TW202106696A

TW202106696A - Composition for organic electroluminescent element, organic electroluminescent element, production method therefor, and display device

Info

Publication number: TW202106696A
Application number: TW109116593A
Authority: TW
Inventors: 梶山良子; 長山和弘; 飯田宏一朗
Original assignee: 日商三菱化學股份有限公司
Priority date: 2019-05-20
Filing date: 2020-05-19
Publication date: 2021-02-16
Also published as: JPWO2020235562A1; CN113874467A; WO2020235562A1; KR20220010598A

Abstract

The present invention relates to a composition for an organic electroluminescent element comprising: a compound represented by formula (1) wherein a triazine ring has been substituted at a specific position; and a compound represented by formula (2), whereof the maximum light-emission wavelength is a shorter wave than that of the compound represented by formula (1); and a solvent.

Description

有機電場發光元件用組成物、有機電場發光元件及其製造方法及顯示裝置Composition for organic electroluminescence element, organic electroluminescence element, method of manufacturing the same, and display device

本發明是有關於一種對於形成有機電場發光元件（以下有時稱為「有機EL（Electro-Luminescence）元件」）的發光層而言有用的有機電場發光元件用組成物。本發明而且是有關於一種具有使用該有機電場發光元件用組成物而形成的發光層的有機電場發光元件及其製造方法、以及具有該有機電場發光元件的顯示裝置。The present invention relates to a composition for an organic electroluminescence element useful for forming a light-emitting layer of an organic electroluminescence element (hereinafter sometimes referred to as an "organic EL (Electro-Luminescence) element"). The present invention also relates to an organic electroluminescence element having a light-emitting layer formed using the composition for an organic electroluminescence element, a method of manufacturing the same, and a display device having the organic electroluminescence element.

有機EL照明或有機EL顯示器等利用有機EL元件的各種電子裝置正在實用化。有機電場發光元件因施加電壓低而消耗電力小，亦能夠進行三原色發光，因此不僅開始應用於大型的顯示器監視器，亦開始應用於以行動電話或智慧型手機為代表的中小型顯示器。有機電場發光元件是藉由將發光層或電荷注入層、電荷傳輸層等多個層積層而製造。目前，多數有機電場發光元件是藉由於真空下蒸鍍有機材料而製造，但真空蒸鍍法中，蒸鍍製程複雜，生產性差。藉由真空蒸鍍法而製造的有機電場發光元件極難實現照明或顯示器的面板的大型化。Various electronic devices using organic EL elements, such as organic EL lighting and organic EL displays, are being put into practical use. Organic electroluminescent elements consume little power due to low applied voltage and can emit light in three primary colors. Therefore, they have begun to be used not only in large-scale display monitors, but also in small and medium-sized displays such as mobile phones and smart phones. Organic electroluminescent devices are manufactured by laminating multiple layers such as a light-emitting layer, a charge injection layer, and a charge transport layer. At present, most organic electroluminescent devices are manufactured by evaporating organic materials under vacuum. However, in the vacuum evaporation method, the evaporation process is complicated and the productivity is poor. The organic electroluminescent element manufactured by the vacuum vapor deposition method is extremely difficult to realize the enlargement of the panel of the illumination or display.

近年來，作為效率良好地製造可用於大型的顯示器或照明的有機電場發光元件的製程，研究有濕式成膜法（塗佈法）。濕式成膜法與真空蒸鍍法相比，具有可容易地形成穩定的層的優點，因此被期待應用於顯示器或照明裝置的量產化或大型顯示器。為了藉由濕式成膜法來製造有機電場發光元件，所使用的材料需要全部為可溶解於有機溶媒中而作為油墨來使用的材料。使用材料的溶解性差時，需要長時間加熱等操作，因此存在使用前材料劣化的可能性。進而，若無法在溶液狀態下長時間保持均勻狀態，則會發生材料自溶液的析出，從而不能利用噴墨裝置等進行成膜。對於濕式成膜法中所使用的材料，要求迅速溶解於有機溶媒、及溶解後不析出而保持均勻狀態這兩個意義上的溶解性。In recent years, as a process for efficiently manufacturing organic electroluminescent elements that can be used for large-scale displays or lighting, a wet film formation method (coating method) has been studied. Compared with the vacuum vapor deposition method, the wet film formation method has the advantage of being able to easily form a stable layer, and therefore is expected to be applied to mass production of displays or lighting devices or large displays. In order to manufacture an organic electroluminescent element by a wet film formation method, all the materials used need to be materials that can be dissolved in an organic solvent and used as an ink. When the solubility of the used material is poor, it requires long-term heating and other operations, so there is a possibility that the material will deteriorate before use. Furthermore, if the uniform state cannot be maintained in the solution state for a long period of time, precipitation of the material from the solution will occur, making it impossible to form a film using an inkjet device or the like. The material used in the wet film forming method requires solubility in the two senses of dissolving quickly in an organic solvent and maintaining a uniform state without precipitation after dissolution.

作為濕式成膜法相對於真空蒸鍍法而言的優點，可列舉能夠於一個層中使用更多的材料種的方面。真空蒸鍍法中，當材料種增加時，難以將蒸鍍速度控制為固定，與此相對，濕式成膜法中，即便材料種增加，只要各材料溶解於有機溶媒中，便能夠製作固定的成分比的油墨。近年來，嘗試了利用該優點於油墨中使用兩種以上銥錯合物來提高有機電場發光元件的發光效率或降低驅動電壓，以改善有機電場發光元件的性能（例如，專利文獻1及專利文獻2）。As an advantage of the wet film formation method over the vacuum vapor deposition method, it is possible to use more kinds of materials in one layer. In the vacuum vapor deposition method, it is difficult to control the vapor deposition rate to a fixed rate when the material types increase. In contrast, in the wet film formation method, even if the material types increase, as long as each material is dissolved in an organic solvent, it can be fixed. The composition ratio of the ink. In recent years, attempts have been made to use this advantage to use two or more iridium complexes in inks to increase the luminous efficiency of organic electroluminescent elements or reduce the driving voltage to improve the performance of organic electroluminescent elements (for example, Patent Literature 1 and Patent Literature 2).

另一方面，關注材料的化學結構，而嘗試了將配位子中包含三嗪環取代於特定的位置的苯基吡啶的銥錯合物用作白色發光元件中的紅色發光材料（例如，專利文獻3及專利文獻4）。 [現有技術文獻] [專利文獻]On the other hand, focusing on the chemical structure of the material, an attempt was made to use an iridium complex containing a phenylpyridine with a triazine ring substituted at a specific position in the ligand as a red light-emitting material in a white light-emitting element (for example, patent Document 3 and Patent Document 4). [Prior Art Literature] [Patent Literature]

[專利文獻1]國際公開第2015/192939號 [專利文獻2]國際公開第2016/015815號 [專利文獻3]國際公開第2017/154884號 [專利文獻4]日本專利特開2018-83941號公報[Patent Document 1] International Publication No. 2015/192939 [Patent Document 2] International Publication No. 2016/015815 [Patent Document 3] International Publication No. 2017/154884 [Patent Document 4] Japanese Patent Laid-Open No. 2018-83941

[發明所欲解決之課題] 然而，於所述現有技術中，對於顯示器用途，於有機電場發光元件的性能的方面無法說是充分的，特別是要求紅色元件中進一步降低驅動電壓、提高發光效率、改善驅動壽命。本發明特別是於紅色元件中能夠藉由濕式成膜法來製造有機電場發光元件，課題在於提供一種與先前相比，驅動電壓低、發光效率高、驅動壽命長的有機電場發光元件。 [解決課題之手段][The problem to be solved by the invention] However, in the prior art, for display applications, the performance of the organic electroluminescent element cannot be said to be sufficient. In particular, it is required to further reduce the driving voltage, increase the luminous efficiency, and improve the driving life of the red element. In particular, the present invention can manufacture organic electroluminescent devices by wet film formation among red devices. The problem is to provide an organic electroluminescent device with lower driving voltage, higher luminous efficiency, and long driving life than before. [Means to solve the problem]

本發明人等為了靈活應用可於一個層中使用更多的材料種的濕式成膜法的優點，鑒於所述課題而進行了深入研究。其結果發現，藉由製成將最大發光波長相對短的銥錯合物用作輔助摻雜劑，將配位子中包含三嗪環取代於特定的位置的苯基吡啶的銥錯合物用作紅色元件中的發光摻雜劑，將輔助摻雜劑與發光摻雜劑溶解於溶媒中的有機電場發光元件用組成物，並使用其來製作有機電場發光元件，有機電場發光元件的性能提高，從而完成了本發明。另外，亦發現，藉由以比輔助摻雜劑大的組成比來使用作為發光摻雜劑的所述銥錯合物，有機電場發光元件的性能進一步提高。In order to flexibly apply the advantages of the wet film formation method that can use more material types in one layer, the inventors of the present invention conducted intensive studies in view of the above-mentioned problems. As a result, it was found that by preparing an iridium complex compound with a relatively short maximum emission wavelength as an auxiliary dopant, a ligand containing a triazine ring substituted at a specific position of a phenylpyridine complex was used as an auxiliary dopant. Used as a light-emitting dopant in a red device, a composition for an organic electroluminescent device that dissolves auxiliary dopants and a light-emitting dopant in a solvent, and uses it to make an organic electroluminescent device, which improves the performance of the organic electroluminescent device , Thereby completing the present invention. In addition, it has also been found that by using the iridium complex as a light-emitting dopant at a composition ratio larger than that of the auxiliary dopant, the performance of the organic electroluminescent device is further improved.

本發明的有機電場發光元件用組成物含有相對於發光摻雜劑而言最大發光波長為短波的銥錯合物作為輔助摻雜劑，並含有配位子中包含三嗪環取代於特定的位置的苯基吡啶的銥錯合物作為發光摻雜劑。因此，能夠製造比先前驅動電壓低、發光效率高、驅動壽命長的有機電場發光元件。進而，本發明的有機電場發光元件用組成物藉由使發光摻雜劑的組成比大於輔助摻雜劑的組成比，而可適宜地抑制自輔助摻雜劑的發光，從而能夠製作具有更鮮明的發光色的有機電場發光元件。The composition for an organic electroluminescent element of the present invention contains an iridium complex with a short wavelength maximum emission wavelength as an auxiliary dopant relative to the light-emitting dopant, and contains a triazine ring substituted in a specific position in the ligand. The iridium complex of phenylpyridine is used as a light emitting dopant. Therefore, it is possible to manufacture an organic electroluminescent element that has a lower driving voltage, higher luminous efficiency, and longer driving life than conventional ones. Furthermore, the composition for an organic electroluminescent device of the present invention can appropriately suppress the light emission of the self-assisted dopant by making the composition ratio of the light-emitting dopant greater than the composition ratio of the auxiliary dopant, thereby making it possible to produce more vivid Organic electroluminescent elements with different luminous colors.

