone, ethyllactate, and n-hexyl acetate. These solvents can be used alone or in admixture of two or more.

Further, when the aniline derivative used in the present invention does not have an NH structure in the molecule, for example, when it has a substituent on the nitrogen atom at the 9-position of carbazole, it preferably has a substituent on all the nitrogen atoms. If so, it will be easier to prepare the varnish using only the low polar solvents shown below.
Specific examples of the low polar solvent include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetraline, cyclohexylbenzene and decylbenzene; 1-octanol, 1-nonanol, 1-decanol and the like. Alibo alcohol solvents; ethers such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, etc. Solvents: 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 thereof include ester solvents, and these may be used alone or in combination of two or more.

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 10.0 mass. It is about%, preferably about 0.5 to 5.0% by mass, and more preferably about 1.0 to 3.0% by mass in consideration of improving the coatability of the varnish.
The viscosity of the charge-transporting varnish of the present invention is appropriately determined according to 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., and the surface tension is usually 1 to 50 mPa · s. It is 20 to 50 mN / m at 25 ° C.
The viscosity and surface tension of the charge-transporting varnish of the present invention can be determined by changing the types of organic solvents used, their ratios, solid content concentration, etc., in consideration of various factors such as the coating method used and the desired film thickness. It is adjustable.
In the present invention, the solid content means a component other than the solvent.

In the present invention, the method for preparing the charge-transporting varnish is not particularly limited, but for example, a method in which the above-mentioned aniline derivative is dissolved in a part of a solvent to be used and the remaining solvent is added thereto, or Examples thereof include a method in which all the solvents used are first mixed and the above-mentioned aniline derivative is dissolved therein.

In the preparation of the charge-transporting varnish of the present invention, from the viewpoint of obtaining a thin film having higher flatness with good reproducibility, a charge-transporting substance, a dopant substance, etc. are dissolved in an organic solvent, and then a filter on the order of submicrometers is obtained. It is desirable to filter using such as.
Further, if necessary, heating may be performed as long as the components of the varnish are not deteriorated.

Since the charge-transporting thin film of the present invention described above can be easily produced, it can be suitably used when producing an electronic device, particularly an organic EL device.
In this case, the charge-transporting thin film can be formed by applying the charge-transporting varnish of the present invention on a substrate and firing it.
The method for applying the varnish 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 atmosphere but also in an inert gas such as nitrogen or in a vacuum can be used. However, depending on the type of dopant substance used with the aniline derivative, a thin film having charge transportability may be obtained with good reproducibility by firing the varnish in an atmospheric 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, and the like. When the obtained thin film is used as a hole injection layer for an organic EL device, it is preferably about 140 to 250 ° C., more preferably about 145 to 240 ° C., but the charge transporting varnish of the present invention is fired at a low temperature of 200 ° C. or lower. However, a thin film having good charge transportability can be obtained.
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. For example, heating may be performed on 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 when used as a hole injection layer, a hole transport layer, or a hole injection transport layer of an organic EL element, it is usually 3 to 300 nm, but 5 to 200 nm is preferable. .. As a method of changing the film thickness, there are a method of changing the solid content concentration in the varnish, a method of changing the amount of the solution on the substrate at the time of coating, and the like.

The organic EL element of the present invention has a pair of electrodes, and has a charge transport layer made of the above-mentioned charge transport thin film of the present invention between these electrodes.
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 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) Antenna / 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 layers". 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 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 prepared from the charge-transporting varnish containing the above-mentioned aniline derivative used in the present invention comprises an anode and a light emitting layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer in an organic EL device. Although it can be used as a functional layer provided between the two, it is suitable for a hole injection layer.

Examples of materials and methods used for producing an organic EL device using a charge-transporting varnish containing the above-mentioned aniline derivative used in the present invention include, but are not limited to these. No.

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. The electrodes are preferably washed with alcohol, pure water, or the like, or surface-treated with UV ozone treatment, oxygen-plasma treatment, or the like in advance within a range that does not adversely affect the electrodes.
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 gold, silver, copper, indium, and alloys thereof.

Materials that form the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimers, and 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 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).} Examples thereof include naphthacene derivatives such as rubrene, quinacridone derivatives, and fused polycyclic aromatic rings such as perylene.

Examples of the material for forming the electron transport layer / whole block layer include an oxydiazole derivative, a triazole derivative, a phenanthroline derivative, a phenylquinoxaline derivative, a benzimidazole derivative, a pyrimidine derivative and the like.

