TW201627272A

TW201627272A - Charge-transporting varnish

Info

Publication number: TW201627272A
Application number: TW104131470A
Authority: TW
Inventors: Shoji Moriyama; Hirofumi Ota
Original assignee: Nissan Chemical Ind Ltd
Priority date: 2014-09-29
Filing date: 2015-09-23
Publication date: 2016-08-01
Also published as: WO2016052252A1; JPWO2016052252A1; TWI663147B; JP6601405B2; CN106660939B; KR20170066307A; KR102416124B1; CN106660939A

Abstract

A charge-transporting substance which comprises an arylamine derivative represented by formula (1), the charge-transporting substance showing satisfactory solubility in organic solvents. When a thin film produced from a charge-transporting varnish which contains the charge-transporting substance is applied as a hole injection layer, then an organic EL element having excellent luminance characteristics is rendered possible. [In formula (1), R1 to R8 each independently represent a hydrogen atom, etc.; Ar1 represents a phenyl group, etc.; n is an integer of 1 to 3; and X represents a divalent organic group represented by formula (2a) or (2b). (In formulae (2a) and (2b), R9 and R10 each independently represent a C1-20 alkyl group, etc.; R11 and R12 each independently represent a hydrogen atom or a fluorine atom; R13 to R20 each independently represent a hydrogen atom, etc.; and m is an integer of 1 to 4)].

Description

電荷輸送性清漆 Charge transport varnish

本發明係關於電荷輸送性清漆。 The present invention relates to a charge transporting varnish.

有機電致發光(以下，稱為有機EL)元件係使用由有機化合物所構成之電荷輸送性薄膜作為發光層或電荷注入層。尤其，電洞注入層係負責陽極與電洞輸送層或與發光層之電荷之交換，在為了達成有機EL元件之低驅動電壓及高亮度上展現重要之功能。 In the organic electroluminescence (hereinafter referred to as an organic EL) device, a charge transporting film composed 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 the exchange of the anode and the hole transport layer or the charge of the light-emitting layer, and exhibits an important function in order to achieve a low driving voltage and high brightness of the organic EL element.

電荷輸送性薄膜之形成方法係大致區別為由蒸鍍法所代表之乾式製程與由旋轉塗佈法所代表之濕式製程，若比較此等各製程時，濕式製程能更有效率地製造大面積且高平坦性之薄膜。因此，在有機EL顯示器朝向大面積化前進之現在，希望有在濕式製程下能形成之電洞注入層。 The method for forming a charge transporting film is roughly distinguished by a dry process represented by an evaporation method and a wet process represented by a spin coating method, and the wet process can be more efficiently manufactured by comparing the processes. Large area and high flatness film. Therefore, it is desirable to have a hole injection layer which can be formed in a wet process as the organic EL display is advanced toward a large area.

然而，在有機EL元件之初期特性及壽命特性，及其製造製程上仍有諸多未解決之課題。為了解決此等各式各樣之課題，既有各種關於有機EL元件用之機能性薄膜形成用材料之探討。作為其之一環，已逐漸探討關於具有電洞注入性之電荷輸送性物質至今。 However, there are still many unsolved problems in the initial characteristics and lifetime characteristics of organic EL elements and their manufacturing processes. In order to solve various problems of the above, various materials for forming a functional thin film for an organic EL device have been discussed. As one of the rings, a charge transporting substance having a hole injecting property has been gradually explored to date.

作為具有電洞注入性之電荷輸送性物質，已知有芳基聯苯胺衍生物。例如，已提出將使作為芳基聯苯胺衍生物之四芳基聯苯胺進行交聯成茀構造或環己烷構造者作為電荷輸送性物質(例如參照專利文獻1~5)。 As the charge transporting substance having a hole injecting property, an aryl benzidine derivative is known. For example, it has been proposed to crosslink a tetraarylbenzidine which is an arylbenzidine derivative into a hydrazine structure or a cyclohexane structure as a charge transporting substance (see, for example, Patent Documents 1 to 5).

然而，目前尚未發現關於電荷輸送性物質係使用2個氮原子皆係具有與氫原子之鍵結之芳基聯苯胺衍生物之交聯物之例。 However, it has not been found yet that the charge transporting substance is a crosslinked product in which two nitrogen atoms are linked to an aryl benzidine derivative bonded to a hydrogen atom.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]歐洲專利申請案公開第2684932號說明書 [Patent Document 1] European Patent Application Publication No. 2848932

[專利文獻2]國際公開第2013/022419號 [Patent Document 2] International Publication No. 2013/022419

[專利文獻3]國際公開第2014/009310號 [Patent Document 3] International Publication No. 2014/009310

[專利文獻4]特開2002-179630號公報 [Patent Document 4] JP-A-2002-179630

[專利文獻5]歐洲專利申請案公開第650955號說明書 [Patent Document 5] European Patent Application Publication No. 650955

本發明係有鑑於此種情事所完成者，其目的在於提供一種電洞注入性優異之新穎電荷輸送性物質及包含此之電荷輸送性清漆、由該清漆所得之電荷輸送性薄膜及其製造方法、以及具有該薄膜之有機EL元件。 The present invention has been made in view of such circumstances, and an object thereof is to provide a novel charge transporting material excellent in hole injectability and a charge transporting varnish containing the same, and a charge transporting film obtained from the varnish And a method for producing the same, and an organic EL device having the film.

本發明者等為了達成上述目的經過重複精心探討之結果，發現包含聯苯胺構造之特定芳基胺衍生物具有對有機溶劑之優異溶解性，且由使其溶解於有機溶劑而調製成之清漆能取得發揮高電荷輸送性之薄膜，及將該薄膜適用於有機EL元件之電洞注入層時，能取得亮度特性優異之元件，進而完成了本發明。 The inventors of the present invention have repeatedly conducted intensive investigations to achieve the above object, and have found that a specific arylamine derivative containing a benzidine structure has excellent solubility in an organic solvent, and can be prepared by dissolving it in an organic solvent. When a film exhibiting high charge transport property is obtained and the film is applied to a hole injection layer of an organic EL device, an element having excellent luminance characteristics can be obtained, and the present invention has been completed.

即，本發明為提供以下者。 That is, the present invention provides the following.

1.一種電荷輸送性物質，其係由式(1)所表示之芳基胺衍生物所構成； [式中，R¹~R⁸係互相獨立表示氫原子、鹵素原子、或可經Z¹取代之碳數1~20之烷基或碳數1~20之烷氧基，Ar¹表示可經Z²取代之碳數6~20之芳基，n表示1~3之整數，X表示式(2a)或(2b)所表示之2價有機基， (式中，R⁹及R¹⁰係互相獨立表示碳數1~20之烷基、碳數1~20之氟烷基、可經Z²取代之碳數6~20之芳基，或 R⁹與R¹⁰亦可結合形成碳數3~21之縮環之環式烴基，R¹¹及R¹²係互相獨立表示氫原子或氟原子，R¹³~R²⁰係互相獨立表示氫原子、碳數1~20之烷基、碳數1~20之氟烷基、或Z³，m表示1~4之整數) A charge transporting substance comprising an arylamine derivative represented by the formula (1); [wherein, R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms or a carbon number of 1 to 20 which may be substituted by Z ¹ , and Ar ¹ represents a Z ^{2 is} substituted with an aryl group having 6 to 20 carbon atoms, n is an integer of 1 to 3, and X represents a divalent organic group represented by the formula (2a) or (2b). (wherein R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted by Z ² , or R ⁹ And R ¹⁰ may also be combined to form a cyclic hydrocarbon group having a carbon number of 3 to 21, and R ¹¹ and R ¹² each independently represent a hydrogen atom or a fluorine atom, and R ¹³ to R ²⁰ are independently of each other and represent a hydrogen atom and a carbon number of 1. ~20 alkyl, carbon number 1-20 fluoroalkyl, or Z ³ , m represents an integer from 1 to 4)

Z¹表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、羧酸基、或可經Z³取代之碳數6~20之芳基或碳數2~20之雜芳基；Z²表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、羧酸基，或可經Z³取代之碳數1~20之烷基、碳數2~20之烯基或碳數2~20之炔基；Z³表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、或羧酸基]。 Z ¹ represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a decyl group, a sulfonic acid group, a carboxylic acid group, or an aryl group having a carbon number of 6 to 20 which may be substituted by Z ³ or a carbon number of 2~ a heteroaryl group of 20; Z ² represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a decyl group, a sulfonic acid group, a carboxylic acid group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by Z ³ a base, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms; and Z ³ represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a decyl group, a sulfonic acid group, or a carboxylic acid group. ].

2.如1之電荷輸送性物質，其中前述X為一種選自式(3a)~(3h)所表示之2價有機基； 2. The charge transporting substance according to 1, wherein X is a divalent organic group selected from the group consisting of formulas (3a) to (3h);

3.一種電荷輸送性材料，其係包含如1或2之電荷輸送性物質。 A charge transporting material comprising a charge transporting substance such as 1 or 2.

4.一種電荷輸送性清漆，其係包含如1或2之電荷輸送性物質與有機溶劑。 A charge transporting varnish comprising a charge transporting substance such as 1 or 2 and an organic solvent.

5.如4之電荷輸送性清漆，其中更包含摻質物質。 5. A charge transporting varnish as in 4, which further comprises a dopant substance.

6.如5之電荷輸送性清漆，其中前述摻質物質包含雜多酸。 6. A charge transporting varnish according to 5, wherein said dopant substance comprises Heteropolyacids.

7.一種電荷輸送性薄膜，其係使用如4~6中任一項之電荷輸送性清漆所製作者。 A charge transporting film produced by using the charge transporting varnish of any one of 4 to 6.

8.一種有機電致發光元件，其係具有如7之電荷輸送性薄膜。 An organic electroluminescence device comprising a charge transporting film of 7, for example.

9.一種電荷輸送性薄膜之製造方法，其係將如4~6中任一項之電荷輸送性清漆塗佈於基材上並使溶劑蒸發。 A method for producing a charge transporting film, which comprises applying a charge transporting varnish according to any one of 4 to 6 to a substrate and evaporating the solvent.

本發明之電荷輸送性物質即芳基胺衍生物係容易溶解於有機溶劑，使此與摻質一同溶解於有機溶劑即能容易地調製成電荷輸送性清漆。 The arylamine derivative which is a charge transporting substance of the present invention is easily dissolved in an organic solvent, and this can be easily prepared into a charge transporting varnish by dissolving it together with a dopant in an organic solvent.

由本發明之電荷輸送性清漆所製作之薄膜由於展現高電荷輸送性，故能適宜做為以有機EL元件為首之電子裝置用之薄膜。尤其，藉由將此薄膜適用於有機EL元件之電洞注入層，即能取得亮度特性優異之有機EL元件。 Since the film produced by the charge transporting varnish of the present invention exhibits high charge transportability, it can be suitably used as a film for an electronic device including an organic EL device. In particular, when the film is applied to a hole injection layer of an organic EL device, an organic EL device excellent in luminance characteristics can be obtained.

又，本發明之電荷輸送性清漆即使在使用旋轉塗佈法或狹縫塗佈法等能大面積成膜之各種濕式製程之情況，仍能再現性良好地製造電荷輸送性優異之薄膜，故亦能充分對應近年來有機EL元件領域中之進展。 Moreover, even in the case of various wet processes capable of forming a large-area film, such as a spin coating method or a slit coating method, the charge-transporting varnish of the present invention can produce a film excellent in charge transportability with good reproducibility. Therefore, it can fully cope with the progress in the field of organic EL elements in recent years.

又，從本發明之電荷輸送性清漆所得之薄膜亦能使用作為防帶電膜或有機薄膜太陽電池之陽極緩衝層等。 Further, the film obtained from the charge transporting varnish of the present invention can also be used as an antistatic film or an anode buffer layer of an organic thin film solar cell.

以下，更詳細說明關於本發明。 Hereinafter, the present invention will be described in more detail.

本發明之電荷輸送性物質係由式(1)所表示之芳基胺衍生物所構成。 The charge transporting substance of the present invention is composed of an arylamine derivative represented by the formula (1).

在此，電荷輸送性係意指與導電性同義，且係與電洞輸送性同義。電荷輸送性物質可為其自身具有電荷輸送性者，亦可為與摻雜物質一同使用時具有電荷輸送性者。電荷輸送性清漆可為其自身具有電荷輸送性者，亦可為藉此而得之固形膜係具有電荷輸送性者。 Here, the charge transportability means synonymous with conductivity and is synonymous with hole transportability. The charge transporting substance may have a charge transporting property for itself, or may have a charge transporting property when used together with a dopant. The charge transporting varnish may have a charge transporting property by itself, or a solid film obtained therefrom may have a charge transporting property.

式(1)中，R¹~R⁸係互相獨立表示氫原子、鹵素原子，或可經Z¹取代之碳數1~20之烷基或碳數1~20之烷氧基。 In the formula (1), R ¹ to R ⁸ each independently represent a hydrogen atom or a halogen atom, or an alkyl group having 1 to 20 carbon atoms or a carbon number of 1 to 20 which may be substituted by Z ¹ .

作為鹵素原子，可舉出如氟原子、氯原子、溴原子、碘原子等。 The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

作為碳數1~20之烷基之具體例，可為直鏈狀、分枝鏈狀、環狀之任意者，可舉出例如，甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、n-己基、n-庚基、n-辛基、n-壬基、n-癸基等之碳數1~20之直鏈或分枝鏈狀烷基；環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、雙環丁基、雙環戊基、雙環己基、雙環庚基、雙環辛基、雙環壬基、雙環癸基等之碳數3~20之環狀烷基等。 Specific examples of the alkyl group having 1 to 20 carbon atoms may be any of a linear chain, a branched chain, and a cyclic ring, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Carbon of n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, etc. a straight or branched chain alkyl group of 1 to 20; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, bicyclobutyl, Bicyclopentyl, dicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclic guanidine a cyclic alkyl group having a carbon number of 3 to 20, such as a bis-indenyl group or the like.

作為碳數1~20之烷氧基之具體例，其中之烷基可為直鏈狀、分枝鏈狀、環狀之任意者，可舉出例如，甲氧基、乙氧基、n-丙氧基、i-丙氧基、c-丙氧基、n-丁氧基、i-丁氧基、s-丁氧基、t-丁氧基、c-丁氧基、n-戊氧基、1-甲基-n-丁氧基、2-甲基-n-丁氧基、3-甲基-n-丁氧基、1,1-二甲基-n-丙氧基、c-戊氧基、2-甲基-c-丁氧基、n-己氧基、1-甲基-n-戊氧基、2-甲基-n-戊氧基、1,1-二甲基-n-丁氧基、1-乙基-n-丁氧基、1,1,2-三甲基-n-丙氧基、c-己氧基、1-甲基-c-戊氧基、1-乙基-c-丁氧基、1,2-二甲基-c-丁氧基、n-庚氧基、n-辛氧基、n-壬氧基、n-癸氧基等。 Specific examples of the alkoxy group having 1 to 20 carbon atoms may be any of a linear chain, a branched chain, and a cyclic group, and examples thereof include a methoxy group, an ethoxy group, and an n- group. Propyloxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, c-butoxy, n-pentyloxy , 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, c -pentyloxy, 2-methyl-c-butoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 1,1-dimethyl Base-n-butoxy, 1-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, c-hexyloxy, 1-methyl-c-pentyloxy , 1-ethyl-c-butoxy, 1,2-dimethyl-c-butoxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy Wait.

Ar¹表示可經Z²取代之碳數6~20之芳基。 Ar ¹ represents an aryl group having 6 to 20 carbon atoms which may be substituted by Z ² .