即，本發明的主旨如下。 [1] 一種有機電場發光元件用組成物，包含下述式（1）所表示的化合物、最大發光波長相較於所述式（1）所表示的化合物而為短波的下述式（2）所表示的化合物、及溶媒。That is, the gist of the present invention is as follows. [1] A composition for an organic electroluminescent element, comprising a compound represented by the following formula (1) and the following formula (2) whose maximum emission wavelength is shorter than the compound represented by the formula (1) The compound and solvent shown.

[化1]

[化1]

[所述式中，R¹ 、R² 分別獨立地為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R¹ 、R² 的情況下，該些可分別相同亦可不同；於存在多個R¹ 的情況下，相鄰的R¹ 可彼此鍵結而形成環； a為0～4的整數，b為0～3的整數； R³ 、R⁴ 分別獨立地為氫原子、氟原子、氯原子、溴原子、碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數2～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～20的（雜）芳基；該些基亦可進而具有取代基；於存在多個R³ 、R⁴ 的情況下，該些可分別相同亦可不同； L¹ 表示有機配位子，m為1～3的整數][In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and 3 ～20 (hetero)aryloxy groups, C1-C20 alkylsilyl groups, C6-C20 arylsilyl groups, C2-C20 alkylcarbonyl groups, C7-20 aryl groups A carbonyl group, an alkylamino group having 1 to 20 carbons, an arylamino group having 6 to 20 carbons, or a (hetero)aryl group having 3 to 30 carbons; these groups may further have substituents; In the case of R ¹ and R ² , these may be the same or different respectively; when there are multiple R ¹ , adjacent R ¹ may be bonded to each other to form a ring; a is an integer of 0-4, b is an integer of 0 to 3; R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbons, and a (hetero)aralkyl group having 7 to 40 carbons , Alkoxy groups with 1-20 carbons, (hetero)aryloxy groups with 3-20 carbons, alkylsilyl groups with 1-20 carbons, arylsilyl groups with 6-20 carbons, 2 to carbons 20 alkylcarbonyl group, arylcarbonyl group having 7-20 carbons, alkylamino group having 2-20 carbons, arylamino group having 6-20 carbons, or (hetero)aryl group having 3-20 carbons ; These groups may further have substituents; when there are multiple R ³ and R ⁴ , these may be the same or different; L ¹ represents an organic ligand, and m is an integer of 1 to 3]

[化2]

[化2]

[所述式中，R⁵ 為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁵ 的情況下，該些可相同亦可不同； c為0～4的整數；環A為吡啶環、吡嗪環、嘧啶環、咪唑環、噁唑環、噻唑環、喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯（azatriphenylene）環、咔啉（carboline）環、苯並噻唑環、苯並噁唑環中的任一者；環A可具有取代基，所述取代基為氟原子、氯原子、溴原子、碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數2～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～20的（雜）芳基；另外，鍵結於環A的相鄰的取代基彼此可鍵結而進而形成環；於存在多個環A的情況下，該些可相同亦可不同； L² 表示有機配位子，n為1～3的整數][In the above formula, R ⁵ is a C 1-20 alkyl group, a C 7-40 (hetero)aralkyl group, a C 1-20 alkoxy group, a C 3-20 (hetero) Aryloxy group, C1-C20 alkylsilyl group, C6-C20 arylsilyl group, C2-C20 alkylcarbonyl group, C7-20 arylcarbonyl group, C1-C12 group 20 alkylamino groups, carbon 6-20 arylamino groups, or carbon 3-30 (hetero)aryl groups; these groups may further have substituents; when there are more than one R ⁵ , These may be the same or different; c is an integer from 0 to 4; ring A is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, a quinoline ring, an isoquinoline ring, and quinoline Any one of an oxazoline ring, a quinoxaline ring, an azatriphenylene ring, a carboline ring, a benzothiazole ring, and a benzoxazole ring; ring A may have a substituent, so The substituents are fluorine atom, chlorine atom, bromine atom, C1-C20 alkyl group, C7-40 (hetero)aralkyl group, C1-C20 alkoxy group, C3-C20 (Hetero)aryloxy group, C1-C20 alkylsilyl group, C6-C20 arylsilyl group, C2-C20 alkylcarbonyl group, C7-20 arylcarbonyl group, An alkylamino group having 2 to 20 carbons, an arylamino group having 6 to 20 carbons, or a (hetero)aryl group having 3 to 20 carbons; in addition, adjacent substituents bonded to ring A may be mutually Bonded to form a ring; when there are multiple rings A, these may be the same or different; L ² represents an organic ligand, and n is an integer from 1 to 3]

[2] 如所述[1]所述的有機電場發光元件用組成物，其中所述式（1）所表示的化合物的組成比於質量份換算中為所述式（2）所表示的化合物的組成比以上。 [3] 如所述[1]或[2]所述的有機電場發光元件用組成物，其中所述式（1）所表示的化合物為下述式（1-1）所表示的化合物。[2] The composition for an organic electroluminescence element according to [1], wherein the composition ratio of the compound represented by the formula (1) is the compound represented by the formula (2) in terms of parts by mass The composition ratio above. [3] The composition for an organic electroluminescent device according to [1] or [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

[化3]

[化3]

[所述式中，R¹ 、R² 、a、b、L¹ 、m與所述式（1）中的R¹ 、R² 、a、b、L¹ 、m分別意義相同； R⁶ 、R⁷ 分別獨立地為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁶ 、R⁷ 的情況下，該些可分別相同亦可不同； d、e分別獨立地為0～5的整數][In the ^{^{formula, R 1, R 2, a}} , b, L 1, m and (1) the formula wherein R ^{^{1, R 2, a, b}} , L 1, m are the same meaning; R ^6, R ^{7 is} each independently an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and a (hetero)aryloxy group having 3 to 20 carbons. , Alkylsilyl group with 1-20 carbons, arylsilyl group with 6-20 carbons, alkylcarbonyl group with 2-20 carbons, arylcarbonyl group with 7-20 carbons, alkane with 1-20 carbons Amino group, arylamino group having 6 to 20 carbon atoms, or (hetero)aryl group having 3 to 30 carbon atoms; these groups may further have substituents; when there are multiple R ⁶ and R ⁷ , These may be the same or different; d and e are each independently an integer of 0-5]

[4] 如所述[1]或[2]所述的有機電場發光元件用組成物，其中所述式（1）所表示的化合物為下述式（1-2）所表示的化合物。[4] The composition for an organic electroluminescent device according to [1] or [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (1-2).

[化4]

[化4]

[所述式中，R² ～R⁴ 、b、L¹ 、m與所述式（1）中的R² ～R⁴ 、b、L¹ 、m分別意義相同； R¹⁴ ～R¹⁶ 為取代基，於存在多個R¹⁴ ～R¹⁶ 的情況下，該些可分別相同亦可不同； i為0～4的整數][In the ^{^{formula, R 2 ~ R 4, b}} , L 1, m and (1) of the formula R ^{^{2 ~ R 4, b, L}} 1, m are the same meaning; R ¹⁴ ~ R ¹⁶ is substituted In the case where there are a plurality of R ¹⁴ to R ¹⁶ , these may be the same or different; i is an integer from 0 to 4]

[5] 如所述[3]所述的有機電場發光元件用組成物，其中所述式（1-1）所表示的化合物為下述式（1-3）所表示的化合物。[5] The composition for an organic electroluminescent device according to [3], wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-3).

[化5]

[化5]

[所述式中，R² 、R⁶ 、R⁷ 、b、d、e、L¹ 、m與所述式（1-1）中的R² 、R⁶ 、R⁷ 、b、d、e、L¹ 、m分別意義相同； R¹⁴ ～R¹⁶ 為取代基，於存在多個R¹⁴ ～R¹⁶ 的情況下，該些可分別相同亦可不同； i為0～4的整數][In the formula, R ^2, R ^6, the ^{R 7, b, d, e} , L 1, m in the formula ^{^{(1-1) R 2, R 6}} , R 7, b, d, e , L ¹ and m respectively have the same meaning; R ¹⁴ to R ¹⁶ are substituents, and when there are multiple R ¹⁴ to R ¹⁶ , these may be the same or different; i is an integer from 0 to 4]

[6] 如所述[1]至[5]中任一項所述的有機電場發光元件用組成物，其中所述式（2）所表示的化合物為下述式（2-1）所表示的化合物。[6] The composition for an organic electroluminescent element according to any one of [1] to [5], wherein the compound represented by the formula (2) is represented by the following formula (2-1) compound of.

[化6]

[化6]

[所述式中，環A、L² 、n與所述式（2）中的環A、L² 、n分別意義相同； R⁸ 為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁸ 的情況下，該些可相同亦可不同； f為0～5的整數][In the formula, Ring ^A, L ^2, n in the formula (2) in ring A, L ² n are the same meaning,; R ⁸ is alkyl having 1 to 20 carbon atoms from 7 to 40 (Hetero)aralkyl group, alkoxy group with 1-20 carbons, (hetero)aryloxy group with 3-20 carbons, alkylsilyl group with 1-20 carbons, aryl group with 6-20 carbons Silyl group, alkylcarbonyl group with 2-20 carbons, arylcarbonyl group with 7-20 carbons, alkylamino group with 1-20 carbons, arylamino group with 6-20 carbons, or 3-20 carbons The (hetero)aryl group of 30; these groups may further have substituents; when there are a plurality of R ⁸ , these may be the same or different; f is an integer of 0-5]

[7] 如所述[1]至[6]中任一項所述的有機電場發光元件用組成物，其中所述式（1）中的m不足3，L¹ 具有選自由下述式（3）、式（4）及式（5）所組成的群組中的至少一種結構。[7] The composition for an organic electroluminescent element according to any one of [1] to [6], wherein m in the formula (1) is less than 3, and L ¹ is selected from the following formula ( 3) At least one structure in the group consisting of formula (4) and formula (5).