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). Metal fluoride, etc., but is not limited to these.
Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy and the like.
Examples of the material for forming the electron block layer include 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 material constituting the anode and the cathode and the layer formed between them differs depending on whether the element having the bottom emission structure or the top emission structure is manufactured. Therefore, the material is appropriately selected in consideration of this point.
Normally, in the element of the bottom emission structure, a transparent anode is used on the substrate side and light is extracted from the substrate side, whereas in the element of the top emission structure, a reflective anode made of metal is used and the direction is opposite to that of the substrate. Since light is extracted from a certain transparent electrode (cathode) side, for example, regarding the anode material, a transparent anode such as ITO is used when manufacturing an element having a bottom emission structure, and Al is used when manufacturing an element having a top emission structure. Reflecting anodes such as / Nd are used respectively.

The organic EL device of the present invention may be sealed together with a water catching agent or the like, if necessary, in accordance with a conventional method in order to prevent deterioration of characteristics.

As described above, the charge transporting varnish of the present invention is suitable for forming a functional layer provided between an anode and a light emitting layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer of an organic EL device. In addition to being used, 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, It can also be used to form a charge transporting thin film in an electronic device such as an organic electric field extinguishing element, a light emitting electronic chemical battery, a quantum dot light emitting diode, a quantum laser, an organic laser diode, and an organic Plasmon light emitting device.

Hereinafter, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples. The devices used are as follows.
(1) MALDI-TOF-MS: autoflex III smart beam manufactured by Bruker Co., Ltd.
(2) ^{1 1} H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.
(3) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Industry 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 Industry Co., Ltd.
(7) Measurement of element current density: Multi-channel IVL measuring device manufactured by EHC Co., Ltd. (8) Measurement of refractive index (n): Multi-entry angle spectroscopic ellipsometer VASE manufactured by JA Woolam Japan

[1] Production of aniline derivative [Synthesis example 1] Production of aniline derivative A

(1) Synthesis of N, N-bis (3-nitrophenyl) -9-phenyl-9H-carbazole-3-amine 1.00 g of bis (3-nitrophenyl) amine, 3-bromo-9-phenyl-9H- 1.37 g of carbazole, 0.0678 g of bis (dibenzylideneacetone) palladium, di-t-butyl (2', 4', 6'-triisopropyl- [1,1'-diphenyl] -2-yl) phosphine (tBuXPhos) ) 0.0983 g, 1.61 g of potassium carbonate, and 10 mL of toluene were placed in a reaction vessel, replaced with nitrogen, and then stirred at 100 ° C. for 24.5 hours. After completion of the reaction, toluene and saturated brine were added to separate the solutions. The organic layer was filtered through silica gel, and then the filtrate was concentrated. Chloroform and hexane are added to the concentrated residue to make a solution, which is then purified by column chromatography (the eluent is a mixed solvent of chloroform / hexane) to obtain the desired N, N-bis (3-nitrophenyl) -9-phenyl. 1.02 g of -9H-carbazole-3-amine was obtained (yield: 53%).
MALDI-TOF-MS m / Z found: 499.86 ([M] ⁺ calcd: 500.15)

(2) Synthesis of N1- (3-aminophenyl) -N1- (9-phenyl-9H-carbazole-3-yl) benzene-1,3-diamine N, N-bis (3-nitrophenyl) -9- After putting 0.603 g of phenyl-9H-carbazole-3-amine 0.603 g, 5% palladium / carbon (manufactured by NE Chemcat, AER type, 50% water content) 0.0582 g, and 9 mL of tetrahydrofuran into the reaction vessel, hydrogen was added to the inside of the reaction vessel. It was replaced and stirred at 50 ° C. for 24 hours. After cooling to room temperature, the reaction solution was filtered through Celite (using Celite 545). The filtrate was dried to obtain 0.486 g of the desired N1- (3-aminophenyl) -N1- (9-phenyl-9H-carbazole-3-yl) benzene-1,3-diamine (yield). : 92%).
^{1 1} H-NMR (500 MHz, CDCl ₃ ) δ [ppm]: 8.00 (d, J = 8.0 Hz, 1H), 7.92 (m, 1H), 7.56-7.60 (m, 4H) ), 7.45 (m, 1H), 7.37-7.38 (m, 2H), 7.32 (d, J = 8.5Hz, 1H), 7.20-7.23 (m, 2H) ), 6.98-7.02 (m, 2H), 6.52 (d, J = 8.0Hz, 2H), 6.45 (m, 2H), 6.29-6.31 (m, 2H) ).