作為碳數6~20之芳基之具體例，可舉出如苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等。 Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, and a 1-phenanthryl group. 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and the like.

n表示1~3之整數，較佳為1。 n represents an integer of 1 to 3, preferably 1.

X表示式(2a)或(2b)所表示之2價有機基。 X represents a divalent organic group represented by the formula (2a) or (2b).

R⁹及R¹⁰係互相獨立表示碳數1~20之烷基、碳數1~20之氟烷基、可經Z²取代之碳數6~20之芳基，或表示R⁹與R¹⁰結合形成碳數3~21之亦可縮環之環式烴基，R¹¹及R¹²係互相獨立表示氫原子或氟原子，R¹³~R²⁰係互相獨立表示氫原子、碳數1~20之烷基、碳數1~20之氟烷基，或Z³。 R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted by Z ² , or R ⁹ and R ¹⁰ The ring-shaped hydrocarbon group which can form a condensed ring having a carbon number of 3 to 21 is bonded, and R ¹¹ and R ¹² each independently represent a hydrogen atom or a fluorine atom, and R ¹³ to R ²⁰ are independently of each other and represent a hydrogen atom and a carbon number of 1 to 20. An alkyl group, a fluoroalkyl group having 1 to 20 carbon atoms, or Z ³ .

作為碳數1~20之烷基、碳數6~20之芳基，可舉出與上述相同者。 Examples of the aryl group having 1 to 20 carbon atoms and 6 to 20 carbon atoms are the same as those described above.

作為碳數1~20之氟烷基之具體例，可為直鏈狀、分枝鏈狀、環狀之任意者，可舉出例如，三氟甲基、五氟乙基、2,2,2-三氟乙基、七氟丙基、2,2,3,3,3-五氟丙基、2,2,3,3-四氟丙基、2,2,2-三氟-1-(三氟甲基)乙基、九氟丁基、4,4,4-三氟丁基、十一氟戊基、2,2,3,3,4,4,5,5,5-九氟戊基、2,2,3,3,4,4,5,5-八氟戊基、十三氟己基、2,2,3,3,4,4,5,5,6,6,6-十一氟己基、2,2,3,3,4,4,5,5,6,6-十氟己基、3,3,4,4,5,5,6,6,6-九氟己基等。 Specific examples of the fluoroalkyl group having 1 to 20 carbon atoms may be any of a linear chain, a branched chain, and a cyclic ring, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, and 2,2. 2-Trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1 -(trifluoromethyl)ethyl, nonafluorobutyl, 4,4,4-trifluorobutyl, undecafluoropentyl, 2,2,3,3,4,4,5,5,5- Nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, decafluorohexyl, 2,2,3,3,4,4,5,5,6,6 ,6-undefluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6- Nonafluorohexyl and the like.

m表示1~4之整數，較佳為1。 m represents an integer of 1 to 4, preferably 1.

又，作為R⁹與R¹⁰結合而形成之碳數3~21之亦可縮環之環式烴基，可舉出如下述式所示者，但並不受限於此等者。 In addition, the cyclic hydrocarbon group which may be a condensed ring having 3 to 21 carbon atoms which is formed by the combination of R ⁹ and R ¹⁰ may be exemplified by the following formula, but is not limited thereto.

(式中，「‧」係表示與亞甲基鏈之結合部位。) (In the formula, "‧" indicates the binding site to the methylene chain.)

Z¹表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、羧酸基，或可經Z³取代之碳數6~20之芳基或碳數2~20之雜芳基，Z²表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、羧酸基，或可經Z³取代之碳數1~20之烷基、碳數2~20之烯基或碳數2~20之炔基，Z³表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、或羧酸基。 Z ¹ represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a decyl group, a sulfonic acid group, a carboxylic acid group, or an aryl group having a carbon number of 6 to 20 which may be substituted by Z ³ or a carbon number of 2~ a heteroaryl group of 20, Z ² represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a decyl group, a sulfonic acid group, a carboxylic acid group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by Z ³ a base, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, and Z ³ represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a decyl group, a sulfonic acid group, or a carboxylic acid group. .

作為此等鹵素原子、碳數1~20之烷基、碳數6~20之芳基，可舉出如與上述相同者。 Examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those described above.

作為碳數2~20之雜芳基之具體例，可舉出如2-噻吩基、3-噻吩基、2-呋喃基、3-呋喃基、2-噁唑基、4-噁唑基、5-噁唑基、3-異噁唑基、4-異噁唑基、5-異噁唑基、2-噻唑基、4-噻唑基、5-噻唑基、3-異噻唑基、4-異噻唑基、5-異噻唑基、2-咪唑基、4-咪唑基、2-吡啶基、3-吡啶基、4-吡啶基等。 Specific examples of the heteroaryl group having 2 to 20 carbon atoms include a 2-thienyl group, a 3-thienyl group, a 2-furyl group, a 3-furyl group, a 2-oxazolyl group, and a 4-oxazolyl group. 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4- Isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl and the like.

作為碳數2~20之烯基之具體例，可舉出如乙烯基、n-1-丙烯基、n-2-丙烯基、1-甲基乙烯基、n-1-丁烯基、n-2-丁烯基、n-3-丁烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、1-乙基乙烯基、1-甲基-1-丙烯基、1-甲基-2-丙烯基、n-1-戊烯基、n-1-癸烯基、n-1-二十烯基等。 Specific examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, an n-1-propenyl group, an n-2-propenyl group, a 1-methylvinyl group, an n-1-butenyl group, and n. 2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propene A group, a 1-methyl-2-propenyl group, an n-1-pentenyl group, an n-1-decenyl group, an n-1-icosyl group, and the like.

作為碳數2~20之炔基之具體例，可舉出如乙炔基、n-1-丙炔基、n-2-丙炔基、n-1-丁炔基、n-2-丁炔基、n-3-丁炔基、1-甲基-2-丙炔基、n-1-戊炔基、n-2-戊炔基、n-3-戊炔基、n-4-戊炔基、1-甲基-n-丁炔基、2-甲基-n-丁炔基、3-甲基-n-丁炔基、1,1-二甲基-n-丙炔基、n-1-己炔基、n-1-癸炔基、n-1-十五炔基、n-1-二十炔基等。 Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, and n-2-butyne. Base, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentyl Alkynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butyne 1,1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecenyl, n-1-eicoyl, etc. .

此等之中，作為R¹~R⁸係以互相獨立為氫原子、碳數1~6之烷基、碳數1~6之烷氧基為佳，以互相獨立為氫原子、甲基、乙基、甲氧基為較佳，以皆係氫原子為更較佳。 Among these, R ¹ to R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and each independently represents a hydrogen atom or a methyl group. Ethyl or methoxy is preferred, and more preferably a hydrogen atom.

作為Ar¹，以可經Z²取代之苯基為佳，以非取代之苯基為較佳。 As Ar ¹ , a phenyl group which may be substituted by Z ^{2 is} preferred, and an unsubstituted phenyl group is preferred.

作為R⁹及R¹⁰，以碳數1~6之烷基、碳數1~6之氟烷基、可經Z²取代之碳數6~18之芳基、R⁹與R¹⁰結合而成之下述式所表示之環式烴基為佳，以甲基、R⁹與R¹⁰結合而成之下述式所表示之環式烴基為較佳。 R ⁹ and R ^{10 are a combination} of an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms which may be substituted by Z ² , and R ⁹ and R ¹⁰ . The cyclic hydrocarbon group represented by the following formula is preferred, and a cyclic hydrocarbon group represented by the following formula in which a methyl group, R ⁹ and R ^{10 are} combined is preferred.

作為R¹¹及R¹²，以皆係氫原子為佳。 As R ¹¹ and R ¹² , a hydrogen atom is preferred.

作為R¹³~R²⁰，以互相獨立為氫原子、甲基、乙基、三氟甲基、鹵素原子為佳，以皆係氫原子為較佳。 R ¹³ to R ^{20 are} preferably each independently a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group or a halogen atom, and all of them are preferably a hydrogen atom.

(式中，「‧」表示與亞甲基鏈之結合部位。) (In the formula, "‧" indicates the binding site to the methylene chain.)

因此，X係以式(3a)~(3h)所表示之任意之2價有機基為適宜。 Therefore, X is preferably an arbitrary divalent organic group represented by the formula (3a) to (3h).

其中，亦以式(3a’)~(3h’)所表示任意之2價有機基的情況為更佳。 Further, it is more preferable that the arbitrary divalent organic group represented by the formula (3a') to (3h') is also used.

尚且，上述烷基、氟烷基、烷氧基、烯基及炔基之碳數係以10以下為佳，較佳為6以下，更佳為4以下。 Further, the carbon number of the alkyl group, the fluoroalkyl group, the alkoxy group, the alkenyl group and the alkynyl group is preferably 10 or less, more preferably 6 or less, still more preferably 4 or less.

又，芳基及雜芳基之碳數係以14以下為佳，較佳為10以下，更佳為6以下。 Further, the carbon number of the aryl group and the heteroaryl group is preferably 14 or less, more preferably 10 or less, still more preferably 6 or less.

上述芳基胺衍生物之分子量通常在300~5,000，但從提高溶解性之觀點，以4,000以下為佳，較佳為3,000以下，更佳為2,000以下。 The molecular weight of the arylamine derivative is usually from 300 to 5,000. From the viewpoint of improving solubility, it is preferably 4,000 or less, more preferably 3,000 or less, still more preferably 2,000 or less.

本發明之式(1)所示之芳基胺衍生物係使聯苯基化合物與二胺化合物在觸媒存在下使其反應而能製造者，但不受限於此製造法。 The arylamine derivative represented by the formula (1) of the present invention can be produced by reacting a biphenyl compound and a diamine compound in the presence of a catalyst. However, it is not limited to this manufacturing method.

例如，具有X係式(2a)所示之2價有機基之芳基胺衍生物(6)係使式(4)所示之聯苯基化合物與式(5)所示之二胺化合物在觸媒存在下進行反應而能取得。 For example, the arylamine derivative (6) having a divalent organic group represented by the formula X (2a) is a biphenyl compound represented by the formula (4) and a diamine compound represented by the formula (5). It can be obtained by reacting in the presence of a catalyst.

(式中，Z表示鹵素原子或擬鹵素基，R¹~R¹⁰、R¹³~R²⁰、Ar¹及n係表示與上述相同意義。) (wherein Z represents a halogen atom or a pseudohalogen group, and R ¹ to R ¹⁰ , R ¹³ to R ²⁰ , Ar ¹ and n represent the same meanings as described above.)

又，具有X係式(2b)所示之2價有機基之芳基胺衍生物(8)係使式(4)所示之聯苯基化合物與式(7)所示之二胺化合物在觸媒存在下進行反應而能取得。 Further, the arylamine derivative (8) having a divalent organic group represented by the formula X (2b) is a biphenyl compound represented by the formula (4) and a diamine compound represented by the formula (7). It can be obtained by reacting in the presence of a catalyst.

(式中，Z表示鹵素原子或擬鹵素基，R¹~R⁸、R¹¹~R²⁰、 Ar¹、m及n係表示與上述相同意義。) (wherein Z represents a halogen atom or a pseudohalogen group, and R ¹ to R ⁸ , R ¹¹ to R ²⁰ , Ar ¹ , m and n represent the same meanings as described above.)

作為鹵素原子，可舉出與上述相同者。 The halogen atom is the same as the above.

作為擬鹵素基，可舉出如甲烷磺醯氧基、三氟甲烷磺醯氧基、九氟丁烷磺醯氧基等之(氟)烷基磺醯氧基；苯磺醯氧基、甲苯磺醯氧基等之芳香族磺醯氧基等。 Examples of the pseudohalogen group include (fluoro)alkylsulfonyloxy group such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group; benzenesulfonyloxy group; toluene; An aromatic sulfonyloxy group such as a sulfonyloxy group.

式(5)所表示之二胺化合物與式(4)所表示之聯苯基化合物之添加比係相對於二胺化合物之全NH基之物質量而言，可將聯苯基化合物作成當量以上，但適宜為1~1.2當量程度。 The addition ratio of the diamine compound represented by the formula (5) to the biphenyl compound represented by the formula (4) is such that the biphenyl compound can be made equivalent or more with respect to the mass of the total NH group of the diamine compound. , but suitable for the range of 1 to 1.2 equivalents.

作為上述反應所使用之觸媒，可舉出例如，氯化銅、溴化銅、碘化銅等之銅觸媒；Pd(PPh₃)₄(肆(三苯基膦)鈀)、Pd(PPh₃)₂Cl₂(雙(三苯基膦)二氯鈀)、Pd(dba)₂(雙(亞苄基丙酮)鈀)、Pd₂(dba)₃(參(亞苄基丙酮)二鈀)、Pd(P-t-Bu₃)₂(雙(三(t-丁基)膦)鈀)等之鈀觸媒等。此等觸媒係可單獨使用，亦可將2種以上組合使用。又，此等觸媒係亦可與公知適宜之配位子一同使用。 The catalyst used in the above reaction may, for example, be a copper catalyst such as copper chloride, copper bromide or copper iodide; Pd(PPh ₃ ) ₄ (yttrium (triphenylphosphine)palladium), Pd ( PPh ₃ ) ₂ Cl ₂ (bis(triphenylphosphine)dichloropalladium), Pd(dba) ₂ (bis(benzylideneacetone)palladium), Pd ₂ (dba) ₃ (gins (benzylideneacetone) 2 Palladium catalysts such as palladium) and Pd(Pt-Bu ₃ ) ₂ (bis(tris(t-butyl)phosphine)palladium). These catalysts may be used singly or in combination of two or more. Moreover, these catalysts can also be used together with well-known and suitable ligands.

觸媒之使用量係將使用之二胺化合物作成1mol時，可做成0.001~0.5mol程度，但適宜為0.01~0.1mol程度。 When the amount of the catalyst used is 1 mol, the amount of the diamine compound to be used is 0.001 to 0.5 mol, but it is preferably 0.01 to 0.1 mol.

又，在使用配位子時，其使用量係相對於所使用之金屬錯合物，可做成0.1~5當量，但適宜為1~2當量。 Further, when a ligand is used, the amount used is 0.1 to 5 equivalents, preferably 1 to 2 equivalents, per mole of the metal complex used.

上述反應亦可在溶劑中進行。在使用溶劑時，其之種類只要係不對反應造成不良影響者，即無特別限制。作為具體例，可舉出如脂肪族烴類(戊烷、n-己烷、n-辛烷、n-癸烷、十氫萘等)、鹵化脂肪族烴類(氯仿、二氯甲烷、二氯乙烷、四氯化碳等)、芳香族烴類(苯、硝基苯、甲苯、o-茬、m-茬、p-茬、均三甲苯等)、鹵化芳香族烴類(氯苯、溴苯、o-二氯苯、m-二氯苯、p-二氯苯等)、醚類(二乙基醚、二異丙基醚、t-丁基甲基醚、四氫呋喃、二噁烷、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等)、酮類(丙酮、甲基乙基酮、甲基異丁基酮、二-n-丁基酮、環己酮等)、醯胺類(N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等)、內醯胺及內酯類(N-甲基吡咯啶酮、γ-丁內酯等)、脲類(N,N-二甲基咪唑啉酮、四甲基脲等)、亞碸類(二甲亞碸、環丁碸等)、腈類(乙腈、丙腈、丁腈等)等，此等之溶劑係可單獨使用，亦可混合2種以上使用。 The above reaction can also be carried out in a solvent. When a solvent is used, the type thereof is not particularly bad if it does not adversely affect the reaction. limit. Specific examples thereof include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decahydronaphthalene, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, and two). Ethylene chloride, carbon tetrachloride, etc., aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-茬, m-茬, p-茬, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene) , bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, Cyclohexanone, etc., guanamines (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), indoleamines and lactones (N-methylpyrrolidone, Γ-butyrolactone, etc., urea (N,N-dimethylimidazolidinone, tetramethylurea, etc.), fluorene (dimethyl hydrazine, cyclobutyl hydrazine, etc.), nitrile (acetonitrile, propyl The solvent may be used singly or in combination of two or more kinds thereof, such as a nitrile or a nitrile.