[化7]

[化7]

[所述式（3）～式（5）中，R⁹ 、R¹⁰ 與所述式（1）中的R¹ 意義相同，於存在多個R⁹ 、R¹⁰ 的情況下，該些可分別相同亦可不同； R¹¹ ～R¹³ 分別獨立地為氫原子、可經氟原子取代的碳數1～20的烷基、可經碳數1～20的烷基取代的苯基、或鹵素原子； g為0～4的整數；h為0～4的整數；環B為吡啶環、嘧啶環、咪唑環、喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環、苯並噻唑環或苯並噁唑環；環B亦可進而具有取代基][In the formulas (3) to (5), R ⁹ and R ¹⁰ have the same meaning as ^{R 1} in the formula (1). In ^{the case where there are multiple R 9} and R ¹⁰ , these can be separated The same or different; R ¹¹ to R ¹³ are each independently a hydrogen atom, a C 1-20 alkyl group which may be substituted with a fluorine atom, a phenyl group which may be substituted with a C 1-20 alkyl group, or a halogen atom ; G is an integer from 0 to 4; h is an integer from 0 to 4; ring B is a pyridine ring, pyrimidine ring, imidazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, aza Triphenylene ring, carboline ring, benzothiazole ring or benzoxazole ring; ring B may further have substituents]

[8] 如所述[1]至[7]中任一項所述的有機電場發光元件用組成物，其中所述式（1）中的a為1，或者所述式（1）中的a為2以上的整數且不具有相鄰的R¹ 相互鍵結而成的環。 [9] 一種有機電場發光元件的製造方法，包括使用如所述[1]至[8]中任一項所述的有機電場發光元件用組成物並藉由濕式成膜法來形成發光層的步驟。 [10] 一種有機電場發光元件，具有使用如所述[1]至[8]中任一項所述的有機電場發光元件用組成物而形成的發光層。 [11] 一種顯示裝置，具有如所述[10]所述的有機電場發光元件。 [發明的效果][8] The composition for an organic electroluminescent element according to any one of [1] to [7], wherein a in the formula (1) is 1, or in the formula (1) a is an integer of 2 or more and does not have ^{a ring in which adjacent R 1} are bonded to each other. [9] A method of manufacturing an organic electroluminescence element, comprising using the composition for an organic electroluminescence element as described in any one of [1] to [8] and forming a light-emitting layer by a wet film forming method A step of. [10] An organic electroluminescence element having a light-emitting layer formed using the composition for an organic electroluminescence element according to any one of [1] to [8]. [11] A display device having the organic electroluminescence element described in [10]. [Effects of the invention]

根據本發明，特別是於紅色元件中可藉由濕式成膜法來製造有機電場發光元件，可提供一種與先前相比，驅動電壓低、發光效率高、驅動壽命長的有機電場發光元件。According to the present invention, the wet film forming method can be used to manufacture the organic electroluminescent device especially in the red device, and it is possible to provide an organic electroluminescent device with lower driving voltage, higher luminous efficiency, and long driving life than before.

以下，詳細地說明本發明的實施形態，但本發明並不限定於以下的實施形態，可於其主旨的範圍內進行各種變形來實施。再者，本說明書中，（雜）芳烷基、（雜）芳氧基、（雜）芳基分別表示可含有雜原子的芳烷基、可含有雜原子的芳氧基、可含有雜原子的芳基。「可含有雜原子」表示形成芳基、芳烷基或芳氧基的主骨架中的芳基骨架的碳原子中的一個或兩個以上的碳原子被取代為雜原子。作為雜原子，可列舉氮原子、氧原子、硫原子、磷原子、矽原子等，其中就耐久性的觀點而言，較佳為氮原子。Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. Furthermore, in this specification, (hetero)aralkyl, (hetero)aryloxy, and (hetero)aryl respectively represent an aralkyl group that may contain a heteroatom, an aryloxy group that may contain a heteroatom, and an aryloxy group that may contain a heteroatom.的aryl. "May contain heteroatoms" means that one or two or more of the carbon atoms forming the aryl skeleton in the main skeleton of the aryl group, aralkyl group, or aryloxy group are substituted with heteroatoms. As a hetero atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, etc. are mentioned, Among them, a nitrogen atom is preferable from a durability viewpoint.

[發光摻雜劑] 本實施形態的有機電場發光元件用組成物包含下述式（1）所表示的化合物，所述化合物主要作為發光摻雜劑來發揮功能。式（1）所表示的化合物可僅含有一種，亦可含有多種。另外，成為發光摻雜劑的化合物可包含式（1）所表示的化合物以外的成為發光摻雜劑的化合物，該情況下，相對於成為發光摻雜劑的化合物的合計，式（1）所表示的化合物的合計含量較佳為設為50質量%以上，更佳為100質量%。即，更佳為僅為式（1）所表示的化合物。[Luminescent Dopant] The composition for an organic electroluminescent element of this embodiment contains a compound represented by the following formula (1), and the compound mainly functions as a light-emitting dopant. The compound represented by formula (1) may contain only one type, or may contain multiple types. In addition, the compound that becomes a light-emitting dopant may include a compound that becomes a light-emitting dopant other than the compound represented by the formula (1). In this case, with respect to the total of the compounds that become the light-emitting dopant, the compound represented by the formula (1) The total content of the compounds shown is preferably 50% by mass or more, more preferably 100% by mass. That is, it is more preferable to be only the compound represented by formula (1).

[化8]

[化8]

所述式（1）中，R¹ 、R² 分別獨立地為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基。該些基亦可進而具有取代基。於存在多個R¹ 、R² 的情況下，該些可分別相同亦可不同。於存在多個R¹ 的情況下，相鄰的R¹ 可彼此鍵結而形成環。 a為0～4的整數，b為0～3的整數。In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and a carbon (Hetero)aryloxy group with 3-20, alkylsilyl group with 1-20 carbons, arylsilyl group with 6-20 carbons, alkylcarbonyl group with 2-20 carbons, 7-20 carbons An arylcarbonyl group, an alkylamino group having 1 to 20 carbons, an arylamino group having 6 to 20 carbons, or a (hetero)aryl group having 3 to 30 carbons. These groups may further have a substituent. When there are a plurality of R ¹ and R ² , these may be the same or different. When there are a plurality of R ¹ , adjacent R ¹ may be bonded to each other to form a ring. a is an integer of 0-4, and b is an integer of 0-3.

R³ 、R⁴ 分別獨立地為氫原子、氟原子、氯原子、溴原子、碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數2～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～20的（雜）芳基。該些基亦可進而具有取代基。於存在多個R³ 、R⁴ 的情況下，該些可分別相同亦可不同。 L¹ 表示有機配位子，m為1～3的整數。R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, and an alkane having 1 to 20 carbons. Oxy group, (hetero)aryloxy group with 3-20 carbons, alkylsilyl group with 1-20 carbons, arylsilyl group with 6-20 carbons, alkylcarbonyl group with 2-20 carbons, carbon number A 7-20 arylcarbonyl group, an alkylamino group having 2-20 carbons, an arylamino group having 6-20 carbons, or a (hetero)aryl group having 3-20 carbons. These groups may further have a substituent. When there are a plurality of R ³ and R ⁴ , these may be the same or different. L ¹ represents an organic ligand, and m is an integer of 1-3.

就耐久性的方面而言，R¹ ～R⁴ 分別獨立地更佳為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數6～20的芳基胺基、或者碳數3～30的（雜）芳基或碳數3～20的（雜）芳基，進而佳為碳數1～20的烷基、碳數7～40的（雜）芳烷基或碳數3～20的（雜）芳基，更進而佳為碳數1～20的烷基、碳數7～40的芳烷基或碳數6～20的芳基。 R¹ ～R⁴ 可進而具有的取代基較佳為選自後述的取代基群Z中的取代基。於a為2以上的情況下，鄰接的兩個R¹ 可相互鍵結而形成環。In terms of durability, R ¹ to R ⁴ are each independently more preferably an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, and an arylamine having 6 to 20 carbons. Group, or (hetero)aryl group having 3 to 30 carbons or (hetero)aryl group having 3 to 20 carbons, more preferably alkyl having 1 to 20 carbons, (hetero)arane having 7 to 40 carbons A group or a (hetero)aryl group having 3 to 20 carbons, more preferably an alkyl group having 1 to 20 carbons, an aralkyl group having 7 to 40 carbons, or an aryl group having 6 to 20 carbons. The substituent that R ¹ to R ⁴ may further have is preferably a substituent selected from the substituent group Z described later. When a is 2 or more, two adjacent R ¹ may be bonded to each other to form a ring.

作為存在多個R¹ 且相鄰的R¹ 相互鍵結而形成環者，例如可列舉芴、萘、二苯並噻吩、二苯並呋喃。就穩定性的觀點而言，特別是較佳為芴。就使發光波長長波長化的觀點而言，較佳為相鄰的R¹ 相互鍵結而形成環者。Examples of those having a plurality of R ¹ and adjacent R ¹ being bonded to each other to form a ring include fluorene, naphthalene, dibenzothiophene, and dibenzofuran. From the viewpoint of stability, fluorene is particularly preferred. From the viewpoint of increasing the emission wavelength, it is preferable that adjacent R ¹ are bonded to each other to form a ring.

另外，就不使發光波長長波長化的觀點而言，較佳為相鄰的R¹ 不相互鍵結，而非形成環者。即，較佳為式（1）中的a為1、或者a為2以上且不具有相鄰的R¹ 相互鍵結而成的環。In addition, from the viewpoint of not increasing the emission wavelength, it is preferable that adjacent R ^{1 are} not bonded to each other, rather than forming a ring. That is, it is preferable that a in the formula (1) is 1, or a is 2 or more and does not have ^{a ring in which adjacent R 1} are bonded to each other.

關於a，就容易製造的方面而言，較佳為0，就可提高耐久性及溶解性的方面而言，較佳為1或2，進而佳為1。關於b，就容易製造的方面而言，較佳為0，就可提高溶解性的方面而言，較佳為1。就大量存在包含三嗪環的受電子性高的結構、LUMO更穩定化的方面而言，m較佳為2或3，進而佳為3。Regarding a, in terms of ease of manufacture, 0 is preferred, and in terms of improving durability and solubility, 1 or 2 is preferred, and 1 is more preferred. Regarding b, 0 is preferable in terms of ease of manufacture, and 1 is preferable in terms of improving solubility. In terms of a large amount of electron-accepting structures including triazine rings and more stable LUMO, m is preferably 2 or 3, and more preferably 3.