(3) Synthesis of aniline derivative A N1- (3-aminophenyl) -N1- (9-phenyl-9H-carbazole-3-yl) benzene-1,3-diamine 0.451 g, 3- obtained above. 1.45 g of bromo-9-phenyl-9H-carbazole, 0.0234 g of palladium acetate, and 0.539 g of sodium-t-butoxide were placed in a reaction vessel, substituted with nitrogen, 10 mL of toluene, and separately prepared phenyldi-t. 0.84 mL (concentration: 54.0 g / L) of a toluene solution of −butylphosphine was added, and the mixture was stirred at 90 ° C. for 1.5 hours. After cooling to room temperature, toluene and saturated brine were added to separate the solutions. The organic layer was filtered through silica gel, and then the filtrate was concentrated. The obtained concentrate was added dropwise to a mixed solvent of methanol / ethyl acetate, and the mixture was stirred at room temperature. The slurry solution was filtered, and the obtained filter medium was dried to obtain 0.855 g of the desired aniline derivative A (yield: 59%).
MALDI-TOF-MS m / Z found: 2620.94 ([M] ⁺ calcd: 2620.08)

[2] Preparation of charge-transporting varnish [Example 1-1]
3-Phenoxy was added to a mixture of 0.221 g of the aniline derivative A obtained in Synthesis Example 1 and 0.196 g of the aryl sulfonic acid ester B represented by the following formula synthesized according to the method described in International Publication No. 2017/217455. A solution obtained by adding 3.0 g of toluene and 7 g of butyl benzoate and stirring at room temperature to dissolve the solution was filtered through a syringe filter having a pore size of 0.2 μm to obtain a charge-transporting varnish.

[Comparative Example 1-1]
A charge transporting varnish was obtained in the same manner as in Example 1-1, except that the aniline derivative A was changed to the aniline derivative C represented by the following formula synthesized according to the method described in International Publication No. 2015/050253. rice field.

[3] Production of thin film and evaluation of film physical characteristics [Example 2-1 and Comparative Example 2-1]
The varnishes prepared in Example 1-1 and Comparative Example 1-1 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 with a coating film was calcined at 200 ° C. for 15 minutes or 230 ° C. for 15 minutes in an air atmosphere to form a uniform thin film having a thickness of 50 nm on the quartz substrate.
The refractive index n (average refractive index at wavelengths of 400 nm to 800 nm) of the obtained thin film was measured. The results are shown in Table 1.

As shown in Table 1, it can be seen that the refractive index of the thin film obtained from the varnish of the present invention is higher than that in the case of using an aniline derivative having a similar structure.

[4] Fabrication of single-layer device and evaluation of characteristics [Example 3-1]
The varnish prepared in Example 1-1 is applied to an ITO substrate using a spin coater, dried at 120 ° C. for 1 minute, and further fired at 200 ° C. for 15 minutes or 230 ° C. for 15 minutes to form a charge-transporting thin film. Was produced. An aluminum thin film was formed on this using a thin film deposition apparatus (vacuum degree 4.0 × 10 ^{-5 Pa) to obtain a single-layer device.} 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 thickness of 150 nm is used, and an O ₂ plasma cleaning device (150 W, 30 seconds) is used before use. Removed impurities on the surface. The vapor deposition was carried out under the condition of a vapor deposition rate of 0.2 nm / sec. The film thickness of the aluminum thin film was 80 nm.

The current density of the single-layer device manufactured above was measured at a drive voltage of 3 V. The results are shown in Table 2.

As shown in Table 2, the charge-transporting thin film of the present invention exhibited excellent charge-transporting properties not only when fired at a high temperature but also when fired at a low temperature.

[5] Fabrication and characterization of hole-only elements [Example 4-1]
Using the varnish prepared in Example 1-1 and the same substrate as the ITO substrate used in Example 3-1 to prepare a charge-transporting thin film on the ITO substrate in the same manner as in Example 3-1.
Next, α-NPD (N, N'-di (1-naphthyl) -N, N'-diphenyl was used on the ITO substrate on which the thin film was formed using a vapor deposition apparatus (vacuum degree 1.0 x 10 ^{-5 Pa).} Benzidine) was formed into a 30 nm film at 0.2 nm / sec. An 80 nm aluminum thin film was laminated on this in the same manner as in Example 3-1 to produce a hole-only element.

[Comparative Example 4-1]
A hole-only element was produced in the same manner as in Example 4-1 except that the varnish prepared in Comparative Example 1-1 was used instead of the varnish prepared in Example 1-1.

For each hole-only element manufactured above, the current density at a drive voltage of 3 V was measured. The results are shown in Table 3.

As shown in Table 3, the charge-transporting thin film obtained from the varnish of Comparative Example containing an aniline derivative having a similar structure is often used as a hole transport layer, that is, a decrease in current density when fired at 200 ° C. While a remarkable deterioration in hole injection into α-NPD was observed, in the charge-transporting thin film of the example, such deterioration was not observed when fired at 200 ° C., and the thin film was excellent. It showed a hole-injecting property.

Claims (10)

A charge-transporting varnish containing an aniline derivative represented by the following formula (1) and an organic solvent.

[In the formula, Ph ¹ independently represents a group represented by the formula (P1) or the formula (P2), but at least one is a group represented by the formula (P1).