反應溫度適宜設定在所使用之溶劑融點至沸點為止之範圍內即可，尤其係以0~200℃程度為佳，以20~150℃為較佳。 The reaction temperature is preferably set within the range from the melting point of the solvent to the boiling point, and particularly preferably from 0 to 200 ° C, preferably from 20 to 150 ° C.

反應結束後依循常法進行後處理，即能取得目的之芳基胺衍生物。 After the completion of the reaction, the post-treatment is carried out according to the usual method, whereby the desired arylamine derivative can be obtained.

尚且，式(4)所示之聯苯基化合物係使Ar¹NH₂(Ar¹表示與上述相同意義)與4,4’-二鹵化或二擬鹵化聯苯基化合物在與上述相同之觸媒下進行反應而能取得。 Further, the biphenyl compound represented by the formula (4) is such that Ar ¹ NH ₂ (Ar ¹ represents the same meaning as described above) and the 4,4′-dihalogenated or di-halogenated biphenyl compound are in the same touch as above. It can be obtained by reacting under the medium.

作為式(1)所表示之芳基胺衍生物之具體例，可舉出如下述式所表示者，但並非係受限於此等。尚且，式中Y¹及Y²係各別代表以下所示之1價有機基。 Specific examples of the arylamine derivative represented by the formula (1) include those represented by the following formulas, but are not limited thereto. Further, in the formula, each of Y ¹ and Y ² represents a monovalent organic group shown below.

本發明之電荷輸送性清漆雖為包含由式(1)所表示之芳基胺衍生物所構成之電荷輸送性物質與有機溶劑者，但因應取得之薄膜之用途，在提升其電荷輸送能力等目的上，亦可包含摻質物質。 The charge transporting varnish of the present invention is a charge transporting material and an organic solvent comprising an arylamine derivative represented by the formula (1), but the charge transporting ability is improved in accordance with the use of the obtained film. The purpose may also include a dopant substance.

作為摻質物質，只要係會溶解於清漆所使用之至少1種溶劑者，即無特別限定，能無機系之摻質物質、有機系之摻質物質之任意者。 The dopant substance is not particularly limited as long as it is dissolved in at least one solvent used in the varnish, and any of the inorganic dopant substance and the organic dopant substance can be used.

作為無機系之摻質物質，可舉出如氯化氫、硫酸、硝酸、磷酸等之無機酸；氯化鋁(III)(AlCl₃)、四氯化鈦(IV)(TiCl₄)、三溴化硼(BBr₃)、三氟化硼醚錯合物(BF₃‧OEt₂)、氯化鐵(III)(FeCl₃)、氯化銅(II)(CuCl₂)、五氯化銻(V)(SbCl₅)、五氟化銻(V)(SbF₅)、五氟化砷(V)(AsF₅)、五氟化磷(PF₅)、參(4-溴苯基)鋁六氯銻酸鹽(TBPAH)等之金屬鹵化物；Cl₂、Br₂、I₂、ICl、ICl₃、IBr、IF₄等之鹵素；磷鉬酸、磷鎢酸等之雜多酸等。 Examples of the inorganic dopants include inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; aluminum (III) chloride (AlCl ₃ ), titanium tetrachloride (IV) (TiCl ₄ ), and tribromination. Boron (BBr ₃ ), boron trifluoride ether complex (BF ₃ ‧OEt ₂ ), iron (III) chloride (FeCl ₃ ), copper (II) chloride (CuCl ₂ ), antimony pentachloride (V) ) (SbCl ₅ ), antimony pentafluoride (V) (SbF ₅ ), arsenic pentafluoride (V) (AsF ₅ ), phosphorus pentafluoride (PF ₅ ), ginseng (4-bromophenyl) aluminum hexachloro a metal halide such as citrate (TBPAH); a halogen such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF ₄ or the like; a heteropoly acid such as phosphomolybdic acid or phosphotungstic acid.

作為有機系之摻雜物質，可舉出如苯磺酸、甲苯磺酸、p-苯乙烯磺酸、2-萘磺酸、4-羥基苯磺酸、5-磺柳酸、p-十二基苯磺酸、二己基苯磺酸、2,5-二己基苯磺酸、二丁基萘磺酸、6,7-二丁基-2-萘磺酸、十二基萘磺酸、3-十二基-2-萘磺酸、己基萘磺酸、4-己基-1-萘磺酸、辛基萘磺酸、2-辛基-1-萘磺酸、己基萘磺酸、7-己基-1-萘磺酸、6-己基-2-萘磺酸、二壬基萘磺酸、2,7-二壬基-4-萘磺酸、二壬基萘二磺酸、2,7-二壬基-4,5-萘二磺酸、國際公開第2005/000832號記載之1,4-苯並二噁烷二磺酸化合物、國際公開第2006/025342號記載之芳基磺酸化合物、國際公開第2009/096352號記載之芳基磺酸化合物、聚苯乙烯磺酸等之芳基碸化合物；10-樟腦磺酸等之非芳基碸化合物；7,7,8,8-四氰基醌二甲烷(TCNQ)、2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)等之有機氧化劑。 Examples of the doping substance of the organic system include benzenesulfonic acid, toluenesulfonic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfuric acid, and p-tweldium. Benzobenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3 - dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 7- Hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dimercapto-4-naphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, 2,7 - Dimercapto-4,5-naphthalene disulfonic acid, 1,4-benzodioxane disulfonic acid compound described in International Publication No. 2005/000832, and arylsulfonic acid described in International Publication No. 2006/025342 a compound, an arylsulfonic acid compound described in International Publication No. 2009/096352, An aryl sulfonium compound such as polystyrene sulfonic acid; a non-aryl hydrazine compound such as 10-camphorsulfonic acid; 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro- An organic oxidizing agent such as 5,6-dicyano-1,4-benzoquinone (DDQ).

此等無機系及有機系之摻雜物質係可單獨使用1種類，亦可將2種類以上組合使用。 These inorganic and organic doping substances may be used alone or in combination of two or more.

此等摻雜物質之中則以雜多酸為適宜，藉由使用雜多酸做為摻雜物質，即能取得不僅展現來自以銦錫氧化物(ITO)、銦鋅氧化物(IZO)所代表之透明電極之高電洞接受能力，且展現來自以鋁所代表之金屬陽極之高電洞接受能力之電荷輸送性優異之薄膜。 Among these doping substances, heteropoly acid is suitable, and by using a heteropoly acid as a dopant, it can be obtained not only by indium tin oxide (ITO) or indium zinc oxide (IZO). The high-hole acceptance capability of the transparent electrode is represented, and the film exhibiting excellent charge transportability from the high-hole accepting ability of the metal anode represented by aluminum is exhibited.

雜多酸係指由代表性地以式(B1)所示之Keggin型或式(B2)所示之Dawson型之化學構造所示之具有雜原子位於分子中心之構造，且係釩(V)、鉬(Mo)、鎢(W)等之含氧酸即同素聚合酸與異種元素之含氧酸進行縮合而成之多元酸。作為此種異種元素之含氧酸，主要可舉出如矽(Si)、磷(P)、砷(As)之含氧酸。 The heteropoly acid refers to a structure having a hetero atom located at the center of the molecule, represented by a Keggin type represented by the formula (B1) or a chemical structure of the Dawson type represented by the formula (B2), and is vanadium (V). An oxyacid such as molybdenum (Mo) or tungsten (W) is a polybasic acid obtained by condensing an oxo acid of a homologous element with an oxo acid of a different element. As the oxo acid of such a different element, an oxo acid such as cerium (Si), phosphorus (P) or arsenic (As) is mainly mentioned.

作為雜多酸之具體例，可舉出如磷鉬酸、矽鉬酸、磷鎢酸、矽鎢酸、磷鎢鉬酸等，此等係可單獨使用，亦可將2種以上組合使用。尚且，本發明使用之雜多酸係能取得作為市售品，又，亦能藉由公知方法進行合成。 Specific examples of the heteropoly acid include phosphomolybdic acid, hydrazine molybdate, phosphotungstic acid, decanoic acid, and phosphotungstic acid. These may be used singly or in combination of two or more. Further, the heteropoly acid system used in the present invention can be obtained as a commercially available product, and can also be combined by a known method. to make.

尤其，摻質物質係單獨由1種類之雜多酸所構成時，該1種類之雜多酸係以磷鎢酸或磷鉬酸為佳，但以磷鎢酸為最適宜。又，摻質物質係由2種類以上之雜多酸所構成時，該2種類以上之雜多酸之一係以磷鎢酸或磷鉬酸為佳，但以磷鎢酸為較佳。 In particular, when the dopant substance is composed of one type of heteropoly acid alone, the heteropoly acid of the one type is preferably phosphotungstic acid or phosphomolybdic acid, but phosphotungstic acid is most preferable. Further, when the dopant substance is composed of two or more kinds of heteropolyacids, one of the two or more types of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, but phosphotungstic acid is preferred.

尚且，雜多酸在元素分析等之定量分析下，即使係元素之數量多於或少於一般式所示之構造者，其只要係取得作為市售品或藉由公知之合成方法適宜合成者，皆能使用在本發明中。 Further, in the quantitative analysis of elemental analysis or the like, even if the number of the elemental elements is more or less than that of the structure represented by the general formula, it is preferably obtained as a commercial product or a synthetic compound by a known synthesis method. Both can be used in the present invention.

即，例如一般而言，磷鎢酸係以化學式H₃(PW₁₂O₄₀)‧nH₂O所示，而磷鉬酸係以化學式H₃(PMo₁₂O₄₀)‧nH₂O所表示，在定量分析下，此式中之P(磷)、O(氧)或W(鎢)或Mo(鉬)之數量即使為較多者或較少者，只要其係取得作為市售品者，或依照公知之合成方法所適宜合成者，皆能使用在本發明中。此時，本發明所規定之雜多酸之質量並非係指合成物或市售品中之純粹磷鎢酸之質量(磷鎢酸含量)，而係指在能取得作為市售品之形態及公知合成法下能單離之形態中，包含水合水或其他雜質等之狀態下之全質量。 That is, for example, in general, the phosphotungstic acid is represented by the chemical formula H ₃ (PW ₁₂ O ₄₀ ) ‧nH ₂ O, and the phosphomolybdic acid is represented by the chemical formula H ₃ (PMo ₁₂ O ₄₀ )‧nH ₂ O, Under quantitative analysis, if the amount of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is larger or smaller, as long as it is obtained as a commercial product, Or those suitable for synthesis according to well-known synthetic methods can be used in the present invention. In this case, the quality of the heteropolyacid specified in the present invention does not refer to the mass of the pure phosphotungstic acid (phosphoric acid content) in the composition or the commercial product, but refers to the form which can be obtained as a commercial product and It is known that the total mass in a state in which it can be separated in the synthesis method includes hydrated water or other impurities.

又，亦能適宜使用芳基磺酸化合物作為摻雜物質。尤其以式(7)或(8)所表示之芳基磺酸化合物為佳。 Further, an arylsulfonic acid compound can also be suitably used as the dopant. In particular, an arylsulfonic acid compound represented by the formula (7) or (8) is preferred.

A¹表示O或S，但以O為佳。 A ¹ represents O or S, but O is preferred.

A²表示萘環或蒽環，但以萘環為佳。 A ² represents a naphthalene ring or an anthracene ring, but a naphthalene ring is preferred.

A³表示2~4價之全氟聯苯基，p表示A¹與A³之結合數係且滿足2≦p≦4之整數，A³為2價之全氟聯苯基，且p係以2為佳。 A ³ represents a 2 to 4 valence perfluorobiphenyl group, p represents a combination of A ¹ and A ³ and satisfies an integer of 2≦p≦4, A ³ is a divalent perfluorobiphenyl group, and p is a system Take 2 as the best.

q表示結合於A²之磺酸基數，且係滿足1≦q≦4之整數，但以2為最佳。 q represents the number of sulfonic acid groups bonded to A ² and is an integer satisfying 1 ≦ q ≦ 4, but 2 is most preferable.

A⁴~A⁸係互相獨立表示氫原子、鹵素原子、氰基、碳數1~20之烷基、碳數1~20之鹵化烷基、或碳數2~20之鹵化烯基，A⁴~A⁸之中至少3各為鹵素原子。 A ⁴ to A ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms, and A ⁴ At least 3 of each of ~A ⁸ are halogen atoms.

作為碳數1~20之鹵化烷基，可舉出如三氟甲基、2,2,2-三氟乙基、1,1,2,2,2-五氟乙基、3,3,3-三氟丙基、2,2,3,3,3-五氟丙基、1,1,2,2,3,3,3-七氟丙基、4,4,4-三氟丁基、3,3,4,4,4-五氟丁基、2,2,3,3,4,4,4-七氟丁基、1,1,2,2,3,3,4,4,4-九氟丁基等。 Examples of the halogenated alkyl group 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 Base, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4, 4,4-nonafluorobutyl and the like.

作為碳數2~20之鹵化烯基，可舉出如全氟乙烯基、全氟丙烯基(烯丙基)、全氟丁烯基等。 Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include a perfluorovinyl group, a perfluoropropenyl group (allyl), and a perfluorobutenyl group.

其他，作為鹵素原子、碳數1~20之烷基之例，可舉出與上述相同者，但鹵素原子係以氟原子為佳。 Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms are the same as those described above, but the halogen atom is preferably a fluorine atom.

此等之中，以A⁴~A⁸為氫原子、鹵素原子、氰基、碳數1~10之烷基、碳數1~10之鹵化烷基或碳數 2~10之鹵化烯基，且A⁴~A⁸之中至少3個為氟原子為佳，以氫原子、氟原子、氰基、碳數1~5之烷基、碳數1~5之氟化烷基或碳數2~5之氟化烯基，且A⁴~A⁸之中至少3個為氟原子為較佳，以氫原子、氟原子、氰基、碳數1~5之全氟烷基或碳數1~5之全氟烯基，且A⁴、A⁵及A⁸皆係氟原子為更較佳。 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, a halogenated alkyl group having 1 to 10 carbon atoms or a halogenated alkenyl group having 2 to 10 carbon atoms. And at least 3 of A ⁴ to A ⁸ are preferably a fluorine atom, and a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms or a carbon number of 2 a fluorinated alkenyl group of ~5, and at least 3 of A ⁴ to A ⁸ are preferably a fluorine atom, and a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms or a carbon number of 1 More preferably, a perfluoroalkenyl group of ~5, and A ⁴ , A ⁵ and A ^{8 are} all fluorine atoms.

尚且，全氟烷基係指烷基之氫原子全部被氟原子所取代之基，全氟烯基係指烯基之氫原子全部被氟原子取代之基。 Further, the perfluoroalkyl group means a group in which all hydrogen atoms of the alkyl group are substituted by a fluorine atom, and the perfluoroalkenyl group means a group in which all hydrogen atoms of the alkenyl group are substituted by a fluorine atom.

r表示結合於萘環之磺酸基數，且係滿足1≦r≦4之整數，但以2~4為佳，以2為最佳。 r represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer of 1≦r≦4, preferably 2 to 4, and most preferably 2.