L¹ 為有機配位子，無特別限制，較佳為一價的二齒配位子，更佳為選自下述化學式中。再者，化學式中的虛線表示配位鍵。於存在兩個有機配位子L¹ 的情況下，有機配位子L¹ 可具有互不相同的結構。另外，m為3時，不存在L¹ 。於式（1）中的m不足3的情況下，L¹ 較佳為具有選自由下述式（3）、式（4）及式（5）所組成的群組中的至少一種結構。L ¹ is an organic ligand and is not particularly limited. It is preferably a monovalent bidentate ligand, and more preferably selected from the following chemical formulas. Furthermore, the dotted line in the chemical formula represents a coordinate bond. In the case where there are two organic ligands L ¹ , the organic ligands L ¹ may have different structures from each other. In addition, when m is 3, L ¹ does not exist. When m in formula (1) is less than 3, L ¹ preferably has at least one structure selected from the group consisting of the following formula (3), formula (4), and formula (5).

[化9]

[化9]

所述式（3）、式（4）、式（5）中，R⁹ 、R¹⁰ 與所述式（1）中的R¹ 意義相同。即，選自與作為R¹ 而選擇的取代基相同的群組，較佳的例子亦相同，亦可進而具有取代基。於存在多個R⁹ 、R¹⁰ 的情況下，該些可分別相同亦可不同。 R¹¹ ～R¹³ 分別獨立地為氫原子、可經氟原子取代的碳數1～20的烷基、可經碳數1～20的烷基取代的苯基、或鹵素原子。 g為0～4的整數。h為0～4的整數。環B為吡啶環、嘧啶環、咪唑環、喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環、苯並噻唑環或苯並噁唑環。環B可進而具有取代基。In the formula (3), formula (4), and formula (5), R ⁹ and R ¹⁰ have the same meaning as ^{R 1} in the formula (1). That is, it is selected from the ^{same group as the substituent selected as R 1} , and preferable examples are also the same, and it may further have a substituent. When there are a plurality of R ⁹ and R ¹⁰ , these may be the same or different. R ¹¹ to R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbons which may be substituted with a fluorine atom, a phenyl group which may be substituted with an alkyl group of 1 to 20 carbons, or a halogen atom. g is an integer of 0-4. h is an integer of 0-4. Ring B is a pyridine ring, a pyrimidine ring, an imidazole ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a quinoxaline ring, an azatriphenylene ring, a carboline ring, a benzothiazole ring or a benzoxazole Azole ring. Ring B may further have a substituent.

R⁹ 、R¹⁰ 、環B可進而具有的取代基較佳為選自後述的取代基群Z中的取代基。進而佳的R⁹ 、R¹⁰ 分別獨立地為碳數1～20的烷基、或可經碳數1～20的烷基取代的碳數6～30的芳基。此處，碳數6～30的芳基是指單環、2環縮合環、3環縮合環、或者單環、2環縮合環、或3環縮合環連結多個而成的基。The substituent that R ⁹ , R ¹⁰ , and ring B may further have is preferably a substituent selected from the substituent group Z described later. More ^{preferably, R 9} and R ¹⁰ are each independently an alkyl group having 1 to 20 carbons, or an aryl group having 6 to 30 carbons which may be substituted with an alkyl group having 1 to 20 carbons. Here, the aryl group having 6 to 30 carbon atoms refers to a group formed by connecting a plurality of monocyclic rings, bicyclic condensed rings, tricyclic condensed rings, or monocyclic, bicyclic condensed rings, or tricyclic condensed rings.

關於g、h，就容易製造的方面而言，較佳為0，就可提高溶解性的方面而言，較佳為1或2，進而佳為1。 R¹¹ 至R¹³ 分別獨立地表示氫原子、可經氟原子取代的碳數1～20的烷基、可經碳數1～20的烷基取代的苯基、或鹵素原子，更佳為R¹¹ 與R¹³ 為甲基或第三丁基，R¹² 為氫原子、碳數1～20的烷基、或苯基。Regarding g and h, 0 is preferred in terms of ease of production, and 1 or 2 is preferred in terms of improving solubility, and 1 is more preferred. R ¹¹ to R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, a phenyl group which may be substituted by an alkyl group having 1 to 20 carbon atoms, or a halogen atom, more preferably R ¹¹ and R ¹³ are a methyl group or a tertiary butyl group, and R ¹² is a hydrogen atom, a C 1-20 alkyl group, or a phenyl group.

就耐久性的方面而言，環B較佳為吡啶環、嘧啶環、咪唑環，進而佳為吡啶環。就耐久性的方面及可提高溶解性的方面而言，環B上的氫原子較佳為經碳數1～20的烷基、碳數7～40的（雜）芳烷基、或碳數3～20的（雜）芳基取代。另外，就容易製造的方面而言，環B上的氫原子較佳為不被取代。進而，環B上的氫原子容易於用作有機電場發光元件時生成激子，因此就可提高發光效率的方面而言，較佳為經可具有取代基的苯基或萘基取代。苯基或萘基可具有的取代基較佳為選自後述的取代基群Z中的取代基。In terms of durability, ring B is preferably a pyridine ring, a pyrimidine ring, or an imidazole ring, and more preferably a pyridine ring. In terms of durability and improved solubility, the hydrogen atom on ring B is preferably an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, or a carbon number 3-20 (hetero) aryl substitution. In addition, in terms of ease of manufacture, the hydrogen atom on the ring B is preferably unsubstituted. Furthermore, the hydrogen atom on the ring B is likely to generate excitons when used as an organic electroluminescence element. Therefore, it is preferable to substitute a phenyl group or a naphthyl group which may have a substituent in terms of improving the luminous efficiency. The substituent that the phenyl group or the naphthyl group may have is preferably a substituent selected from the substituent group Z described later.

另外，環B容易於輔助摻雜劑上生成激子，因此就可提高發光效率的方面而言，較佳為喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環。其中，就耐久性的方面及顯示紅色發光的方面而言，更佳為喹啉環、異喹啉環、喹唑啉環。進而佳的環B的取代基為碳數1～20的烷基、或可經碳數1～20的烷基取代的碳數6～20的芳基。此處，碳數6～20的芳基是指單環、2環縮合環、3環縮合環、或者單環、2環縮合環、或3環縮合環連結多個而成的基。In addition, ring B is prone to generate excitons on the auxiliary dopant. Therefore, in terms of improving the luminous efficiency, it is preferably a quinoline ring, an isoquinoline ring, a quinazoline ring, a quinoxaline ring, and an azaline ring. Triphenylene ring, carboline ring. Among them, the quinoline ring, the isoquinoline ring, and the quinazoline ring are more preferable in terms of durability and the point of exhibiting red light emission. A further preferred substituent of ring B is an alkyl group having 1 to 20 carbons, or an aryl group having 6 to 20 carbons which may be substituted with an alkyl group having 1 to 20 carbons. Here, the aryl group having 6 to 20 carbon atoms refers to a group formed by connecting a plurality of monocyclic rings, bicyclic condensed rings, tricyclic condensed rings, or monocyclic, bicyclic condensed rings, or tricyclic condensed rings.

關於作為本實施形態的有機電場發光元件用組成物中所含的發光摻雜劑的、式（1）所表示的化合物，較佳為作為R³ 、R⁴ 可具有取代基的苯基的化合物，即下述式（1-1）所表示的化合物。Regarding the compound represented by formula (1) as the light-emitting dopant contained in the composition for the organic electroluminescent element of the present embodiment, a compound represented by a phenyl group which may have substituents ^{for R 3} and R ^{4 is preferred} , That is, the compound represented by the following formula (1-1).

[化10]

[化10]

[所述式中，R¹ 、R² 、a、b、L¹ 、m與式（1）中的R¹ 、R² 、a、b、L¹ 、m分別意義相同； R⁶ 、R⁷ 分別獨立地為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁶ 、R⁷ 的情況下，該些可分別相同亦可不同； d、e分別獨立地為0～5的整數][In the ^{^{^{formula, R 1, R 2, 1}}} , R 2, a, b, L 1, m are the same meaning ^a, b, L ^1, m in the formula R (1) is; R ^6, R ⁷ Each independently is an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, a (hetero)aryloxy group having 3 to 20 carbons, and carbon Alkylsilyl group with 1-20, arylsilyl group with 6-20 carbons, alkylcarbonyl group with 2-20 carbons, arylcarbonyl group with 7-20 carbons, alkylamine with 1-20 carbons Group, an arylamino group with 6 to 20 carbons, or a (hetero)aryl group with 3 to 30 carbons; these groups may further have substituents; when there are multiple R ⁶ and R ⁷ , the These may be the same or different; d and e are each independently an integer from 0 to 5]

就耐久性的方面而言，R⁶ 、R⁷ 更佳為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基，進而佳為碳數1～20的烷基、碳數7～40的（雜）芳烷基或碳數3～20的（雜）芳基，更進而佳為碳數1～20的烷基或碳數7～40的芳烷基。 R⁶ 、R⁷ 可進而具有的取代基較佳為選自後述的取代基群Z中的取代基。In terms of durability, R ⁶ and R ^{7 are more} preferably an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an arylamino group having 6 to 20 carbons, or A (hetero)aryl group having 3 to 30 carbons, more preferably an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, or a (hetero)aryl group having 3 to 20 carbons, more preferably More preferably, it is an alkyl group having 1 to 20 carbons or an aralkyl group having 7 to 40 carbons. The substituent that R ⁶ and R ⁷ may further have is preferably a substituent selected from the substituent group Z described later.

關於d、e，就容易製造的方面而言，較佳為0，就可提高耐久性及溶解性的方面而言，較佳為1或2，進而佳為1。關於b，就容易製造的方面而言，較佳為0，就可提高溶解性的方面而言，較佳為1。Regarding d and e, 0 is preferable in terms of ease of manufacture, and 1 or 2 is more preferable in terms of improving durability and solubility, and 1 is more preferable. Regarding b, 0 is preferable in terms of ease of manufacture, and 1 is preferable in terms of improving solubility.

本實施形態的有機電場發光元件用組成物中所含的式（1）所表示的發光摻雜劑較佳為a為2以上且鄰接的R¹ 彼此鍵結而形成了芴環的結構。其中，較佳為式（1-2）所表示的化合物。The light-emitting dopant represented by formula (1) contained in the composition for an organic electroluminescence element of the present embodiment preferably has a structure in which a is 2 or more and adjacent R ¹ are bonded to each other to form a fluorene ring. Among them, the compound represented by formula (1-2) is preferred.