(In the formula, R ^{1 to} R ⁴ are each independently substituted with a hydrogen atom, a cyano group, or a cyano group, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. , An alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.)
Ar ⁰ independently represents a group represented by the formula (B0).

(In the formula, Ar ^B represents a phenylene group which may be substituted with an arbitrary substituent other than a single bond or an E group (excluding those containing a pyridine ring. The same shall apply hereinafter), and Ar ^B is the phenylene group. In the case of, it may be a part of a fused ring formed by bonding with ^{Ar G or other aromatic rings.}
Ar ^G represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be independently substituted with any substituent other than the E group.
E represents a single bond, −C (R ^a ) ₂ −, −NR ^b −, −NH−, N, −O− or −S−.
R ^a independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a hetero atom, and when R ^a is the monovalent hydrocarbon group, R ^a is used. It may be bonded to each other to form a ring with a carbon atom, and R ^b represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
When Ar ^B is a single bond, E is a single bond, and Ar ^G is a naphthyl group which may be substituted with an arbitrary substituent other than the E group.
When E is a −C ( ^Ra ) ₂ -group, Ar ^B and Ar ^G are bonded to each other to form a fused ring, otherwise Ar ^B and Ar ^G are bonded to each other. It may form a fused ring,
n ^{G is the number of Ar G} groups attached to E. If E is N, it represents 2, otherwise it represents 1, and ^{if there are two Ar G} groups, they are bound to each other. A fused ring may be formed together with the nitrogen atom. )
k represents an integer of 1 or more. ] The charge-transporting varnish according to claim 1, wherein Ar ⁰ is a group represented by any of the formulas (B1) to (B16) independently.

(In the formula, R ^{5 to} R ²⁵ , R ^{28 to} R ^49, and R ^{51 to} R ¹⁹⁴ are independently hydrogen atoms, halogen atoms, nitro groups, cyano groups, or halogen atoms, nitro groups, or cyano groups. May be substituted, diphenylamino group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or 2 carbon atoms. Representing a heteroaryl group of ~ 20, R ²⁶ and R ²⁷ may be independently substituted with a hydrogen atom, Z ¹ or an alkyl group having 1 to 20 carbon atoms, even if substituted with ^{Z 1.} an alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group or Z ² in Z ¹ in optionally substituted alkynyl group having 2 to 20 carbon atoms, Z ² carbon atoms which may be substituted with 6-20 is represents a heteroaryl group having a carbon number of 2 to 20 even if, R ⁵⁰ is a hydrogen atom, an alkyl group having carbon atoms which may be have 1-20 substituted with Z ^1, optionally substituted by Z ¹ an alkenyl group having 2 to 20 carbon atoms, substituted with an aryl group or Z ² in Z ¹ in optionally substituted alkynyl group having 2 to 20 carbon atoms, Z ² carbon atoms which may be substituted with 6-20 Represents a heteroaryl group having 2 to 20 carbon atoms which may be ^{substituted, and Z 1} is an aryl having 6 to 20 carbon atoms which may be substituted with a halogen atom, a nitro group, a cyano group, a diphenylamino group, or Z ^3. Represents a group or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with ^{Z 3, where Z 2} is a halogen atom, a nitro group, a cyano group, a diphenylamino group, or a carbon which may be substituted with ^{Z 3.} C 1 -C 20 alkyl group, an alkynyl group an alkenyl group or Z ³ may 2-20 carbon atoms substituted with a Z ³ good 2-20 carbon atoms which may be substituted by, Z ³ is Representing a halogen atom, a nitro group, a cyano group or a diphenylamino group, Ar ⁴ has 6 to 20 carbon atoms which may be independently substituted with a di (aryl group having 6 to 20 carbon atoms) amino group. Represents an aryl group.) The charge-transporting varnish according to claim 2, wherein the aniline derivative represented by the formula (1) is represented by any of the formulas (1-1) to (1-4).

(Ar ^{1 to} Ar ³ are different groups represented by any of the above formulas (B1) to (B16), and in each of the formulas, Ar ¹ all represent the same group, and Ar ² Represents all the same groups, and Ar ^{3 represents all the same groups.) The number of groups (nm} ) represented by the formula (P1) and ^{the number of groups (n p} ) represented by the formula (P2) satisfy 0.5 ≦ ^nm / ( ^nm + n ^p ). The charge transporting varnish according to any one of claims 1 to 3. The charge transporting varnish according to any one of claims 1 to 4, which contains a dopant substance. The charge-transporting varnish according to claim 5, wherein the dopant substance is an aryl sulfonic acid ester compound. A charge-transporting thin film produced by using the charge-transporting varnish according to any one of claims 1 to 6. The electronic device including the charge transporting thin film according to claim 7. The organic electroluminescence device including the charge transporting thin film according to claim 7. The organic electroluminescence device according to claim 9, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.