使用作為摻雜物質之芳基磺酸化合物之分子量並非係受到特別限定者，若考慮到在與電荷輸送性寡聚物一同時對於有機溶劑之溶解性時，則以2000以下為佳，較佳為1500以下。 The molecular weight of the arylsulfonic acid compound to be used as the dopant is not particularly limited. When considering the solubility to the organic solvent together with the charge transporting oligomer, it is preferably 2,000 or less, preferably. It is 1500 or less.

以下，例示本發明中使用作為摻雜物質之適宜芳基磺酸化合物之具體例，但並非係受限於此等。 Hereinafter, specific examples of a suitable arylsulfonic acid compound used as a dopant in the present invention are exemplified, but are not limited thereto.

本發明之電荷輸送性清漆中包含摻雜物質時，摻雜物質之使用量由於在考量到摻雜物質之種類、所欲之電荷輸送性之程度等才適宜決定，故無法一概規定，一般而言，在質量比下，相對於電荷輸送性物質1，可在0.01~50之範圍內，但從提升取得薄膜之電荷輸送性之觀點，較佳為0.1~20，更佳為0.2~10之範圍內。 The charge transporting varnish of the present invention contains a dopant substance When the amount of the dopant used is determined in consideration of the type of the dopant, the degree of the desired charge transportability, etc., it cannot be generally specified. Generally, the mass ratio is relative to the charge transportability. The substance 1 may be in the range of 0.01 to 50, but is preferably in the range of 0.1 to 20, more preferably 0.2 to 10, from the viewpoint of improving the charge transportability of the film.

作為在調製電荷輸送性清漆時所使用之有機溶劑，可使用能良好地溶解電荷輸送性物質及因應必要所使用之摻雜物質之高溶解性溶劑。 As the organic solvent used in the preparation of the charge transporting varnish, a highly soluble solvent which can dissolve the charge transporting substance and the dopant which is used as necessary can be used.

作為此種高溶解性溶劑，可舉出例如，環己酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、1,3-二甲基-2-咪唑啉酮、二乙二醇單甲基醚等之有機溶劑，但並非係受限於此等者。此等溶劑係能單獨使用1種或將2種以上混合使用，其使用量係相對於清漆所使用之溶劑全體而言，可作成5~100質量%。 Examples of such a highly soluble solvent include cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3. An organic solvent such as dimethyl-2-imidazolidinone or diethylene glycol monomethyl ether, but is not limited thereto. These solvents can be used singly or in combination of two or more kinds, and the amount thereof can be 5 to 100% by mass based on the total amount of the solvent used in the varnish.

尚且，電荷輸送性物質及摻雜物質係以在任意之上述溶劑中成為完全溶解，或均勻分散之狀態為佳，又以完全溶解為較佳。 Further, the charge transporting substance and the dopant substance are preferably completely dissolved or uniformly dispersed in any of the above solvents, and are preferably completely dissolved.

又，本發明中，藉由使清漆含有至少一種在25℃下具有10~200mPa‧s，尤其係具有35~150mPa‧s之黏度，且在常壓(大氣壓)下沸點為50~300℃，尤其係150~250℃之高黏度有機溶劑，即可變得容易調整清漆之黏度，其結果係變得能調製出因應所使用之塗佈方法且再現性良好地賦予高平坦性薄膜之清漆。 Further, in the present invention, the varnish contains at least one 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 at normal pressure (atmospheric pressure). In particular, the viscosity of the varnish can be easily adjusted by using a high-viscosity organic solvent of 150 to 250 ° C. As a result, it is possible to prepare a varnish which imparts a high flatness film in accordance with the coating method to be used and which is excellent in reproducibility.

作為高黏度有機溶劑，可舉出例如，環己醇、乙二醇、乙二醇二環氧丙基醚、1,3-辛二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、丙二醇、己二醇等，但並非係受限於此等者。此等溶劑係可單獨使用，亦可將2種以上混合使用。 Examples of the high viscosity organic solvent include cyclohexanol and ethylene. Alcohol, ethylene glycol diepoxypropyl ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butane Alcohol, 1,4-butanediol, propylene glycol, hexanediol, etc., but are not limited thereto. These solvents may be used singly or in combination of two or more.

本發明中相對於清漆所使用之溶劑全體，高黏度有機溶劑之添加比例係以在不使固體析出之範圍內為佳，只要係不使固體析出，其添加比例係以5~90質量%為佳。 In the present invention, the ratio of the addition of the high-viscosity organic solvent to the entire solvent used in the varnish is preferably in the range in which the solid is not precipitated, and the addition ratio is 5 to 90% by mass as long as the solid is not precipitated. good.

並且，在提升對基板之濕潤性、調整溶劑之表面張力、調整極性、調整沸點等之目的上，相對於清漆所使用之溶劑全體而言，亦能在1~90質量%，較佳在1~50質量%之比例下混合其他溶劑。 Further, the purpose of improving the wettability of the substrate, adjusting the surface tension of the solvent, adjusting the polarity, and adjusting the boiling point can be 1 to 90% by mass, preferably 1%, based on the total amount of the solvent used for the varnish. Mix other solvents at a ratio of ~50% by mass.

作為此種溶劑，可舉出例如，丙二醇單甲基醚、乙二醇單丁基醚、二乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、二乙二醇單乙基醚、二丙酮醇、γ-丁內酯、乳酸乙酯、n-己基乙酸酯等，但並非係受限於此等。此等溶劑係能單獨使用1種或將2種以上混合使用。 Examples of such a solvent include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, γ-butyrolactone Ethyl lactate, n-hexyl acetate, etc., but are not limited thereto. These solvents can be used alone or in combination of two or more.

本發明之清漆之黏度係因應所製作之薄膜厚度等或固形分濃度等而適宜設定者，通常在25℃下為1~50mPa‧s。 The viscosity of the varnish of the present invention is suitably set depending on the thickness of the film to be produced, the solid content concentration, etc., and is usually 1 to 50 mPa·s at 25 °C.

又，本發明中電荷輸送性清漆之固形分濃度係在考量到清漆黏度及表面張力等或所製作之薄膜厚度等後而適宜設定者，通常為0.1~10.0質量%程度，若考慮到提升清漆之塗佈性時，則以0.5~5.0質量%程度為佳，較佳為1.0~3.0質量%程度。 Further, in the present invention, the solid content concentration of the charge transporting varnish is suitably set after considering the viscosity of the varnish, the surface tension, or the thickness of the film to be produced, and is usually 0.1 to 10.0% by mass, in consideration of lifting varnish. The coating property is preferably from 0.5 to 5.0% by mass, preferably from 1.0 to 3.0% by mass.

藉由將以上所說明之電荷輸送性清漆塗佈於基材上進行燒成，即能在基材上使電荷輸送性薄膜形成。 By applying the charge transporting varnish described above to a substrate and baking it, the charge transporting film can be formed on the substrate.

作為清漆之塗佈方法，並非係受到特別限定者，可舉出如浸漬法、旋轉塗佈法、轉印印刷法、輥塗法、刷毛塗佈法、噴墨法、噴霧法、狹縫塗佈法等，因應塗佈方法而調節清漆之黏度及表面張力為佳。 The coating method of the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, and a slit coating method. For the buffing method, it is preferred to adjust the viscosity and surface tension of the varnish in accordance with the coating method.

燒成環境並非係受到特別限定者，但以大氣環境為佳。 The firing environment is not particularly limited, but it is preferably an atmospheric environment.

燒成溫度係在考量到取得之薄膜之用途、賦予取得之薄膜之電荷輸送性程度、溶劑之種類或沸點等後，在100~260℃程度之範圍內適宜設定者，在將取得之薄膜使用作為有機EL元件之電洞注入層時，則以140~250℃程度為佳，以145~240℃程度為較佳。 The calcination temperature is preferably set in the range of 100 to 260 ° C after considering the use of the obtained film, the degree of charge transportability of the obtained film, the type of solvent, or the boiling point, etc., and the film to be used is used. When the hole injection layer of the organic EL element is used, it is preferably about 140 to 250 ° C, more preferably about 145 to 240 ° C.

尚且，於燒成之際，在使其展現較高均勻成膜性，或於基材上使其進行反應之目的上，亦可施加2段階以上之溫度變化，加熱係使用例如加熱板或烤箱等，使用適當機器進行即可。 Further, at the time of firing, a temperature change of two or more steps may be applied for the purpose of exhibiting a high uniform film forming property or reacting on a substrate, and the heating system may be, for example, a hot plate or an oven. Wait, use a suitable machine.

電荷輸送性薄膜之膜厚並無特別限定，在有機EL元件內使用作為電洞注入層時，以5~200nm為佳。作為改變膜厚之方法，如有改變清漆中之固形分濃度，或改變塗佈時基板上之溶液量等之方法。 The film thickness of the charge transporting film is not particularly limited, and when it is used as a hole injection layer in an organic EL device, it is preferably 5 to 200 nm. As a method of changing the film thickness, there is a method of changing the solid content concentration in the varnish, or changing the amount of the solution on the substrate at the time of coating.

作為使用本發明之電荷輸送性清漆製作有機 EL元件時之使用材料，或製作方法，可舉出如下述者，但並非係受到此等所限定者。 Making organic using the charge transporting varnish of the present invention The material to be used in the case of the EL element, or the production method, may be, for example, the following, but it is not limited thereto.

所使用之電極基板係以預先進行利用洗淨劑、醇、純水等之液體洗淨使其淨化者為佳，例如，陽極基板係在使用之前進行UV臭氧處理、氧-電漿處理等之表面處理為佳。但，陽極材料係將有機物作為主成分時，亦可不進行表面處理。 The electrode substrate to be used is preferably purified by washing with a liquid such as a detergent, alcohol, or pure water in advance, and for example, the anode substrate is subjected to UV ozone treatment, oxygen-plasma treatment, or the like before use. Surface treatment is preferred. However, when the anode material has an organic substance as a main component, it may not be subjected to surface treatment.

具有由從本發明之電荷輸送性清漆而得之薄膜所構成之電洞注入層之有機EL元件之製作方法之例係如以下所示。 An example of a method of producing an organic EL device having a hole injection layer composed of a film obtained from the charge transporting varnish of the present invention is as follows.

藉由上述方法，在陽極基板上塗佈本發明之電荷輸送性清漆並進行燒成，而在電極上製成電洞注入層。將此導入於真空蒸鍍裝置內，依電洞輸送層、發光層、電子輸送層、電子注入層/電洞阻擋層、陰極金屬之順序進行蒸鍍而作成有機EL元件。尚且，因應必要，亦可在發光層與電洞輸送層之間設置電子阻擋層。 By the above method, the charge transporting varnish of the present invention is applied onto an anode substrate and fired, and a hole injection layer is formed on the electrode. This was introduced into a vacuum vapor deposition apparatus, and vapor deposition was carried out in the order of the hole transport layer, the light-emitting layer, the electron transport layer, the electron injection layer/hole barrier layer, and the cathode metal to form an organic EL device. Further, an electron blocking layer may be provided between the light-emitting layer and the hole transport layer as necessary.

作為陽極材料，可舉出由銦錫氧化物(ITO)、銦鋅氧化物(IZO)所代表之透明電極，或由鋁所代表之金屬或由此等合金等所構成之金屬陽極，亦以已實施平坦化處理者為佳。亦能使用具有高電荷輸送性之聚噻吩衍生物或聚苯胺衍生物。 Examples of the anode material include a transparent electrode represented by indium tin oxide (ITO) or indium zinc oxide (IZO), or a metal anode composed of a metal represented by aluminum or the like, and the like. It is better to have a flattening process. A polythiophene derivative or a polyaniline derivative having high charge transportability can also be used.

尚且，作為構成金屬陽極之其他金屬，可舉出如鈧、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、釔、鋯、鈮、鉬、釕、銠、鈀、鎘、銦、鈧、鑭、鈰、鐠、釹、鉅、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿、鉿、鉈、鎢、錸、鋨、銥、鉑、金、鈦、鉛、鉍獲此等合金等，但並非係受限於此等者。 Further, as other metals constituting the metal anode, there may be mentioned, for example, ruthenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, lanthanum, zirconium, hafnium, molybdenum, niobium, tantalum, palladium, Cadmium, indium, antimony, bismuth, antimony, bismuth, antimony, Giant, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, platinum, gold, titanium, lead, seizure, etc. Restricted by this.

作為形成電洞輸送層之材料，可舉出如(三苯基胺)二聚物衍生物、[(三苯基胺)二聚物]螺二聚物、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-聯苯胺(α-NPD)、N,N’-雙(萘-2-基)-N,N’-雙(苯基)-聯苯胺、N,N’-雙(3-甲基苯基)-N,N’-雙(苯基)-聯苯胺、N,N’-雙(3-甲基苯基)-N,N’-雙(苯基)-9,9-旋環雙茀、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-9,9-旋環雙茀、N,N’-雙(3-甲基苯基)-N,N’-雙(苯基)-9,9-二甲基-茀、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-9,9-二甲基-茀、N,N’-雙(3-甲基苯基)-N,N’-雙(苯基)-9,9-二苯基-茀、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-9,9-二苯基-茀、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-2,2’-二甲基聯苯胺、2,2’,7,7’-肆(N,N-二苯基胺基)-9,9-旋環雙茀、9,9-雙[4-(N,N-雙-聯苯-4-基-胺基)苯基]-9H-茀、9,9-雙[4-(N,N-雙-萘-2-基-胺基)苯基]-9H-茀、9,9-雙[4-(N-萘-1-基-N-苯基胺基)-苯基]-9H-茀、2,2’,7,7’-肆[N-萘基(苯基)-胺基]-9,9-旋環雙茀、N,N’-雙(菲-9-基)-N,N’-雙(苯基)-聯苯胺、2,2’-雙[N,N-雙(聯苯-4-基)胺基]-9,9-旋環雙茀、2,2’-雙(N,N-二苯基胺基)-9,9-旋環雙茀、二-[4-(N,N-二(p-甲苯基)胺基)-苯基]環己烷、2,2’,7,7’-四(N,N-二(p-甲苯基))胺基-9,9-旋環雙茀、 N,N,N’,N’-四-萘-2-基-聯苯胺、N,N,N’,N’-四-(3-甲基苯基)-3,3’-二甲基聯苯胺、N,N’-二(萘基)-N,N’-二(萘-2-基)-聯苯胺、N,N,N’,N’-四(萘基)-聯苯胺、N,N’-二(萘-2-基)-N,N’-二苯基聯苯胺-1,4-二胺、N¹,N⁴-二苯基-N¹,N⁴-二(m-甲苯基)苯-1,4-二胺、N²,N²,N⁶,N⁶-四苯基萘-2,6-二胺、參(4-(喹啉-8-基)苯基)胺、2,2’-雙(3-(N,N-二(p-甲苯基)胺基)苯基)聯苯、4,4’,4”-參[3-甲基苯基(苯基)胺基]三苯基胺(m-MTDATA)、4,4’,4”-參[1-萘基(苯基)胺基]三苯基胺(1-TNATA)等之三芳基胺類、5,5”-雙-{4-[雙(4-甲基苯基)胺基]苯基}-2,2’：5’,2”-聯三噻吩(BMA-3T)等之寡噻吩類等。 Examples of the material for forming the hole transport layer include (triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, and N, N'-bis (naphthalene). 1-yl)-N,N'-bis(phenyl)-benzidine (α-NPD), N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-linked Aniline, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine, N,N'-bis(3-methylphenyl)-N,N' - bis(phenyl)-9,9-cyclocyclobiguanide, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-cyclohexane, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-dimethyl-anthracene, N,N'-bis(naphthalen-1-yl)- N,N'-bis(phenyl)-9,9-dimethyl-anthracene, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9 -diphenyl-fluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-diphenyl-fluorene, N,N'-bis (naphthalene -1-yl)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine, 2,2',7,7'-indole (N,N-diphenylamino) -9,9-cyclohexane, 9,9-bis[4-(N,N-bis-biphenyl-4-yl-amino)phenyl]-9H-indole, 9,9-bis[4 -(N,N-bis-naphthalen-2-yl-amino)phenyl]-9H-indole, 9,9-bis[4-(N-naphthalen-1-yl-N-phenylamino)- Phenyl]-9H-indole, 2,2',7,7'-indole[N-naphthyl(phenyl)-amino]-9,9-cyclocyclic guanidine, N,N'-bis(phenanthrene) -9-base) -N,N'-bis(phenyl)-benzidine, 2,2'-bis[N,N-bis(biphenyl-4-yl)amino]-9,9-cyclocyclic guanidine, 2, 2'-bis(N,N-diphenylamino)-9,9-cyclocyclobiguanide, bis-[4-(N,N-bis(p-methylphenyl)amino)-phenyl] ring Hexane, 2,2',7,7'-tetrakis(N,N-bis(p-tolyl))amino-9,9-cyclohexane, N,N,N',N'-four -naphthalen-2-yl-benzidine, N,N,N',N'-tetra-(3-methylphenyl)-3,3'-dimethylbenzidine, N,N'-di(naphthalene -N,N'-bis(naphthalen-2-yl)-benzidine, N,N,N',N'-tetrakis(naphthyl)-benzidine, N,N'-di(naphthalene-2- -N,N'-diphenylbenzidine-1,4-diamine, N ¹ ,N ⁴ -diphenyl-N ¹ ,N ⁴ -di(m-tolyl)benzene-1,4- Diamine, N ² , N ² , N ⁶ , N ⁶ -tetraphenylnaphthalene-2,6-diamine, ginseng (4-(quinolin-8-yl)phenyl)amine, 2,2'-double (3-(N,N-bis(p-tolyl)amino)phenyl)biphenyl, 4,4',4"-gin[3-methylphenyl(phenyl)amino]triphenyl a triarylamine such as an amine (m-MTDATA), 4,4',4"-para-[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5"-double -Oxo-thiophene such as [4-[4-methylphenyl)amino]phenyl}-2,2':5',2"-bitrithiophene (BMA-3T).