[化11]

[化11]

[所述式中，R² ～R⁴ 、b、L¹ 、m與式（1）中的R² ～R⁴ 、b、L¹ 、m分別意義相同； R¹⁴ ～R¹⁶ 為取代基，於存在多個R¹⁴ ～R¹⁶ 的情況下，該些可分別相同亦可不同； i為0～4的整數][In the ^{^{^{formula, R 2 ~ R 4, 2}}} ~ R 4, b, L 1, m are the same meaning ^b, L ^1, m in the formula R (1) is; R ¹⁴ ~ R ¹⁶ is a substituent group, When there are a plurality of R ¹⁴ to R ¹⁶ , these may be the same or different; i is an integer from 0 to 4]

R¹⁴ 是取代於R¹ 為苯基時的R¹ 的取代基，較佳為選自後述的取代基群Z中的取代基。更佳為碳數1～20的烷基、可經碳數1～20的烷基取代的碳數6～30的芳香族烴基。此處，碳數6～30的芳香族烴基是指單環、2～4環縮合環、或者單環或2～4環縮合環連結多個而成的基。進而佳為碳數1～20的烷基，更進而佳為碳數1～8的烷基。 R¹⁵ 、R¹⁶ 是取代於R¹ 的一部分或R¹ 為甲基時的R¹ 的取代基，較佳為各自獨立地為碳數1～20的烷基、可經碳數1～20的烷基取代的碳數6～30的芳香族烴基、碳數1～20的烷氧基、或可經碳數1～20的烷氧基取代的碳數6～30的芳香族烴基。此處，碳數6～30的芳香族烴基是指單環、2～4環縮合環、或者單環或2～4環縮合環連結多個而成的基。更佳為碳數1～20的烷基或者可經碳數1～20的烷基取代的碳數6或12的芳香族烴基，進而佳為碳數1～8的烷基或者可經碳數1～8的烷基取代的碳數6的芳香族烴基。此處，碳數6的芳香族烴結構為苯結構，碳數12的芳香族烴結構為聯苯結構。R ¹⁴ is substituted on R ¹ is a substituted phenyl group when R ^1, the substituent group Z substituent is preferably selected from the group described later. More preferably, it is an alkyl group having 1 to 20 carbons, and an aromatic hydrocarbon group having 6 to 30 carbons which may be substituted with an alkyl group having 1 to 20 carbons. Here, the aromatic hydrocarbon group having 6 to 30 carbon atoms means a monocyclic ring, a condensed ring of 2 to 4 rings, or a group in which a plurality of condensed rings of a monocyclic ring or 2 to 4 rings are connected. It is more preferably an alkyl group having 1 to 20 carbons, and still more preferably an alkyl group having 1 to 8 carbons. R ^15, R ¹⁶ is substituted on R or R ¹ when a part of R ¹ is a methyl group substituted by ^1, preferably are each independently an alkyl group having 1 to 20 carbon atoms, and may be from 1 to 20 carbon atoms An alkyl-substituted aromatic hydrocarbon group with 6 to 30 carbons, an alkoxy group with 1 to 20 carbons, or an aromatic hydrocarbon group with 6 to 30 carbons which may be substituted with an alkoxy group with 1 to 20 carbons. Here, the aromatic hydrocarbon group having 6 to 30 carbon atoms means a monocyclic ring, a condensed ring of 2 to 4 rings, or a group in which a plurality of condensed rings of a monocyclic ring or 2 to 4 rings are connected. More preferably, it is an alkyl group having 1 to 20 carbons or an aromatic hydrocarbon group having 6 or 12 carbons which may be substituted with an alkyl group having 1 to 20 carbons, and more preferably an alkyl group having 1 to 8 carbons or may be substituted with an alkyl group having 1 to 20 carbons. A C6 aromatic hydrocarbon group substituted by an alkyl group of 1-8. Here, the aromatic hydrocarbon structure with carbon number 6 is a benzene structure, and the aromatic hydrocarbon structure with carbon number 12 is a biphenyl structure.

作為R¹⁴ ～R¹⁶ 中的較佳的烷基的具體例，可列舉甲基、乙基、正丙基、正丁基、正戊基、正己基、正辛基、異丙基、異丁基、異戊基、第三丁基、環己基、2-乙基己基等。作為R¹⁴ ～R¹⁶ 中的較佳的芳香族烴基的具體例，可列舉具有一個遊離原子價的苯環、萘環、蒽環、菲環、苝環、稠四苯、芘環、苯並芘環、䓛環、三伸苯（triphenylene）環、螢蒽（fluoranthene）環、聯苯基、三聯苯基等。作為R¹⁵ 、R¹⁶ 中的較佳的烷氧基的具體例，可列舉甲氧基、乙氧基、丙氧基、異丙氧基、己氧基、環己氧基、十八烷基氧基等。Specific examples of preferable alkyl groups in R ¹⁴ to R ¹⁶ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, isopropyl, and isobutyl. Group, isopentyl, tertiary butyl, cyclohexyl, 2-ethylhexyl, etc. Specific examples of preferable aromatic hydrocarbon groups in R ¹⁴ to R ¹⁶ include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetrabenzene, pyrene ring, benzo Pyrene ring, tri-ring, triphenylene ring, fluoranthene ring, biphenyl, terphenyl, etc. Specific examples of preferred alkoxy groups in R ¹⁵ and R ¹⁶ include methoxy, ethoxy, propoxy, isopropoxy, hexyloxy, cyclohexyloxy, and octadecyl Oxy etc.

本實施形態的有機電場發光元件用組成物中所含的式（1-1）所表示的成為發光摻雜劑的化合物進而佳為式（1-3）所表示的化合物。The compound represented by formula (1-1) and used as a light-emitting dopant contained in the composition for an organic electroluminescent element of the present embodiment is more preferably a compound represented by formula (1-3).

[化12]

[化12]

[所述式中，R² 、R⁶ 、R⁷ 、b、d、e、L¹ 、m與式（1-1）中的R² 、R⁶ 、R⁷ 、b、d、e、L¹ 、m分別意義相同； R¹⁴ ～R¹⁶ 為取代基，於存在多個R¹⁴ ～R¹⁶ 的情況下，該些可分別相同亦可不同； i為0～4的整數][In the formula, R ^2, R ^6, the ^{R 7, b, d, e} , L 1, m in the formula ^{^{(1-1) R 2, R 6}} , R 7, b, d, e, L ¹ and m respectively have the same meaning; R ¹⁴ to R ¹⁶ are substituents, and when there are a plurality of R ¹⁴ to R ¹⁶ , these may be the same or different; i is an integer of 0 to 4]

R¹⁴ ～R¹⁶ 所表示的取代基與式（1-2）中的R¹⁴ ～R¹⁶ 所表示的取代基分別意義相同，較佳的範圍亦相同。Substituents are the same meaning of substituents of formula (1-2) R R ¹⁴ ~ R ¹⁶ represented by ¹⁴ ~ R ¹⁶ represented by the preferred ranges are also the same.

以下示出實施例中所示出的化合物以外的本實施形態的有機電場發光元件用組成物中所含的成為發光摻雜劑的式（1）所表示的化合物的較佳的具體例，但本發明並不限定於該些。Preferred specific examples of the compound represented by the formula (1) contained in the composition for the organic electroluminescent element of the present embodiment as a light-emitting dopant other than the compounds shown in the examples are shown below, but The present invention is not limited to these.

[化13]

[化13]

[化14]

[化14]

[化15]

[化15]

[輔助摻雜劑] 本實施形態的有機電場發光元件用組成物包含下述式（2）所表示的化合物，所述化合物主要作為輔助摻雜劑來發揮功能。式（2）所表示的化合物的最大發光波長相較於所述成為發光摻雜劑的式（1）所表示的化合物為短波。因此，於式（2）所表示的輔助摻雜劑變為激發狀態的情況下，發生能量向激發能更小的式（1）所表示的發光摻雜劑的移動，因此，於發光摻雜劑變為激發狀態之後，觀測到自發光摻雜劑的發光。式（2）所表示的化合物可僅含有一種，亦可含有多種。另外，成為輔助摻雜劑的化合物亦可包含式（2）所表示的化合物以外的成為輔助摻雜劑的化合物，但該情況下，相對於成為輔助摻雜劑的化合物的合計，式（2）所表示的化合物的合計含量較佳為設為50質量%以上，更佳為100質量%。即，更佳為僅為式（2）所表示的化合物。[Auxiliary dopant] The composition for an organic electroluminescence element of this embodiment contains a compound represented by the following formula (2), and the compound mainly functions as an auxiliary dopant. The maximum emission wavelength of the compound represented by the formula (2) is shorter than that of the compound represented by the formula (1) as a light-emitting dopant. Therefore, when the auxiliary dopant represented by the formula (2) becomes an excited state, the energy shifts to the light-emitting dopant represented by the formula (1) with a smaller excitation energy. Therefore, the light-emitting dopant After the agent becomes an excited state, luminescence of the self-luminous dopant is observed. The compound represented by formula (2) may contain only one type, or may contain multiple types. In addition, the compound serving as an auxiliary dopant may include compounds serving as auxiliary dopants other than the compound represented by formula (2), but in this case, with respect to the total of the compounds serving as auxiliary dopants, formula (2) The total content of the compounds represented by) is preferably 50% by mass or more, and more preferably 100% by mass. That is, it is more preferable to be only the compound represented by formula (2).

另外，較佳為將式（1）所表示的化合物的組成比設為以質量份換算計為式（2）所表示的化合物的組成比以上。藉此，可抑制自式（2）所表示的輔助摻雜劑直接發光，能量以高的效率自式（2）所表示的輔助摻雜劑向式（1）所表示的發光摻雜劑轉移。因此，能夠以高的效率獲得發光摻雜劑的發光。In addition, it is preferable to set the composition ratio of the compound represented by formula (1) to be greater than or equal to the composition ratio of the compound represented by formula (2) in terms of parts by mass. As a result, direct light emission from the auxiliary dopant represented by formula (2) can be suppressed, and energy transfer from the auxiliary dopant represented by formula (2) to the light-emitting dopant represented by formula (1) with high efficiency . Therefore, the luminescence of the luminescent dopant can be obtained with high efficiency.