作為形成發光層之材料，可舉出如參(8-羥基喹啉)鋁(III)(Alq₃)、雙(8-羥基喹啉)鋅(II)(Znq₂)、雙(2-甲基-8-羥基喹啉)-4-(p-苯基酚根)鋁(III)(BAlq)、4,4’-雙(2,2-二苯基乙烯基)聯苯、9,10-二(萘-2-基)蒽、2-t-丁基-9,10-二(萘-2-基)蒽、2,7-雙[9,9-二(4-甲基苯基)-茀-2-基]-9,9-二(4-甲基苯基)茀、2-甲基-9,10-雙(萘-2-基)蒽、2-(9,9-旋環雙茀-2-基)-9,9-旋環雙茀、2,7-雙(9,9-旋環雙茀-2-基)-9,9-旋環雙茀、2-[9,9-二(4-甲基苯基)-茀-2-基]-9,9-二(4-甲基苯基)茀、2,2’-二芘基-9,9-旋環雙茀、1,3,5-參(芘-1-基)苯、9,9-雙[4-(芘基)苯基]-9H-茀、2,2’-二(9,10-二苯基蒽)、2,7-二芘基-9,9-旋環雙茀、1,4-二(芘-1-基)苯、1,3-二(芘-1-基)苯、6,13-二(聯苯-4- 基)稠五苯、3,9-二(萘-2-基)苝、3,10-二(萘-2-基)苝、參[4-(芘基)-苯基]胺、10,10’-二(聯苯-4-基)-9,9’-聯蒽、N,N’-二(萘-1-基)-N,N’-二苯基-[1,1’：4’,1”：4”,1'''-四聯苯基]-4,4'''-二胺、4,4’-二[10-(萘-1-基)蒽-9-基]聯苯、二苯並{[f,f’]-4,4’,7,7’-四苯基}二茚並[1,2,3-cd：1’,2’,3’-lm]苝、1-(7-(9,9’-聯蒽-10-基)-9,9-二甲基-9H-茀-2-基)芘、1-(7-(9,9’-聯蒽-10-基)-9,9-二己基-9H-茀-2-基)芘、1,3-雙(咔唑-9-基)苯、1,3,5-參(咔唑-9-基)苯、4,4’,4”-參(咔唑-9-基)三苯基胺、4,4’-雙(咔唑-9-基)聯苯、4,4’-雙(咔唑-9-基)-2,2’-二甲基聯苯、2,7-雙(咔唑-9-基)-9,9-二甲基茀、2,2’,7,7’-肆(咔唑-9-基)-9,9-旋環雙茀、2,7-雙(咔唑-9-基)-9,9-二(p-甲苯基)茀、9,9-雙[4-(咔唑-9-基)-苯基]茀、2,7-雙(咔唑-9-基)-9,9-旋環雙茀、1,4-雙(三苯基矽基)苯、1,3-雙(三苯基矽基)苯、雙(4-N,N-二乙基胺基-2-甲基苯基)-4-甲基苯基甲烷、2,7-雙(咔唑-9-基)-9,9-二辛基茀、4,4”-二(三苯基矽基)-p-三聯苯基、4,4’-二(三苯基矽基)聯苯、9-(4-t-丁基苯基)-3,6-雙(三苯基矽基)-9H-咔唑、9-(4-t-丁基苯基)-3,6-雙三苯甲基-9H-咔唑、9-(4-t-丁基苯基)-3,6-雙(9-(4-甲氧基苯基)-9H-茀-9-基)-9H-咔唑、2,6-雙(3-(9H-咔唑-9-基)苯基)吡啶、三苯基(4-(9-苯基-9H-茀-9-基)苯基)矽烷、9,9-二甲基-N,N-二苯基-7-(4-(1-苯基-1H-苯並[d]咪唑-2-基)苯基)-9H-茀-2-胺、3,5- 雙(3-(9H-咔唑-9-基)苯基)吡啶、9,9-旋環雙茀-2-基-二苯基-膦氧化物、9,9’-(5-(三苯基矽基)-1,3-伸苯基)雙(9H-咔唑)、3-(2,7-雙(二苯基磷醯基)-9-苯基-9H-茀-9-基)-9-苯基-9H-咔唑、4,4,8,8,12,12-六(p-甲苯基)-4H-8H-12H-12C-氮雜二苯並[cd,mn]芘、4,7-二(9H-咔唑-9-基)-1,10-啡啉、2,2’-雙(4-(咔唑-9-基)苯基)聯苯、2,8-雙(二苯基磷醯基)二苯並[b,d]噻吩、雙(2-甲基苯基)二苯基矽烷、雙[3,5-二(9H-咔唑-9-基)苯基]二苯基矽烷、3,6-雙(咔唑-9-基)-9-(2-乙基-己基)-9H-咔唑、3-(二苯基磷醯基)-9-(4-(二苯基磷醯基)苯基)-9H-咔唑、3,6-雙[(3,5-二苯基)苯基]-9-苯基咔唑等，亦可藉由與發光性摻質一同共蒸鍍而形成發光層。 Examples of the material for forming the light-emitting layer include ginseng (8-hydroxyquinoline) aluminum (III) (Alq ₃ ), bis(8-hydroxyquinoline) zinc (II) (Znq ₂ ), and bis (2-A). -8-hydroxyquinoline)-4-(p-phenylphenolate) aluminum (III) (BAlq), 4,4'-bis(2,2-diphenylvinyl)biphenyl, 9,10 -bis(naphthalen-2-yl)anthracene, 2-t-butyl-9,10-di(naphthalen-2-yl)anthracene, 2,7-bis[9,9-di(4-methylphenyl) )-茀-2-yl]-9,9-bis(4-methylphenyl)anthracene, 2-methyl-9,10-bis(naphthalen-2-yl)anthracene, 2-(9,9- Cyclo-biguanidin-2-yl)-9,9-cyclocyclic guanidine, 2,7-bis(9,9-cyclocyclobiguan-2-yl)-9,9-cyclocyclic guanidine, 2- [9,9-bis(4-methylphenyl)-indol-2-yl]-9,9-bis(4-methylphenyl)anthracene, 2,2'-dimercapto-9,9- Cycloindole, 1,3,5-gin (indol-1-yl)benzene, 9,9-bis[4-(indenyl)phenyl]-9H-indole, 2,2'-di (9, 10-diphenylfluorene), 2,7-dimercapto-9,9-cyclobiguanide, 1,4-bis(indol-1-yl)benzene, 1,3-bis(indol-1-yl) Benzene, 6,13-bis(biphenyl-4-yl) fused pentacene, 3,9-di(naphthalen-2-yl)anthracene, 3,10-di(naphthalen-2-yl)anthracene, ginseng [ 4-(indenyl)-phenyl]amine, 10,10'-bis(biphenyl-4-yl)-9,9'-biindole, N,N'-di(naphthalen-1-yl)-N , N'-diphenyl-[1,1':4',1":4",1'''-tetraphenylene]-4,4'''- Amine, 4,4'-bis[10-(naphthalen-1-yl)fluoren-9-yl]biphenyl, dibenzo{[f,f']-4,4',7,7'-tetraphenyl } 茚 [ [1,2,3-cd:1',2',3'-lm]苝, 1-(7-(9,9'-bin-10-yl)-9,9- Dimethyl-9H-indol-2-yl)indole, 1-(7-(9,9'-biindole-10-yl)-9,9-dihexyl-9H-indol-2-yl), 1,3-bis(carbazol-9-yl)benzene, 1,3,5-gin (carbazol-9-yl)benzene, 4,4',4"-gin (carbazol-9-yl) three Phenylamine, 4,4'-bis(carbazol-9-yl)biphenyl, 4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl, 2,7 - bis(carbazol-9-yl)-9,9-dimethylindole, 2,2',7,7'-indole (carbazol-9-yl)-9,9-cyclodane, 2 , 7-bis(carbazol-9-yl)-9,9-di(p-methylphenyl)anthracene, 9,9-bis[4-(carbazol-9-yl)-phenyl]anthracene, 2, 7-bis(carbazol-9-yl)-9,9-cyclobiguanide, 1,4-bis(triphenylphosphonyl)benzene, 1,3-bis(triphenylphosphonyl)benzene, double (4-N,N-Diethylamino-2-methylphenyl)-4-methylphenylmethane, 2,7-bis(carbazol-9-yl)-9,9-dioctyl茀, 4,4"-bis(triphenylindenyl)-p-terphenyl, 4,4'-bis(triphenylindenyl)biphenyl, 9-(4-t-butylphenyl) -3,6-bis(triphenylphosphonyl)-9H-carbazole, 9-(4-t-butylphenyl)-3,6-bistrityl-9H-carbazole, 9-( 4-t-ding Phenyl)-3,6-bis(9-(4-methoxyphenyl)-9H-indol-9-yl)-9H-carbazole, 2,6-bis(3-(9H-carbazole- 9-yl)phenyl)pyridine, triphenyl(4-(9-phenyl-9H-fluoren-9-yl)phenyl)decane, 9,9-dimethyl-N,N-diphenyl- 7-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-9H-indol-2-amine, 3,5-bis(3-(9H-carbazole- 9-yl)phenyl)pyridine, 9,9-cyclobiguanidin-2-yl-diphenyl-phosphine oxide, 9,9'-(5-(triphenylindenyl)-1,3- Phenyl)bis(9H-carbazole), 3-(2,7-bis(diphenylphosphonium)-9-phenyl-9H-indol-9-yl)-9-phenyl-9H- Carbazole, 4,4,8,8,12,12-hexa(p-tolyl)-4H-8H-12H-12C-azadibenzo[cd,mn]芘, 4,7-di (9H -carbazol-9-yl)-1,10-morpholine, 2,2'-bis(4-(carbazol-9-yl)phenyl)biphenyl, 2,8-bis(diphenylphosphonium) Diphenyl[b,d]thiophene, bis(2-methylphenyl)diphenylnonane, bis[3,5-bis(9H-carbazol-9-yl)phenyl]diphenylnonane ,3,6-bis(carbazol-9-yl)-9-(2-ethyl-hexyl)-9H-carbazole, 3-(diphenylphosphonium)-9-(4-(diphenyl) Phosphonic phenyl)-9H-carbazole, 3,6-bis[(3,5-diphenyl)phenyl]-9-phenylcarbazole, etc. Together with evaporation to form a luminescence Floor.

作為發光性摻質，可舉出如3-(2-苯並噻唑基)-7-(二乙基胺基)香豆素、2,3,6,7-四氫-1,1,7,7-四甲基-1H,5H,11H-10-(2-苯並噻唑基)喹嗪基[9,9a,1gh]香豆素、喹吖啶酮、N,N’-二甲基-喹吖啶酮、參(2-苯基吡啶)銥(III)(Ir(ppy)₃)、雙(2-苯基吡啶)(乙醯基丙酮酸根)銥(III)(Ir(ppy)₂(acac))、參[2-(p-甲苯基)吡啶]銥(III)(Ir(mppy)₃)、9,10-雙[N,N-二(p-甲苯基)胺基]蒽、9,10-雙[苯基(m-甲苯基)胺基]蒽、雙[2-(2-羥基苯基)苯並噻唑根]鋅(II)、N¹⁰,N¹⁰,N^10’,N^10’-四(p-甲苯基)-9,9’-聯蒽-10,10’-二胺、N¹⁰,N¹⁰,N^10’,N^10’-四苯基-9,9’-聯蒽-10,10’-二胺、N¹⁰,N^10’- 二苯基-N¹⁰,N^10’-二萘基-9,9’-聯蒽-10,10’-二胺、4,4’-雙(9-乙基-3-咔唑伸乙烯基)-1,1’-聯苯、苝、2,5,8,11-四-t-丁基苝、1,4-雙[2-(3-N-乙基咔唑)乙烯基]苯、4,4’-雙[4-(二-p-甲苯基胺基)苯乙烯基]聯苯、4-(二-p-甲苯基胺基)-4’-[(二-p-甲苯基胺基)苯乙烯基]茋、雙[3,5-二氟-2-(2-吡啶基)苯基-(2-羧基吡啶基)]銥(III)、4,4’-雙[4-(二苯基胺基)苯乙烯基]聯苯、雙(2,4-二氟苯基吡啶根)肆(1-吡唑基)硼酸銥(III)、N,N’-雙(萘-2-基)-N,N’-雙(苯基)-參(9,9-二甲基伸茀基)、2,7-雙{2-[苯基(m-甲苯基)胺基]-9,9-二甲基-茀-7-基}-9,9-二甲基-茀、N-(4-((E)-2-(6((E)-4-(二苯基胺基)苯乙烯基)萘-2-基)乙烯基)苯基)-N-苯基苯胺、fac-銥(III)參(1-苯基-3-甲基苯並咪唑啉-2-亞基-C,C^2’)、mer-銥(III)參(1-苯基-3-甲基苯並咪唑啉-2-亞基-C,C^2’)、2,7-雙[4-(二苯基胺基)苯乙烯基]-9,9-旋環雙茀、6-甲基-2-(4-(9-(4-(6-甲基苯並[d]噻唑-2-基)苯基)蒽-10-基)苯基)苯並[d]噻唑、1,4-二[4-(N,N-二苯基)胺基]苯乙烯基苯、1,4-雙(4-(9H-咔唑-9-基)苯乙烯基)苯、(E)-6-(4-(二苯基胺基)苯乙烯基)-N,N-二苯基萘-2-胺、雙(2,4-二氟苯基吡啶根)(5-(吡啶-2-基)-1H-四唑根)銥(III)、雙(3-三氟甲基-5-(2-吡啶基)吡唑)((2,4-二氟苄基)二苯基亞磷酸)銥(III)、雙(3-三氟甲基-5-(2-吡啶基)吡唑根)(苄基二苯基亞磷酸)銥(III)、雙(1-(2,4-二氟苄基)-3-甲基苯並咪唑鎓)(3-(三氟甲基)-5-(2-吡啶基)-1,2,4-***根)銥(III)、雙(3-三氟甲基-5-(2-吡啶基)吡唑根)(4’,6’-二氟苯基吡啶根)銥(III)、雙(4’,6’-二氟苯基吡啶根)(3,5-雙(三氟甲基)-2-(2’-吡啶基)吡唑根)銥(III)、雙(4’,6’-二氟苯基吡啶根)(3-(三氟甲基)-5-(2-吡啶基)-1,2,4-***根)銥(III)、(Z)-6-荚基-N-(6-荚基喹啉-2(1H)-亞基)喹啉-2-胺-BF₂、(E)-2-(2-(4-(二甲基胺基)苯乙烯基)-6-甲基-4H-吡喃-4-亞基)丙二腈、4-(二氰基亞甲基)-2-甲基-6-久咯啶-9-烯基-4H-吡喃、4-(二氰基亞甲基)-2-甲基-6-(1,1,7,7-四甲基久咯啶-9-烯基)-4H-吡喃、4-(二氰基亞甲基)-2-t-丁基-6-(1,1,7,7-四甲基久咯啶-4-基-乙烯基)-4H-吡喃、參(二苄醯基甲烷)啡啉銪(III)、5,6,11,12-四苯基稠四苯、雙(2-苯並[b]噻吩-2-基-吡啶)(乙醯基丙酮酸根)銥(III)、參(1-苯基異喹啉)銥(III)、雙(1-苯基異喹啉)(乙醯基丙酮酸根)銥(III)、雙[1-(9,9-二甲基-9H-茀-2-基)-異喹啉](乙醯基丙酮酸根)銥(III)、雙[2-(9,9-二甲基-9H-茀-2-基)喹啉](乙醯基丙酮酸根)銥(III)、參[4,4’-二-t-丁基-(2,2’)-聯吡啶]釕(III)‧雙(六氟磷酸酯)、參(2-苯基喹啉)銥(III)、雙(2-苯基喹啉)(乙醯基丙酮酸根)銥(III)、2,8-二-t-丁基-5,11-雙(4-t-丁基苯基)-6,12-二苯基稠四苯、雙(2-苯基苯並噻唑根)(乙醯基丙酮酸根)銥(III)、5,10,15,20-四苯基四苯並卟啉鉑、鋨(II)雙(3-三氟甲基-5-(2-吡啶)-吡唑根)二甲基苯基膦、鋨(II)雙(3-(三氟甲基)-5-(4-t-丁基吡啶基)-1,2,4-***根)二苯基甲基膦、鋨(II)雙(3-(三氟甲基)-5-(2-吡啶基)-1,2,4-***)二甲基苯基膦、鋨(II)雙(3-(三氟甲基)-5-(4-t-丁基吡啶基)-1,2,4-***根)二甲基苯基膦、雙[2-(4-n-己基苯基)喹啉](乙醯基丙酮酸根)銥(III)、參[2-(4-n-己基苯基)喹啉]銥(III)、參[2-苯基-4-甲基喹啉]銥(III)、雙(2-苯基喹啉)(2-(3-甲基苯基)吡啶根)銥(III)、雙(2-(9,9-二乙基-茀-2-基)-1-苯基-1H-苯並[d]咪唑根)(乙醯基丙酮酸根)銥(III)、雙(2-苯基吡啶)(3-(吡啶-2-基)-2H-色烯-2-根)銥(III)、雙(2-苯基喹啉)(2,2,6,6-四甲基庚烷-3,5-酸二根)銥(III)、雙(苯基異喹啉)(2,2,6,6-四甲基庚烷-3,5-二酸根)銥(III)、銥(III)雙(4-苯基噻吩並[3,2-c]吡啶根-N,C^2’)乙醯基丙酮酸根、(E)-2-(2-t-丁基-6-(2-(2,6,6-三甲基-2,4,5,6-四氫-1H-吡咯並[3,2,1-ij]喹啉-8-基)乙烯基)-4H-吡喃-4-亞基)丙二腈、雙(3-三氟甲基-5-(1-異喹啉基)吡唑根)(甲基二苯基膦)釕、雙[(4-n-己基苯基)異喹啉](乙醯基丙酮酸根)銥(III)、鉑(II)八乙基卟吩、雙(2-甲基二苯並[f,h]喹喔啉)(乙醯基丙酮酸根)銥(III)、參[(4-n-己基苯基)氧基喹啉]銥(III)等。 Examples of the luminescent dopant include 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 2,3,6,7-tetrahydro-1,1,7. ,7-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinazinyl [9,9a,1gh]coumarin, quinacridone, N,N'-dimethyl - quinacridone, ginseng (2-phenylpyridine) ruthenium (III) (Ir (ppy) ₃ ), bis (2-phenylpyridine) (ethyl acetonyl pyruvate) ruthenium (III) (Ir (ppy) ₂ (acac)), ginseng [2-(p-methylphenyl)pyridine] ruthenium (III) (Ir(mppy) ₃ ), 9,10-bis[N,N-bis(p-tolyl)amino] Ruthenium, 9,10-bis[phenyl(m-tolyl)amino]indole, bis[2-(2-hydroxyphenyl)benzothiazolyl]zinc(II), N ¹⁰ , N ¹⁰ , N ^{10 ^',} N ^{^10'} - four (p- tolyl) -9,9'-diamine -10,10'- ^{^{anthracene, N 10, N 10, N}} 10 ', N 10' - tetraphenyl-9, 9'-biindole-10,10'-diamine, N ¹⁰ ,N ^10' -diphenyl-N ¹⁰ ,N ^{10 '} -dinaphthyl-9,9'-bin-10,10'- Amine, 4,4'-bis(9-ethyl-3-carbazolevinylidene)-1,1'-biphenyl, anthracene, 2,5,8,11-tetra-t-butylhydrazine, 1 , 4-bis[2-(3-N-ethylcarbazole)vinyl]benzene, 4,4'-bis[4-(di-p-tolylamino)styrene]biphenyl, 4- (di-p-tolylamino)-4'-[(di-p-tolylamino)styryl]indole, double [3,5 -difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)]ruthenium (III), 4,4'-bis[4-(diphenylamino)styryl]biphenyl , bis(2,4-difluorophenylpyridinium) ruthenium (1-pyrazolyl)borate (III), N,N'-bis(naphthalen-2-yl)-N,N'-bis(benzene (), ginseng (9,9-dimethylexene), 2,7-bis{2-[phenyl(m-tolyl)amino]-9,9-dimethyl-indole-7- -9,9-dimethyl-anthracene, N-(4-((E)-2-(6(())(diphenylamino)styryl)) )vinyl)phenyl)-N-phenylaniline, fac-铱(III) ginseng (1-phenyl-3-methylbenzimidazolin-2-ylidene-C, C ^{2 '} ), mer-铱(III) ginseng (1-phenyl-3-methylbenzimidazolin-2-ylidene-C, C ^{2 '} ), 2,7-bis[4-(diphenylamino)styryl ]-9,9-Cyclocyclobiguanide, 6-methyl-2-(4-(9-(4-(6-methylbenzo[d]thiazol-2-yl)phenyl)indole-10- Phenyl)benzo[d]thiazole, 1,4-bis[4-(N,N-diphenyl)amino]styrylbenzene, 1,4-bis(4-(9H-carbazole) -9-yl)styryl)benzene, (E)-6-(4-(diphenylamino)styryl)-N,N-diphenylnaphthalen-2-amine, bis(2,4 -difluorophenylpyridinium)(5-(pyridin-2-yl)-1H-tetrazolone) ruthenium (III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazole) ((2,4-difluoro) (diphenylphosphite) ruthenium (III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazol) (benzyldiphenylphosphite) ruthenium (III), bis ( 1-(2,4-difluorobenzyl)-3-methylbenzimidazole oxime)(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole ) ruthenium (III), bis(3-trifluoromethyl-5-(2-pyridyl)pyrazol) (4',6'-difluorophenylpyridinium) ruthenium (III), double (4',6'-difluorophenylpyridinium)(3,5-bis(trifluoromethyl)-2-(2'-pyridyl)pyrazolone) ruthenium (III), bis(4',6'- Difluorophenylpyridinium) (3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazolyl) ruthenium (III), (Z)-6-podyl- N-(6-Pypoquinoline-2(1H)-ylidene)quinolin-2-amine-BF ₂ , (E)-2-(2-(4-(dimethylamino)styryl) - 6-methyl-4H-pyran-4-ylidene)malononitrile, 4-(dicyanomethylidene)-2-methyl-6-jubryryl-9-alkenyl-4H- Pyran, 4-(dicyanomethylidene)-2-methyl-6-(1,1,7,7-tetramethyljyrrolidin-9-enyl)-4H-pyran, 4- (Dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethylhybroth-4-yl-vinyl)-4H-pyran, ginseng (II) Benzyl methane) morphinium ruthenium (III), 5,6,11,12-tetraphenyl fused tetraphenyl, bis(2-benzo[b]thiophen-2-yl-pyridine) (acetamidine) Pyruvate) ruthenium (III), ginseng (1-phenylisoquinoline) ruthenium (III), bis(1-phenylisoquinoline) (acetylpyruvate) ruthenium (III), bis[1-( 9,9-Dimethyl-9H-indol-2-yl)-isoquinoline](ethylmercaptopyruvate) ruthenium (III), bis[2-(9,9-dimethyl-9H-oxime- 2-yl)quinoline](ethylmercaptopyruvate) ruthenium (III), ginseng [4,4'-di-t-butyl-(2,2')-bipyridyl] ruthenium (III) ‧ double Hexafluorophosphate), ginseng (2-phenylquinoline) ruthenium (III), bis(2-phenylquinoline) (ethionylpyruvate) ruthenium (III), 2,8-di-t-butyl -5,11-bis(4-t-butylphenyl)-6,12-diphenyl fused tetraphenyl, bis(2-phenylbenzothiazolyl) (ethylpyruvylate) ruthenium (III) , 5,10,15,20-tetraphenyltetrabenzoporphyrin platinum, ruthenium (II) bis(3-trifluoromethyl-5-(2-pyridine)-pyrazole) dimethylphenyl Phosphine, ruthenium (II) bis(3-(trifluoromethyl)-5-(4-t-butylpyridyl)-1,2,4-triazol)diphenylmethylphosphine, ruthenium (II) Bis(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole)dimethylphenylphosphine, ruthenium (II) bis(3-(trifluoromethyl) -5-(4-t-butylpyridyl)-1,2,4-triazol)dimethylphenylphosphine, bis[2-(4-n-hexylphenyl)quinoline] (B Mercaptopyruvate) 铱(III), ginseng [2-(4-n- Phenyl) quinoline] ruthenium (III), ginseng [2-phenyl-4-methylquinoline] ruthenium (III), bis(2-phenylquinoline) (2-(3-methylphenyl) Pyridinium) ruthenium (III), bis(2-(9,9-diethyl-indol-2-yl)-1-phenyl-1H-benzo[d]imidazolium) (ethionylpyruvate)铱(III), bis(2-phenylpyridine)(3-(pyridin-2-yl)-2H-chromene-2-yl)ruthenium(III), bis(2-phenylquinoline)(2) , 2,6,6-tetramethylheptane-3,5-acid two) ruthenium (III), bis(phenylisoquinoline) (2,2,6,6-tetramethylheptane-3 ,5-diacid) ruthenium (III), ruthenium (III) bis(4-phenylthieno[3,2-c]pyridinyl-N,C ^{2 '} ) acetylpyruvate, (E)-2 -(2-t-butyl-6-(2-(2,6,6-trimethyl-2,4,5,6-tetrahydro-1H-pyrrolo[3,2,1-ij]quina Phenyl-8-yl)vinyl)-4H-pyran-4-ylidene)malononitrile, bis(3-trifluoromethyl-5-(1-isoquinolinyl)pyrazole) (methyl Diphenylphosphine) ruthenium, bis[(4-n-hexylphenyl)isoquinoline](ethylmercaptopyruvate) ruthenium (III), platinum (II) octaethyl porphin, bis(2-methyl Dibenzo[f,h]quinoxaline)(ethylmercaptopyruvate) ruthenium (III), ginseng [(4-n-hexylphenyl)oxyquinoline] ruthenium (III), and the like.

作為形成電子輸送層/電洞阻擋層之材料，可舉出如8-羥基羥基喹啉-鋰、2,2’,2”-(1,3,5-石油精甲苯基)-參(1-苯基-1-H-苯並咪唑)、2-(4-聯苯基)5-(4-t-丁基苯基)-1,3,4-噁二唑、2,9-二甲基-4,7-二苯基-1,10-啡啉、4,7-二苯基-1,10-啡啉、雙(2-甲基-8-羥基喹啉)-4-(苯基苯酚根)鋁、1,3-雙[2-(2,2’-聯吡啶-6-基)-1,3,4-氧雜二偶氮-5-基]苯、6,6’-雙[5-(聯苯-4-基)-1,3,4-氧雜二偶氮-2-基]-2,2’-聯吡啶、3-(4-聯苯)-4-苯基-5-t-丁基苯基-1,2,4-***、4-(萘-1-基)-3,5-二苯基-4H-1,2,4-***、2,9-雙(萘-2-基)-4,7-二苯基-1,10-啡啉、2,7-雙[2-(2,2’-聯吡啶-6-基)-1,3,4-氧雜二偶氮-5-基]-9,9-二甲基茀、1,3-雙[2-(4-t-丁基苯基)-1,3,4-氧雜二偶氮-5-基]苯、參(2,4,6-三甲基-3-(吡啶-3-基)苯基)硼烷、1-甲基-2-(4-(萘-2-基)苯基)-1H-咪唑[4,5f][1,10]啡啉、2-(萘-2-基)-4,7-二苯基-1,10-啡啉、苯基-二芘基膦氧化物、3,3’,5,5’-四[(m-吡啶基)-苯-3-基]聯苯、1,3,5-參[(3-吡啶基)-苯-3-基]苯、4,4’-雙(4,6-二苯基-1,3,5-三嗪-2-基)聯苯、1,3-雙[3,5-二(吡啶-3-基)苯基]苯、雙(10-羥基苯並[h]喹啉根)鈹、二苯基雙(4-(吡啶-3-基)苯基)矽烷、3,5-二(芘-1-基)吡啶等。 As a material for forming an electron transport layer/hole blocking layer, For example, 8-hydroxyhydroxyquinoline-lithium, 2,2',2"-(1,3,5-petrolefin tolyl)-parade (1-phenyl-1-H-benzimidazole), 2 -(4-biphenyl)5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,9-dimethyl-4,7-diphenyl-1,10 -Porphyrin, 4,7-diphenyl-1,10-morpholine, bis(2-methyl-8-hydroxyquinoline)-4-(phenylphenolate) aluminum, 1,3-double [2 -(2,2'-bipyridyl-6-yl)-1,3,4-oxabisazo-5-yl]benzene, 6,6'-bis[5-(biphenyl-4-yl) -1,3,4-oxabisazo-2-yl]-2,2'-bipyridine, 3-(4-biphenyl)-4-phenyl-5-t-butylphenyl-1 , 2,4-triazole, 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole, 2,9-bis(naphthalen-2-yl)- 4,7-diphenyl-1,10-morpholine, 2,7-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxabisazo-5 -yl]-9,9-dimethylindole, 1,3-bis[2-(4-t-butylphenyl)-1,3,4-oxadisazo-5-yl]benzene, Reference (2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane, 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H- Imidazole [4,5f][1,10]morpholine, 2-(naphthalen-2-yl)-4,7-diphenyl-1,10-morpholine, phenyl-dimercaptophosphine oxide, 3 , 3',5,5'-tetra[(m-pyridyl)-phenyl-3-yl]biphenyl, 1,3,5-para[(3-pyridyl)-phenyl-3-yl]benzene , 4,4'-bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl, 1,3-bis[3,5-di(pyridin-3-yl) Phenyl]benzene, bis(10-hydroxybenzo[h]quinolinyl)indole, diphenylbis(4-(pyridin-3-yl)phenyl)decane, 3,5-di(芘-1- Base) pyridine and the like.