[化16]

[化16]

所述式中，R⁵ 為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基。該些基亦可進而具有取代基。於存在多個R⁵ 的情況下，該些可相同亦可不同。 c為0～4的整數。環A為吡啶環、吡嗪環、嘧啶環、咪唑環、噁唑環、噻唑環、喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環、苯並噻唑環、苯並噁唑環中的任一者。In the above formula, R ⁵ is an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and a (hetero)aryl group having 3 to 20 carbons. An oxy group, an alkylsilyl group with 1 to 20 carbons, an arylsilyl group with 6 to 20 carbons, an alkylcarbonyl group with 2 to 20 carbons, an arylcarbonyl group with 7 to 20 carbons, and 1 to 20 carbons. The alkylamino group, the arylamino group with 6 to 20 carbons, or the (hetero)aryl group with 3 to 30 carbons. These groups may further have a substituent. When there are a plurality of R ⁵ , these may be the same or different. c is an integer of 0-4. Ring A is pyridine ring, pyrazine ring, pyrimidine ring, imidazole ring, oxazole ring, thiazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, azatriphenylene ring, carbohydrate Any one of a morpholine ring, a benzothiazole ring, and a benzoxazole ring.

環A可具有取代基。所述取代基為氟原子、氯原子、溴原子、碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、烷基的碳數為1～20的烷基矽烷基、芳基的碳數為6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數2～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～20的（雜）芳基。另外，鍵結於環A的相鄰的取代基彼此可鍵結而進而形成環。於存在多個環A的情況下，該些可相同亦可不同。 L² 表示有機配位子，n為1～3的整數。Ring A may have a substituent. The substituents are fluorine atom, chlorine atom, bromine atom, C1-C20 alkyl group, C7-40 (hetero)aralkyl group, C1-C20 alkoxy group, C3-C3 The (hetero)aryloxy group of 20, the alkylsilyl group having 1 to 20 carbon atoms in the alkyl group, the arylsilyl group having 6 to 20 carbon atoms in the aryl group, the alkylcarbonyl group having 2 to 20 carbon atoms, and the An arylcarbonyl group having 7 to 20, an alkylamino group having 2 to 20 carbons, an arylamino group having 6 to 20 carbons, or a (hetero)aryl group having 3 to 20 carbons. In addition, adjacent substituents bonded to ring A may be bonded to each other to form a ring. When there are a plurality of rings A, these may be the same or different. L ² represents an organic ligand, and n is an integer of 1-3.

R⁵ 可進而具有的取代基較佳為選自後述的取代基群Z中的取代基。就耐久性的方面而言，R⁵ 更佳為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基，進而佳為碳數1～20的烷基、碳數7～40的（雜）芳烷基或碳數3～20的（雜）芳基。就耐久性的方面及溶解性的方面而言，R⁵ 較佳為可具有取代基的苯基，且鍵結於環A的間（m-）位、銥的對（p-）位。即，較佳為包含下述式（2-1）所表示的化合物。可具有的取代基較佳為選自後述的取代基群Z中的取代基。The substituent that R ⁵ may further have is preferably a substituent selected from the substituent group Z described later. In terms of durability, R ^{5 is more} preferably an alkyl group having 1 to 20 carbon atoms, a (hetero)aralkyl group having 7 to 40 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or 3 carbon atoms. The (hetero)aryl group of ~30 is more preferably an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, or a (hetero)aryl group having 3 to 20 carbons. In terms of durability and solubility, R ^{5 is} preferably a phenyl group which may have a substituent and is bonded to the meta (m-) position of ring A and the para (p-) position of iridium. That is, it is preferable to include a compound represented by the following formula (2-1). The substituent which may be possessed is preferably a substituent selected from the substituent group Z described later.

[化17]

[化17]

[所述式中，環A、L² 、n與式（2）中的環A、L² 、n分別意義相同。 R⁸ 為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基。該些基亦可進而具有取代基。於存在多個R⁸ 的情況下，該些可相同亦可不同。 f為0～5的整數。[In the formula, Ring ^A, L ^2, n and the ring of formula A (2) of the same meaning L ² n, respectively. R ⁸ is alkyl having 1 to 20 carbons, (hetero)aralkyl having 7 to 40 carbons, alkoxy having 1 to 20 carbons, (hetero)aryloxy having 3 to 20 carbons, and carbon number 1-20 alkylsilyl groups, 6-20 arylsilyl groups, 2-20 alkylcarbonyl groups, 7-20 arylcarbonyl groups, and 1-20 alkylamino groups , C6-20 arylamino group, or C3-30 (hetero)aryl group. These groups may further have a substituent. When there are a plurality of R ⁸ , these may be the same or different. f is an integer of 0-5.

R⁸ 可進而具有的取代基較佳為選自後述的取代基群Z中的取代基。關於f，就容易製造的方面而言，較佳為0，就耐久性的方面及可提高溶解性的方面而言，較佳為1或2，進而佳為1。就耐久性的方面而言，環A較佳為吡啶環、嘧啶環、咪唑環，進而佳為吡啶環。The substituent that R ⁸ may further have is preferably a substituent selected from the substituent group Z described later. Regarding f, 0 is preferred in terms of ease of manufacture, and 1 or 2 is more preferred in terms of durability and solubility, and 1 is more preferred in terms of durability. In terms of durability, ring A is preferably a pyridine ring, a pyrimidine ring, or an imidazole ring, and more preferably a pyridine ring.

就耐久性的方面及可提高溶解性的方面而言，環A上的氫原子較佳為經碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數3～20的（雜）芳基取代。另外，就容易製造的方面而言，環A上的氫原子較佳為不被取代。環A上的氫原子容易於用作有機電場發光元件時生成激子，因此就可提高發光效率的方面而言，較佳為經可具有取代基的苯基或萘基取代。In terms of durability and improved solubility, the hydrogen atom on ring A is preferably an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, and a carbon number of 3 ~20 (hetero)aryl substitution. In addition, in terms of ease of manufacture, the hydrogen atom on the ring A is preferably not substituted. The hydrogen atom on the ring A tends to generate excitons when used as an organic electroluminescence element, and therefore, it is preferable to be substituted with a phenyl group or a naphthyl group which may have a substituent in terms of improving the luminous efficiency.

作為環A，就容易於輔助摻雜劑上生成激子、可提高發光效率的方面而言，較佳為喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環。其中，就耐久性的方面而言，較佳為喹啉環、異喹啉環、喹唑啉環。 L² 為有機配位子，無特別限制，但較佳為一價的二齒配位子，更佳的例子與作為L¹ 的較佳的例子而示出者相同。再者，於存在兩個有機配位子L² 的情況下，有機配位子L² 可為互不相同的結構。另外，n為3時，不存在L² 。As the ring A, in terms of easily generating excitons on the auxiliary dopant and improving luminous efficiency, it is preferably a quinoline ring, an isoquinoline ring, a quinazoline ring, a quinoxaline ring, and a azatrile ring. Benzene ring, carboline ring. Among them, in terms of durability, a quinoline ring, an isoquinoline ring, and a quinazoline ring are preferred. L ² is an organic ligand and is not particularly limited, but is preferably a monovalent bidentate ligand, and more preferable examples are the same as those shown as preferable examples of ^{L 1.} Furthermore, when there are two organic ligands L ² , the organic ligands L ² may have different structures from each other. In addition, when n is 3, L ² does not exist.

以下示出實施例中所示出的化合物以外的本實施形態的有機電場發光元件用組成物中所含的成為輔助摻雜劑的式（2）所表示的化合物的較佳的具體例，但本發明並不限定於該些。Preferred specific examples of the compound represented by formula (2) contained in the composition for the organic electroluminescence element of the present embodiment as an auxiliary dopant other than the compounds shown in the examples are shown below, but The present invention is not limited to these.

[化18]

[化18]

[取代基群Z] 作為取代基，可使用烷基、芳烷基、雜芳烷基、烷氧基、芳氧基、雜芳氧基、烷基矽烷基、芳基矽烷基、烷基羰基、芳基羰基、烷基胺基、芳基胺基、芳基或雜芳基。較佳為碳數1～20的烷基、碳數7～40的芳烷基、碳數7～40的雜芳烷基、碳數1～20的烷氧基、碳數6～20的芳氧基、碳數3～20的雜芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、碳數6～30的芳基、或碳數3～30的雜芳基，更具體而言是後述的[取代基的具體例]中記載的取代基。進而佳為碳數1～20的烷基、碳數7～40的芳烷基、碳數1～20的烷氧基、碳數6～20的芳氧基、或碳數6～30的芳基。[Substituent Group Z] As the substituent, an alkyl group, an aralkyl group, a heteroaralkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylsilyl group, an arylsilyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkane group can be used. Amino group, arylamino group, aryl group or heteroaryl group. Preferably, they are an alkyl group having 1 to 20 carbons, an aralkyl group having 7 to 40 carbons, a heteroaralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and an aryl group having 6 to 20 carbons. An oxy group, a heteroaryloxy group having 3 to 20 carbons, an alkylsilyl group having 1 to 20 carbons, an arylsilyl group having 6 to 20 carbons, an alkylcarbonyl group having 2 to 20 carbons, and a carbon number of 7 to 20 aryl carbonyl group, C 1-20 alkylamino group, C 6-20 arylamino group, C 6-30 aryl group, or C 3-30 heteroaryl group, more specifically They are the substituents described in [Specific Examples of Substituents] described later. Further preferred are alkyl groups having 1 to 20 carbons, aralkyl groups having 7 to 40 carbons, alkoxy groups having 1 to 20 carbons, aryloxy groups having 6 to 20 carbons, or aryl groups having 6 to 30 carbons. base.

[取代基的具體例] 所述各化合物結構中的取代基及所述取代基群Z中的取代基的具體例如下所述。作為所述碳數1～20的烷基，可為直鏈、分支或環狀的烷基中的任一者。更具體而言，可列舉甲基、乙基、正丙基、正丁基、正戊基、正己基、正辛基、異丙基、異丁基、異戊基、第三丁基、環己基等。其中，較佳為甲基、乙基、正丁基、正己基、正辛基等直鏈的碳數1～8的烷基。[Specific examples of substituents] The specific examples of the substituent in the structure of each compound and the substituent in the substituent group Z are as follows. The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, or cyclic alkyl groups. More specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, isopropyl, isobutyl, isopentyl, tertiary butyl, cyclo Hexyl etc. Among them, preferred are linear alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, n-butyl, n-hexyl, and n-octyl.