作為形成電子注入層之材料，可舉出如氧化鋰(Li₂O)、氧化鎂(MgO)、氧化鋁(Al₂O₃)、氟化鋰(LiF)、氟化鈉(NaF)、氟化鎂(MgF₂)、氟化銫(CsF)、氟化鍶(SrF₂)、三氧化鉬(MoO₃)、鋁、乙醯基丙酮酸鋰(Li(acac))、乙酸鋰、安息香酸鋰等。 Examples of the material for forming the electron injecting layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), and fluorine. Magnesium (MgF ₂ ), cesium fluoride (CsF), strontium fluoride (SrF ₂ ), molybdenum trioxide (MoO ₃ ), aluminum, lithium acetylacetate (Li(acac)), lithium acetate, benzoic acid Lithium, etc.

作為陰極材料，可舉出如鋁、鎂-銀合金、鋁-鋰合金、鋰、鈉、鉀、銫等。 Examples of the cathode material include aluminum, a magnesium-silver alloy, an aluminum-lithium alloy, lithium, sodium, potassium, rubidium, and the like.

作為形成電子阻擋層之材料，可舉出如參(苯基吡唑)銥等。 Examples of the material for forming the electron blocking layer include ginseng (phenylpyrazole) oxime and the like.

使用本發明之電荷輸送性清漆之PLED元件之製作方法並無特別限定，可舉出如以下之方法。 The method for producing the PLED element using the charge transporting varnish of the present invention is not particularly limited, and examples thereof include the following methods.

在上述有機EL元件製作中，取代實施電洞輸送層、發光層、電子輸送層、電子注入層之真空蒸鍍操作，而藉由依電洞輸送性高分子層、發光性高分子層之順序進行形成，即能製成具有由本發明之電荷輸送性清漆所形成之電荷輸送性薄膜之PLED元件。 In the production of the above-described organic EL device, the vacuum deposition operation of the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer is performed in the order of the hole-transporting polymer layer and the light-emitting polymer layer. Forming, that is, a PLED element having a charge transporting film formed of the charge transporting varnish of the present invention can be produced.

具體而言，在陽極基板上塗佈本發明之電荷輸送性清漆且藉由上述方法製成電洞注入層，並於其上依電洞輸送性高分子層、發光性高分子層之順序進行形成，再蒸鍍陰極而作成PLED元件。 Specifically, the charge transporting varnish of the present invention is applied onto an anode substrate, and a hole injection layer is formed by the above method, and is carried out in the order of the hole transporting polymer layer and the light emitting polymer layer. Forming, and then vapor-depositing the cathode to form a PLED element.

作為所使用之陰極及陽極材料，能使用與上述有機EL元件製作時相同者，且能進形同樣之洗淨處理、表面處理。 As the cathode and anode materials to be used, the same treatment as in the production of the above-described organic EL element can be used, and the same washing treatment and surface treatment can be carried out.

作為電洞輸送性高分子層及發光性高分子層之形成法，可舉出如將電洞輸送性高分子材料或發光性高分子材料、或對此等添加摻雜物質之材料加入溶劑使其溶解，或均勻分散，且塗佈於電洞注入層或電洞輸送性高分子層之上後，藉由分別燒成而成膜之方法。 The method for forming the hole transporting polymer layer and the light-emitting polymer layer is, for example, adding a hole transporting polymer material or a light-emitting polymer material or a material for adding a dopant to the solvent. It is dissolved or uniformly dispersed, and is applied to a hole injection layer or a hole transporting polymer layer, and then formed into a film by firing.

作為電洞輸送性高分子材料，可舉出如聚[(9,9-二己基茀-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,4-二胺基伸苯基)]、聚[(9,9-二辛基茀-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,1’-伸聯苯基-4,4-二胺)]、聚[(9,9-雙{1’-戊烯-5’-基}茀-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,4-二胺基伸苯基)]、以聚倍半矽氧烷封端之聚[N,N’-雙(4-丁基苯基)-N,N’-雙(苯基)-聯苯胺]、聚[(9,9-雙二辛基茀-2,7-二基)-co-(4,4’-(N-(p-丁基苯基))二苯基胺)]等。 Examples of the hole transporting polymer material include poly[(9,9-dihexylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}- 1,4-Diaminophenyl)], poly[(9,9-dioctylfluorene-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}- 1,1'-Exbiphenyl-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}茀-2,7-diyl)-co -(N,N'-bis{p-butylphenyl}-1,4-diaminophenyl)], poly[N,N'-bis(4-) terminated with polysesquioxanes Butylphenyl)-N,N'-bis(phenyl)-benzidine], poly[(9,9-bisdioctylfluoren-2,7-diyl)-co-(4,4'- (N-(p-butylphenyl))diphenylamine)].

作為發光性高分子材料，可舉出如聚(9,9-二烷基茀)(PDAF)等之聚茀衍生物、聚(2-甲氧基-5-(2’-乙基己氧基)-1,4-伸苯基伸乙烯)(MEH-PPV)等之聚伸苯基伸乙烯基衍生物、聚(3-烷基噻吩)(PAT)等之聚噻吩衍生物、聚乙烯咔唑(PVCz)等。 Examples of the luminescent polymer material include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), and poly(2-methoxy-5-(2'-ethylhexyloxy). a polyphenylene derivative such as a poly(phenylene) vinyl derivative such as a poly(3-alkylthiophene) (PAT) or a polyvinyl carbazole (PVCz) and so on.

作為溶劑，可舉出如甲苯、茬、氯仿等，作為溶解或均勻分散法，可舉出如攪拌、加熱攪拌、超音波分散等之方法。 Examples of the solvent include toluene, hydrazine, and chloroform. Examples of the dissolution or uniform dispersion method include stirring, heating and stirring, and ultrasonic dispersion.

塗佈方法並非係受到特別限定者，可舉出如噴墨法、噴霧法、浸漬法、旋轉塗佈法、轉印印刷法、輥塗法、刷毛塗佈法等。尚且，塗佈係在氮、氬等之惰性氣體下進行為佳。 The coating method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating method. Further, it is preferred that the coating be carried out under an inert gas such as nitrogen or argon.

作為燒成之方法，可舉出如在惰性氣體下或真空中，以烤箱或加熱板進行加熱之方法。 As a method of baking, a method of heating by an oven or a hot plate under an inert gas or a vacuum may be mentioned.

[實施例] [Examples]

以下，例舉合成例及實施例，更具體地說明本發明，但本發明並非係受到下述實施例所限定者。尚且，使用之裝置係如以下所示。 Hereinafter, the present invention will be more specifically described by way of Synthesis Examples and Examples, but the present invention is not limited by the following examples. Still, the device used is as follows.

(1)¹H-NMR：日本電子(股)製、ECX-300 (1) ¹ H-NMR: Japan Electronics Co., Ltd., ECX-300

(2)LC/MS：Waters公司製、ZQ2000 (2) LC/MS: Waters company, ZQ2000

(3)基板洗淨：長州產業(股)製基板洗淨裝置(減壓電漿方式) (3) Washing of the substrate: Changzhou Industry (stock) substrate cleaning device (reduced pressure plasma method)

(4)清漆之塗佈：三笠(股)製Spincoater MS-A100 (4) Coating of varnish: Spincoater MS-A100 manufactured by Sanken Co., Ltd.

(5)膜厚測量：(股)小坂研究所製微細形狀測量機Surcoder ET-4000 (5) Film thickness measurement: (s) 坂坂 research Institute Micro shape measuring machine Surcoder ET-4000

(6)EL元件之製作：長州產業(股)製多機能蒸鍍裝置系統C-E2L1G1-N (6) Production of EL components: Changzhou Industry (share) system multi-function evaporation device system C-E2L1G1-N

(7)EL元件之亮度等之測量：(有)Tech World製I-V-L測量系統 (7) Measurement of brightness of EL element, etc.: (Yes) I-V-L measurement system made by Tech World

[1]芳基胺衍生物之合成 [1] Synthesis of arylamine derivatives [合成例1]化合物1之合成 [Synthesis Example 1] Synthesis of Compound 1

對4-溴-4’-碘聯苯基(8.98g、25mmol、東京化成工業(股)製)、苯胺(2.56g、27.5mmol)之甲苯懸濁液(90mL)添加Pd(PPh₃)₄(1.44g、1.25mmol)、t-BuONa(2.88g、30mmol)，氮取代後，加熱迴流10小時。反應結束後，放置冷卻至室溫，以矽藻土過濾。將濃縮過濾液而得之粗生成物以矽膠管柱層析法(析出液：甲苯)進行純化後，將包含化合物1之餾分予以濃縮。對取得之粗生成物添加乙醇/甲苯(3：1(w/w))之混合溶劑，加熱迴流下使其溶解。冷卻至室溫後，過濾析出之固體而取得淡茶色固體之化合物1(6.96g、收率86%)。¹H-NMR及LC/MS之測量結果係如以下所示。 Pd(PPh ₃ ) _{4 was} added to a toluene suspension (90 mL) of 4-bromo-4'-iodobiphenyl (8.98 g, 25 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and aniline (2.56 g, 27.5 mmol). (1.44 g, 1.25 mmol), t-BuONa (2.88 g, 30 mmol), after nitrogen substitution, heated under reflux for 10 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through Celite. The crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (precipitate: toluene), and then the fraction containing the compound 1 was concentrated. A mixed solvent of ethanol/toluene (3:1 (w/w)) was added to the obtained crude product, and the mixture was heated under reflux to dissolve. After cooling to room temperature, the precipitated solid was filtered to obtain Compound 1 (6.96 g, yield 86%) as a pale brown solid. The measurement results of ¹ H-NMR and LC/MS are as follows.

¹H-NMR(300MHz，CDCl₃)：δ 5.79(brs，1H)，6.97(t，J=7.5Hz，1H)，7.10-7.13(m，4H)，7.25-7.32(m，2H)，7.41-7.55(m，6H)。 ¹ H-NMR (300MHz, CDCl ₃ ): δ 5.79 (brs, 1H), 6.97 (t, J = 7.5 Hz, 1H), 7.10-7.13 (m, 4H), 7.25-7.32 (m, 2H), 7.41 -7.55 (m, 6H).

LC/MS(ESI⁺)m/z；324[M+1]⁺ LC/MS (ESI ⁺ ) m/z; 324 [M+1] ⁺

[合成例2]芳基胺衍生物H1之合成 [Synthesis Example 2] Synthesis of arylamine derivative H1

對9,9-雙(4-胺基苯基)茀(1g、2.87mmol、東京化成工業(股)製)、合成例1中取得之化合物1(1.95g、6.0mmol)之茬懸濁液(10mL)添加 Pd(PPh₃)₄(166mg、0.14mmol)、t-BuONa(0.66g、6.89mmol)，氮取代後，加熱迴流4小時。其後，添加合成例1中取得之化合物1(0.37g、1.1mmol)、t-BuONa(0.11g、1.21mmol)，再加熱迴流6小時。反應結束後，放置冷卻至室溫，加入氯仿(40mL)、水(40mL)，在室溫下攪拌30分鐘。藉由過濾收集不溶之固體，並使其溶解於THF後，以矽藻土進行過濾。將濃縮過濾液而得之粗生成物以矽膠管柱層析法(析出液：己烷/乙酸乙酯(1/1(v/v)))進行純化後，將包含芳基胺衍生物H1之餾分予以濃縮。使用乙醇洗淨取得之粗生成物，而取得淡灰色固體之芳基胺衍生物H1(1.15g、收率48%)。¹H-NMR及LC/MS之測量結果係如以下所示。 9,9-bis(4-aminophenyl)anthracene (1 g, 2.87 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and Compound 1 (1.95 g, 6.0 mmol) obtained in Synthesis Example 1 were suspended in ruthenium. (10 mL) Pd(PPh ₃ ) ₄ (166 mg, 0.14 mmol) and t-BuONa (0.66 g, 6.89 mmol) were added, and after nitrogen substitution, the mixture was heated under reflux for 4 hours. Then, the compound 1 (0.37 g, 1.1 mmol) obtained in Synthesis Example 1 and t-BuONa (0.11 g, 1.21 mmol) were added, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and chloroform (40 mL) and water (40 mL) were added, and the mixture was stirred at room temperature for 30 minutes. The insoluble solid was collected by filtration, dissolved in THF, and then filtered over Celite. The crude product obtained by concentrating the filtrate is purified by silica gel column chromatography (precipitate: hexane/ethyl acetate (1/1 (v/v))), and the arylamine derivative H1 is contained. The fraction was concentrated. The obtained crude product was washed with ethanol to obtain an arylamine derivative H1 (1.15 g, yield: 48%) as a pale gray solid. The measurement results of ¹ H-NMR and LC/MS are as follows.

¹H-NMR(300MHz，THF-d₈)：δ 6.77(t，J=7.5Hz，2H)，6.94(d，J=9.0Hz，4H)，7.04-7.33(m，28H)，7.39-7.45(m，10H)，7.78(d，J=6.9Hz，2H)。 ¹ H-NMR (300 MHz, THF-d ₈ ): δ 6.77 (t, J = 7.5 Hz, 2H), 6.94 (d, J = 9.0 Hz, 4H), 7.04-7.33 (m, 28H), 7.39-7.45 (m, 10H), 7.78 (d, J = 6.9 Hz, 2H).

LC/MS(ESI⁺)m/z；835[M+1]⁺ LC/MS (ESI ⁺ ) m/z; 835 [M+1] ⁺

[合成例3]芳基胺衍生物H2之合成 [Synthesis Example 3] Synthesis of arylamine derivative H2

使用1,1-雙(4-胺基苯基)環己烷(0.8g、3mmol、東京化成工業(股)製)、合成例1中取得之化合物1(2.14g、6.6mmol)、Pd(PPh₃)₄(173mg、0.15mmol)、t-BuONa(0.72g、7.5mmol)、茬(8mL)，與合成例2進行相同之操作順序，而取得淡灰色固體之芳基胺衍生物H2(1.26g、收率56%)。¹H-NMR及LC/MS之測量結果係如以下所示。 Using 1,1-bis(4-aminophenyl)cyclohexane (0.8 g, 3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), Compound 1 (2.14 g, 6.6 mmol) obtained in Synthesis Example 1, Pd ( PPh ₃ ) ₄ (173 mg, 0.15 mmol), t-BuONa (0.72 g, 7.5 mmol), and hydrazine (8 mL) were obtained in the same procedure as in Synthesis Example 2 to obtain an arylamine derivative H2 as a light gray solid ( 1.26 g, yield 56%). The measurement results of ¹ H-NMR and LC/MS are as follows.