所述碳數7～40的（雜）芳烷基是指構成直鏈的烷基、分支的烷基或環狀的烷基的氫原子的一部分經芳基或雜芳基進行了取代的基。更具體而言，可列舉2-苯基-1-乙基、枯基、5-苯基-1-戊基、6-苯基-1-己基、7-苯基-1-庚基、四氫萘基等。其中，較佳為5-苯基-1-戊基、6-苯基-1-己基、7-苯基-1-庚基。The (hetero)aralkyl group having 7 to 40 carbon atoms refers to a group in which a part of the hydrogen atoms constituting a linear alkyl group, a branched alkyl group, or a cyclic alkyl group is substituted with an aryl group or a heteroaryl group . More specifically, 2-phenyl-1-ethyl, cumyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, 7-phenyl-1-heptyl, tetrakis Hydronaphthyl and so on. Among them, preferred are 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, and 7-phenyl-1-heptyl.

作為所述碳數1～20的烷氧基的具體例，可列舉甲氧基、乙氧基、丙氧基、異丙氧基、己氧基、環己氧基、十八烷基氧基等。其中，較佳為己氧基。Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a hexyloxy group, a cyclohexyloxy group, and an octadecyloxy group. Wait. Among them, hexyloxy is preferred.

作為所述碳數3～20的（雜）芳氧基的具體例，可列舉苯氧基、4-甲基苯基氧基等。其中，較佳為苯氧基。Specific examples of the (hetero)aryloxy group having 3 to 20 carbon atoms include a phenoxy group and a 4-methylphenyloxy group. Among them, phenoxy is preferred.

作為所述碳數1～20的烷基矽烷基的具體例，可列舉三甲基矽烷基、三乙基矽烷基、三異丙基矽烷基、二甲基苯基、第三丁基二甲基矽烷基、第三丁基二苯基矽烷基等。其中較佳為三異丙基、第三丁基二甲基矽烷基、第三丁基二苯基矽烷基。Specific examples of the alkylsilyl group having 1 to 20 carbon atoms include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, dimethylphenyl group, and tert-butyldimethylsilyl group. Base silyl group, tertiary butyl diphenyl silyl group, etc. Among them, a triisopropyl group, a tertiary butyldimethylsilyl group, and a tertiary butyldiphenylsilyl group are preferred.

作為所述碳數6～20的芳基矽烷基的具體例，可列舉二苯基吡啶基矽烷基、三苯基矽烷基等。其中較佳為三苯基矽烷基。Specific examples of the arylsilyl group having 6 to 20 carbon atoms include a diphenylpyridylsilyl group and a triphenylsilyl group. Among them, a triphenylsilyl group is preferred.

作為所述碳數2～20的烷基羰基的具體例，可列舉乙醯基、丙醯基、三甲基乙醯基、己醯基、癸醯基、環己基羰基等。其中較佳為乙醯基、三甲基乙醯基。Specific examples of the alkylcarbonyl group having 2 to 20 carbon atoms include an acetyl group, a propionyl group, a trimethyl acetyl group, a hexyl group, a decyl group, and a cyclohexyl carbonyl group. Among them, acetyl and trimethyl acetyl are preferred.

作為所述碳數7～20的芳基羰基的具體例，可列舉苯甲醯基、萘甲醯基、苯甲醯亞胺酸基等。其中較佳為苯甲醯基。Specific examples of the arylcarbonyl group having 7 to 20 carbon atoms include a benzyl group, a naphthyl group, a benzimidyl group, and the like. Among them, a benzyl group is preferred.

作為所述碳數1～20的烷基胺基的具體例，可列舉甲基胺基、二甲基胺基、二乙基胺基、乙基甲基胺基、二己基胺基、二辛基胺基、二環己基胺基等。其中較佳為二甲基胺基、二環己基胺基。Specific examples of the alkylamino group having 1 to 20 carbon atoms include methylamino, dimethylamino, diethylamino, ethylmethylamino, dihexylamino, and dioctylamino. Amino, dicyclohexylamino, etc. Among them, dimethylamino and dicyclohexylamino are preferred.

作為所述碳數6～20的芳基胺基的具體例，可列舉苯基胺基、二苯基胺基、二(4-甲苯基)胺基、二(2,6-二甲基苯基)胺基等。其中較佳為二苯基胺基、二(4-甲苯基)胺基。Specific examples of the arylamino group having 6 to 20 carbon atoms include phenylamino group, diphenylamino group, bis(4-tolyl)amino group, and bis(2,6-dimethylbenzene). Group) amine group and so on. Among them, diphenylamino and bis(4-tolyl)amino are preferred.

所述碳數3～30的（雜）芳基是指具有一個遊離原子價的芳香族烴基、芳香族雜環基、多個芳香族烴連結而成的連結芳香族烴基、多個芳香族雜環基連結而成的連結芳香族雜環基、或芳香族烴及芳香族雜環分別任意連結至少一個以上而成的基。作為具體例，可列舉具有一個遊離原子價的苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯並芘環、䓛環、三伸苯環、螢蒽環、呋喃環、苯並呋喃環、二苯並呋喃環、噻吩環、苯並噻吩環、二苯並噻吩環、吡咯環、吡唑環、咪唑環、噁二唑環、吲哚環、咔唑環、吡咯並咪唑環、吡咯並吡唑環、吡咯並吡咯環、噻吩並吡咯環、噻吩並噻吩環、呋喃並吡咯環、呋喃並呋喃環、噻吩並呋喃環、苯並異噁唑環、苯並異噻唑環、苯並咪唑環、吡啶環、吡嗪環、噠嗪環、嘧啶環、三嗪環、喹啉環、異喹啉環、噌啉（cinnoline）環、喹噁啉環、呸啶（perimidine）環、喹唑啉環、喹唑啉酮環、薁（azulene）環等基。作為多個芳香族烴連結而成的連結芳香族烴基，可列舉聯苯基、三聯苯基等。The (hetero)aryl group having 3 to 30 carbon atoms refers to an aromatic hydrocarbon group having a free valence, an aromatic heterocyclic group, a connected aromatic hydrocarbon group formed by connecting a plurality of aromatic hydrocarbons, and a plurality of aromatic heterocyclic groups. A linked aromatic heterocyclic group formed by linking cyclic groups, or a group formed by arbitrarily linking at least one aromatic hydrocarbon and an aromatic heterocyclic ring, respectively. As specific examples, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, terphenylene ring, and fluoranthene ring with one free valence can be cited. Ring, furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carb Azole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring , Benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring , Perimidine (perimidine) ring, quinazoline ring, quinazolinone ring, azulene ring and other groups. Examples of the connected aromatic hydrocarbon group formed by connecting a plurality of aromatic hydrocarbons include biphenyl group, terphenyl group, and the like.

（雜）芳基中，就耐久性的觀點而言，較佳為具有一個遊離原子價的苯環、萘環、二苯並呋喃環、二苯並噻吩環、咔唑環、吡啶環、嘧啶環、三嗪環，其中，更佳為具有一個遊離原子價，且可經碳數為1～8的烷基取代的苯環、萘環或菲環等碳數6～18的芳基、或者具有一個遊離原子價、且可經碳數為1～4的烷基取代的吡啶環，進而佳為具有一個遊離原子價，且可經碳數為1～8的烷基取代的苯環、萘環或菲環等碳數6～18的芳基。Among the (hetero)aryl groups, from the viewpoint of durability, benzene ring, naphthalene ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, pyridine ring, pyrimidine ring having one free valence are preferred. A ring and a triazine ring, among them, more preferably an aryl group with 6 to 18 carbons such as a benzene ring, naphthalene ring or phenanthrene ring which has one free valence and may be substituted by an alkyl group with 1 to 8 carbons, or A pyridine ring which has one free valence and can be substituted by an alkyl group having 1 to 4 carbons, and more preferably a benzene ring and naphthalene ring which has a free valence and can be substituted by an alkyl group having 1 to 8 carbons An aryl group having 6 to 18 carbon atoms such as a ring or a phenanthrene ring.

於化合物中的基具有多個取代基的情況下，作為該些取代基的組合，例如可使用芳基與烷基的組合、芳基與芳烷基的組合、或者芳基與烷基、芳烷基的組合，但並不限定於該些。作為芳基與芳烷基的組合，例如可使用苯、聯苯基、三聯苯基與5-苯基-1-戊基、6-苯基-1-己基的組合。When the group in the compound has multiple substituents, as a combination of these substituents, for example, a combination of an aryl group and an alkyl group, a combination of an aryl group and an aralkyl group, or an aryl group and an alkyl group, or an aryl group can be used. The combination of alkyl groups is not limited to these. As a combination of an aryl group and an aralkyl group, for example, a combination of benzene, biphenyl group, terphenyl group, 5-phenyl-1-pentyl group, and 6-phenyl-1-hexyl group can be used.

[最大發光波長] 以下示出本實施形態中的化合物的最大發光波長的測定方法。化合物的最大發光波長可自使材料溶解於有機溶劑中而成的溶液的光致發光光譜或者僅材料的薄膜的光致發光光譜中求出。在為溶液的光致發光的情況下，常溫下，針對於2-甲基四氫呋喃中以濃度1×10^-4 mol/L以下溶解有化合物而成的溶液，利用分光光度計（濱松光子（Hamamatsu Photonics）公司製造的有機EL量子產率測定裝置C9920-02）測定磷光光譜。將表示所得到的磷光光譜強度的最大值的波長作為最大發光波長。在為薄膜的光致發光的情況下，對材料進行真空蒸鍍或溶液塗佈而製作薄膜，利用所述分光光度計測定光致發光，將表示所得到的發光光譜強度的最大值的波長作為最大發光波長。用於發光摻雜劑的化合物及用於輔助摻雜劑的化合物的最大發光波長需要利用同樣的方法求出來進行比較。[Maximum emission wavelength] The method for measuring the maximum emission wavelength of the compound in this embodiment is shown below. The maximum emission wavelength of the compound can be determined from the photoluminescence spectrum of a solution obtained by dissolving the material in an organic solvent or the photoluminescence spectrum of only a thin film of the material. In the case of solution photoluminescence, at room temperature, for ^{a solution containing a compound dissolved in 2-methyltetrahydrofuran at a concentration of 1×10 -4} mol/L or less, using a spectrophotometer (Hamamatsu Photon (Hamamatsu) Photonics) The organic EL quantum yield measuring device C9920-02 manufactured by Photonics) measures the phosphorescence spectrum. The wavelength representing the maximum value of the obtained phosphorescence spectrum intensity was taken as the maximum emission wavelength. In the case of the photoluminescence of a thin film, the material is vacuum deposited or solution coated to produce a thin film, the photoluminescence is measured by the spectrophotometer, and the wavelength representing the maximum value of the obtained luminescence spectrum intensity is taken as Maximum emission wavelength. The maximum emission wavelength of the compound used for the light-emitting dopant and the compound used for the auxiliary dopant needs to be determined by the same method for comparison.