¹H-NMR(300MHz，THF-d₈)：δ 1.46-1.64(m，6H)，2.21-2.23(m，4H)，6.77(t，J=7.5Hz，2H)，7.02-7.32(m，28H)，7.40-7.44(m，8H)。 ¹ H-NMR (300MHz, THF-d ₈ ): δ 1.46-1.64 (m, 6H), 2.21-2.23 (m, 4H), 6.77 (t, J = 7.5 Hz, 2H), 7.02-7.32 (m, 28H), 7.40-7.44 (m, 8H).

LC/MS(ESI⁺)m/z；753[M+1]⁺ LC/MS (ESI ⁺ ) m/z; 753 [M+1] ⁺

[合成例4]芳基胺衍生物H3之合成 [Synthesis Example 4] Synthesis of arylamine derivative H3

使用4,4’-二胺基二苯基甲烷(0.6g、3mmol、東京化成工業(股)製)、合成例1中取得之化合物1(2.14g、6.6mmol)、Pd(PPh₃)₄(173mg、0.15mmol)、t-BuONa(0.72g、7.5mmol)、茬(6mL)，與合成例2進行相同之操作順序而取得淡灰色固體之芳基胺衍生物H3(1.45g、收率71%)。¹H-NMR及LC/MS之測量結果係如以下所示。 4,4'-diaminodiphenylmethane (0.6 g, 3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), Compound 1 (2.14 g, 6.6 mmol) obtained in Synthesis Example 1, and Pd(PPh ₃ ) _{4 were used.} (173 mg, 0.15 mmol), t-BuONa (0.72 g, 7.5 mmol), and hydrazine (6 mL) were obtained in the same procedure as in Synthesis Example 2 to obtain an arylamine derivative H3 (1.45 g, yield 71%). The measurement results of ¹ H-NMR and LC/MS are as follows.

¹H-NMR(300MHz，THF-d₈)：δ 3.82(s，2H)，6.77(t，J=7.5Hz，2H)，7.00-7.20(m，24H)，7.26(brs，2H)，7.32(brs，2H)，7.40-7.44(m，8H)。 ¹ H-NMR (300MHz, THF-d ₈ ): δ 3.82 (s, 2H), 6.77 (t, J = 7.5 Hz, 2H), 7.00-7.20 (m, 24H), 7.26 (brs, 2H), 7.32 (brs, 2H), 7.40-7.44 (m, 8H).

LC/MS(ESI⁺)m/z；685[M+1]⁺ LC/MS (ESI ⁺ ) m/z; 685 [M+1] ⁺

[2]電荷輸送性清漆之調製 [2] Modulation of charge transport varnish [實施例1-1] [Example 1-1]

對芳基胺衍生物H1 0.113g(0.135mmol)及下述式所示之摻質物質D1 0.091g(0.101mmol)之混合物，添加在氮環境下為良溶劑之1,3-二甲基-2-咪唑啉酮7.2g使其溶解。對此溶液添加環己醇1.4g及丙二醇1.4g，充分進行攪拌而取得黃色透明溶液。使用孔徑0.2μm之PTFE製過濾器過濾取得之溶液，而取得黃色透明之電荷輸送性清漆(固形分濃度2.0質量%)。 A mixture of 0.113 g (0.135 mmol) of the arylamine derivative H1 and 0.091 g (0.101 mmol) of the dopant D1 represented by the following formula was added to a 1,3-dimethyl group as a good solvent under a nitrogen atmosphere. 2-imidazolinone 7.2 g was dissolved. To this solution, 1.4 g of cyclohexanol and 1.4 g of propylene glycol were added. Stirring was carried out to obtain a yellow transparent solution. The obtained solution was filtered through a PTFE filter having a pore size of 0.2 μm to obtain a yellow transparent charge transporting varnish (solid content concentration: 2.0% by mass).

尚且，摻質物質D1係根據國際公開第2006/025342號之記載內容所合成者。 Further, the dopant substance D1 is synthesized according to the contents described in International Publication No. 2006/025342.

[實施例1-2] [Example 1-2]

除了使用芳基胺衍生物H1 0.098g(0.117mmol)及摻質物質D1 0.106g(0.117mmol)之混合物以外，其他與實施例1-1同樣地操作而取得黃色透明之電荷輸送性清漆(固形分濃度2.0質量%)。 A yellow transparent charge transport varnish (solid form) was obtained in the same manner as in Example 1-1, except that a mixture of 0.098 g (0.117 mmol) of the arylamine derivative H1 and 0.106 g (0.117 mmol) of the dopant D1 was used. The concentration was 2.0% by mass).

[實施例1-3] [Example 1-3]

除了使用芳基胺衍生物H1 0.062g(0.074mmol)及磷鎢酸(關東化學(股)製)0.247g之混合物以外，其他係與實施例1-1同樣地操作而取得黃色透明之電荷輸送性清漆(固形分濃度3.0質量%)。 A yellow transparent charge transport was obtained in the same manner as in Example 1-1, except that a mixture of 0.062 g (0.074 mmol) of arylamine derivative H1 and 0.247 g of phosphotungstic acid (manufactured by Kanto Chemical Co., Ltd.) was used. Varnish (solid content concentration 3.0% by mass).

[實施例1-4] [Example 1-4]

除了使用芳基胺衍生物H2 0.062g(0.082mmol)及磷鎢酸0.247g之混合物以外，其他係與實施例1-1同樣地操作而取得黃色透明之電荷輸送性清漆(固形分濃度3.0質量%)。 A yellow transparent charge transporting varnish (solid content concentration 3.0 mass) was obtained in the same manner as in Example 1-1, except that a mixture of 0.062 g (0.082 mmol) of arylamine derivative H2 and 0.247 g of phosphotungstic acid was used. %).

[實施例1-5] [Example 1-5]

除了使用芳基胺衍生物H3 0.062g(0.090mmol)及磷鎢酸0.247g之混合物以外，其他係與實施例1-1同樣地操作而取得黃色透明之電荷輸送性清漆(固形分濃度3.0質量%)。 A yellow transparent charge transport varnish (solid content concentration 3.0 mass) was obtained in the same manner as in Example 1-1, except that a mixture of 0.062 g (0.090 mmol) of arylamine derivative H3 and 0.247 g of phosphotungstic acid was used. %).

[3]有機EL元件之製作及初期特性 [3] Fabrication and initial characteristics of organic EL elements

評價電特性時之基板係使用在表面上銦錫氧化物經圖型化成膜厚150nm，且25mm×25mm×0.7t之玻璃基板(以下略稱為ITO基板)。ITO基板係使用O₂電漿洗淨裝置(150W、30秒鐘)去除表面上之雜質後才使用。 The substrate for evaluation of electrical characteristics was a glass substrate (hereinafter abbreviated as ITO substrate) having a thickness of 150 nm and a thickness of 25 mm × 25 mm × 0.7 t on the surface of the indium tin oxide. The ITO substrate was used after removing the impurities on the surface using an O ₂ plasma cleaning device (150 W, 30 seconds).

[實施例2-1] [Example 2-1]

使用旋轉塗佈器將實施例1-1中取得之清漆塗佈於ITO基板後，在80℃下乾燥1分鐘，並且在大氣環境下，以230℃燒成15分鐘而在ITO基板上形成30nm之均勻薄膜。 The varnish obtained in Example 1-1 was applied onto an ITO substrate using a spin coater, and then dried at 80 ° C for 1 minute, and baked at 230 ° C for 15 minutes in an atmosphere to form 30 nm on the ITO substrate. Uniform film.

對已形成薄膜之ITO基板，使用蒸鍍裝置將α-NPD、Alq₃、氟化鋰、及鋁之薄膜依此順序層合而取得有機EL元件。膜厚係分別作成30nm、40nm、0.5nm及100nm，真空度1.0×10^-5Pa，蒸鍍速率係在氟化鋰時為0.02nm/秒，而以外之材料為0.2nm/秒之條件下進行蒸鍍。 An organic EL device was obtained by laminating a film of α- NPD, Alq ₃ , lithium fluoride, and aluminum in this order on the ITO substrate on which the thin film was formed by using a vapor deposition device. The film thicknesses were 30 nm, 40 nm, 0.5 nm, and 100 nm, respectively, and the degree of vacuum was 1.0 × 10 ^-5 Pa. The evaporation rate was 0.02 nm/sec in the case of lithium fluoride, and the material was 0.2 nm/sec. Perform evaporation.

尚且，為了防止空氣中之氧、水等之影響所造成之特性劣化，有機EL元件係藉由密封基板密封後，才評價其特性。密封係依照以下操作順序進行。 Further, in order to prevent deterioration of characteristics due to the influence of oxygen, water, and the like in the air, the organic EL device was evaluated by sealing the substrate after sealing. The sealing is carried out in the following sequence of operations.

在氧濃度5ppm以下、露點-80℃以下之氮環境中，將有機EL元件收納於密封基板之間，藉由接著劑貼合密封基板。此時，將捕水劑(Dynic(股)製、HD-071010W-40)與有機EL元件一同地收納至密封基板內。接著劑係使用(股)MORESCO製、Moresco Moisture cut WB90US(P)。對已貼合之密封基板照射UV光(波長365nm、照射量6,000mJ/cm²)後，在80℃下退火處理1小時而使接著劑硬化。 In a nitrogen atmosphere having an oxygen concentration of 5 ppm or less and a dew point of -80 ° C or less, the organic EL element is housed between the sealing substrates, and the sealing substrate is bonded by an adhesive. At this time, a water-trapping agent (Dynic, HD-071010W-40) was placed in the sealing substrate together with the organic EL element. The following agent was used (manufactured by MORESCO, Moresco Moisture cut WB90US (P). The bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm ² ), and then annealed at 80 ° C for 1 hour to cure the adhesive.

[實施例2-2~2-5] [Example 2-2~2-5]

除了使用實施例1-2~1-5中取得之清漆以外，其他係與實施例2-1相同之方法製成有機EL元件。 An organic EL device was produced in the same manner as in Example 2-1 except that the varnish obtained in Examples 1-2 to 1-5 was used.

使用電流-電壓-亮度測量系統測量實施例2-1~2-5中取得之有機EL元件之電特性。將驅動電壓5V下之電流密度及亮度記載於表1。尚且，各元件之發光面尺寸之面積為2mm×2mm。 The electrical characteristics of the organic EL elements obtained in Examples 2-1 to 2-5 were measured using a current-voltage-brightness measuring system. The current density and luminance at a driving voltage of 5 V are shown in Table 1. Further, the area of the light-emitting surface of each element is 2 mm × 2 mm.

如表1所示，可得知實施例2-1~2-5中製成之有機EL元件在實用性電壓之範圍內可充分地發光。 As shown in Table 1, it is understood that the organic EL elements produced in Examples 2-1 to 2-5 can sufficiently emit light within the range of practical voltage.

從以上可得知，藉由將使用本發明之電荷輸送性物質之薄膜利用作為電洞注入層，即能取得亮度特性優異之有機EL元件。 As described above, it is known that an organic EL device having excellent luminance characteristics can be obtained by using a film using the charge transporting material of the present invention as a hole injection layer.

Claims

一種電荷輸送性物質，其係由式(1)所表示之芳基胺衍生物所構成； [式中，R¹~R⁸係互相獨立表示氫原子、鹵素原子、或可經Z¹取代之碳數1~20之烷基或碳數1~20之烷氧基，Ar¹表示可經Z²取代之碳數6~20之芳基，n表示1~3之整數，X表示式(2a)或(2b)所表示之2價有機基， (式中，R⁹及R¹⁰係互相獨立表示碳數1~20之烷基、碳數1~20之氟烷基、可經Z²取代之碳數6~20之芳基，或R⁹與R¹⁰結合形成碳數3~21之亦可縮環之環式烴基，R¹¹及R¹²係互相獨立表示氫原子或氟原子，R¹³~R²⁰係互相獨立表示氫原子、碳數1~20之烷基、碳數1~20之氟烷基、或Z³，m表示1~4之整數)Z¹表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、羧酸基、或可經Z³取代之碳數6~20之芳基或碳數2~20之雜芳基，Z²表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、羧酸基，或可經Z³取代之碳數1~20之烷基、碳數2~20之烯基或碳數2~20之炔基，Z³表示鹵素原子、硝基、氰基、胺基、醛基、羥基、巰基、磺酸基、或羧酸基]。 A charge transporting substance consisting of an arylamine derivative represented by the formula (1); [wherein, R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms or a carbon number of 1 to 20 which may be substituted by Z ¹ , and Ar ¹ represents a Z ^{2 is} substituted with an aryl group having 6 to 20 carbon atoms, n is an integer of 1 to 3, and X represents a divalent organic group represented by the formula (2a) or (2b). (wherein R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted by Z ² , or R ⁹ And R ^{10 is} bonded to form a cyclic hydrocarbon group having a carbon number of 3 to 21, and R ¹¹ and R ¹² are each independently represent a hydrogen atom or a fluorine atom, and R ¹³ to R ²⁰ are independently of each other and represent a hydrogen atom and a carbon number of 1. ~20 alkyl, carbon number 1-20 fluoroalkyl, or Z ³ , m represents an integer from 1 to 4) Z ¹ represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ³ , and Z ² represents a halogen atom, a nitro group, a cyano group, an amine group, or an aldehyde group. a base, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by Z ³ , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ³ Represents a halogen atom, a nitro group, a cyano group, an amine group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, or a carboxylic acid group].

如請求項1之電荷輸送性物質，其中前述X為一種選自式(3a)~(3h)所表示之2價有機基； The charge transporting substance of claim 1, wherein the X is a divalent organic group selected from the group consisting of formulas (3a) to (3h);

一種電荷輸送性材料，其係包含如請求項1或2之電荷輸送性物質。 A charge transporting material comprising the charge transporting substance of claim 1 or 2.

一種電荷輸送性清漆，其係包含如請求項1或2之電荷輸送性物質，與有機溶劑。 A charge transporting varnish comprising the charge transporting substance as claimed in claim 1 or 2, and an organic solvent.

如請求項4之電荷輸送性清漆，其中更包含摻質物質。 The charge transporting varnish of claim 4, further comprising a dopant.

如請求項5之電荷輸送性清漆，其中前述摻質物質包含雜多酸。 The charge transporting varnish of claim 5, wherein the dopant substance comprises a heteropolyacid.

一種電荷輸送性薄膜，其係使用如請求項4~6中任一項之電荷輸送性清漆所製作者。 A charge transporting film produced by using the charge transporting varnish according to any one of claims 4 to 6.

一種有機電致發光元件，其係具有如請求項7之電荷輸送性薄膜。 An organic electroluminescence device having the charge transporting film as claimed in claim 7.

一種電荷輸送性薄膜之製造方法，其特徵為將如請求項4~6中任一項之電荷輸送性清漆塗佈於基材上並使溶劑蒸發。 A method for producing a charge transporting film, which comprises applying a charge transporting varnish according to any one of claims 4 to 6 to a substrate and evaporating the solvent.