本實施形態的有機電場發光元件用組成物中所含的成為輔助摻雜劑的式（2）所表示的化合物與成為發光摻雜劑的式（1）所表示的化合物相比，最大發光波長為短波。成為發光摻雜劑的化合物的最大發光波長較佳為580 nm以上，更佳為590 nm以上，進而佳為600 nm以上，另外，較佳為700 nm以下，更佳為680 nm以下。藉由使最大發光波長為該範圍，存在可表現出作為有機電場發光元件而較佳的紅色發光材料的較佳顏色的傾向。藉由使成為輔助摻雜劑的化合物的最大發光波長與成為發光摻雜劑的化合物的最大發光波長相距10 nm以上，可有效率地交換能量，因此較佳。The maximum emission wavelength of the compound represented by formula (2) as an auxiliary dopant contained in the composition for an organic electroluminescence element of the present embodiment is greater than that of the compound represented by formula (1) as a light-emitting dopant For shortwave. The maximum emission wavelength of the compound serving as the light-emitting dopant is preferably 580 nm or more, more preferably 590 nm or more, still more preferably 600 nm or more, and more preferably 700 nm or less, and more preferably 680 nm or less. By setting the maximum emission wavelength within this range, there is a tendency that a preferable color of a red light-emitting material, which is preferable as an organic electroluminescence element, can be expressed. Since the maximum emission wavelength of the compound serving as the auxiliary dopant and the maximum emission wavelength of the compound serving as the luminescent dopant are separated by 10 nm or more, energy can be exchanged efficiently, which is preferable.

式（1）所表示的化合物較佳為含有與式（2）所表示的化合物相同或更多。即，基於質量份換算的式（1）所表示的化合物的組成比較佳為式（2）所表示的化合物的組成比以上。式（1）所表示的化合物於質量份換算中，進而佳為含有式（2）所表示的化合物的1倍～3倍。就元件的發光效率及長壽命化的方面而言，特佳為含有1倍～2倍。就可獲得更鮮豔的發光的方面而言，更進而佳為含有2倍以上，就可降低元件的驅動電壓的方面而言，更進而佳為含有不足2倍。藉此，來自輔助摻雜劑的能量更有效率地向發光摻雜劑轉移，因此可獲得高的發光效率，從而可期待元件的長壽命化。The compound represented by formula (1) preferably contains the same or more of the compound represented by formula (2). That is, the composition of the compound represented by formula (1) in terms of parts by mass is preferably more than the composition ratio of the compound represented by formula (2). The compound represented by the formula (1) further preferably contains 1 to 3 times the compound represented by the formula (2) in terms of parts by mass. In terms of the luminous efficiency of the element and the longevity of the device, it is particularly preferable to contain 1 to 2 times. In terms of obtaining more vivid light emission, it is still more preferable to contain 2 times or more, and in terms of reducing the driving voltage of the element, it is still more preferable to contain less than 2 times. By this, energy from the auxiliary dopant is more efficiently transferred to the light-emitting dopant, and therefore, high light-emitting efficiency can be obtained, and a long life of the device can be expected.

[銥錯合物化合物的合成方法] 本實施形態的有機電場發光元件用組成物中所含的輔助摻雜劑以及成為發光摻雜劑的式（2）所表示的化合物及式（1）所表示的化合物均為銥錯合物化合物。以下示出銥錯合物化合物的合成方法。銥錯合物化合物的配位子可藉由已知的方法的組合等來合成。配位子的合成可藉由使芳基硼酸類與鹵化雜芳基類進行鈴木-宮浦偶合反應、與2-甲醯基或醯基苯胺類或相互位於鄰位的醯基-胺基吡啶類等進行弗裡德侖德（Friedlaender）環化反應（化學評論（Chem. Rev.）2009，109，2652或有機反應（Organic Reactions），1982，28（2），37-201）等已知的反應進行合成。[Synthesis method of iridium complex compound] The auxiliary dopant contained in the composition for the organic electroluminescence element of the present embodiment and the compound represented by the formula (2) and the compound represented by the formula (1) serving as the luminescent dopant are all iridium complex compounds . The synthesis method of the iridium complex compound is shown below. The ligand of the iridium complex compound can be synthesized by a combination of known methods and the like. Ligands can be synthesized by Suzuki-Miyaura coupling reaction between aryl boronic acids and halogenated heteroaryls, and 2-methanyl or aniline or acyl-aminopyridines located in the ortho position with each other. Etc. to carry out Friedlaender cyclization reaction (Chem. Rev. 2009, 109, 2652 or Organic Reactions, 1982, 28(2), 37-201) and other known The reaction proceeds to synthesis.

銥錯合物化合物可將所述得到的配位子與氯化銥n水合物等作為原料，藉由已知的方法的組合來合成。以下進行說明。作為銥錯合物化合物的合成方法，可例示：為了容易理解，使用苯基吡啶配位子作為例子的經由下述式[A]所示般的氯交聯銥雙核錯合物的方法（M. G. Colombo，T. C. Brunold，T. Riedener，H. U. Gudel，無機化學（Inorg. Chem.）1994，33，545-550）；自下述式[B]所示般的雙核錯合物進一步將氯交聯與乙醯丙酮交換，轉化為單核錯合物後獲得目標物的方法（S. Lamansky，P. Djurovich，D. Murphy，F. Abdel-Razzaq，R. Kwong，I. Tsyba，M. Borz，B. Mui，R. Bau，M. Thompson，無機化學（Inorg. Chem.），2001，40，1704-1711）等，但不限定於該些。The iridium complex compound can be synthesized by a combination of known methods using the obtained ligand and iridium chloride n-hydrate as raw materials. This will be explained below. As a synthetic method of an iridium complex compound, for easy understanding, a method of crosslinking an iridium binuclear complex compound (MG) using a phenylpyridine ligand as an example via a chlorine crosslinking iridium binuclear complex as shown in the following formula [A] Colombo, TC Brunold, T. Riedener, HU Gudel, Inorganic Chemistry (Inorg. Chem.) 1994, 33, 545-550); from the binuclear complex shown in the following formula [B] to further crosslink chlorine with The method of obtaining the target compound after acetone exchange and conversion into mononuclear complex (S. Lamansky, P. Djurovich, D. Murphy, F. Abdel-Razzaq, R. Kwong, I. Tsyba, M. Borz, B Mui, R. Bau, M. Thompson, Inorganic Chemistry (Inorg. Chem.), 2001, 40, 1704-1711) etc., but not limited to these.

例如，下述式[A]所表示的典型的反應的條件如下。再者，於本說明書中，化學式中的Et是指乙基，Tf是指三氟甲基磺醯基。作為第一階段，藉由第一配位子2當量與氯化銥n水合物1當量的反應而合成氯交聯銥雙核錯合物。溶媒通常使用2-乙氧基乙醇與水的混合溶媒，但亦可使用無溶媒或其他溶媒。亦可過量使用配位子，或者使用鹼等添加劑來促進反應。亦可使用溴等其他交聯性陰離子配位子來代替氯。For example, the typical reaction conditions represented by the following formula [A] are as follows. Furthermore, in this specification, Et in the chemical formula means ethyl, and Tf means trifluoromethylsulfonyl. As the first stage, a chlorine-crosslinked iridium binuclear complex is synthesized by the reaction of 2 equivalents of the first ligand and 1 equivalent of iridium chloride n-hydrate. The solvent is usually a mixed solvent of 2-ethoxyethanol and water, but solvent-free or other solvents can also be used. It is also possible to use excessive amounts of ligands, or use additives such as bases to promote the reaction. Other cross-linking anionic ligands such as bromine can also be used instead of chlorine.

對反應溫度並無特別限制，通常較佳為0℃以上，更佳為50℃以上。另外，較佳為250℃以下，更佳為150℃以下。藉由使反應溫度為該溫度範圍，可不伴隨副產物或分解反應而僅進行目標反應，存在獲得高選擇性的傾向。The reaction temperature is not particularly limited, but it is usually preferably 0°C or higher, and more preferably 50°C or higher. In addition, it is preferably 250°C or lower, more preferably 150°C or lower. By setting the reaction temperature within this temperature range, only the target reaction can be carried out without accompanying by-products or decomposition reactions, and there is a tendency to obtain high selectivity.

[化19]

[化19]

第二階段中，藉由添加三氟甲磺酸銀般的鹵素離子捕捉劑，使其與第二配位子接觸，得到目標錯合物。溶媒通常使用乙氧基乙醇或二甘二甲醚（diglyme），但根據配位子的種類，可無溶媒或使用其他溶媒，亦可混合使用多種溶媒。即便不添加鹵素離子捕捉劑，有時反應亦會進行，因此未必一定需要，但為了提高反應產率，選擇性地合成量子產率更高的面式異構物（facial isomer），添加該捕捉劑是有利的。反應溫度並無特別限制，通常以0℃～250℃的範圍進行。In the second stage, a halogen ion trap like silver triflate is added to contact the second ligand to obtain the target complex. The solvent usually uses ethoxyethanol or diglyme, but depending on the type of ligand, it can be solvent-free or other solvents, or a mixture of multiple solvents can be used. Even if the halogen ion trapping agent is not added, the reaction may sometimes proceed, so it is not necessarily necessary. However, in order to increase the reaction yield, selectively synthesize facial isomers with higher quantum yields and add the trapping agent. The agent is advantageous. The reaction temperature is not particularly limited, and it is usually carried out in the range of 0°C to 250°C.

對下述式[B]所表示的典型的反應條件進行說明。第一階段的雙核錯合物可與式[A]同樣地合成。第二階段藉由使該雙核錯合物與1當量以上的乙醯丙酮般的1,3-二酮化合物、及1當量以上的碳酸鈉般的可抽出該1,3-二酮化合物的活性氫的鹼性化合物反應，轉化為1,3-二酮配位子進行配位的單核錯合物。通常使用可溶解作為原料的雙核錯合物的乙氧基乙醇或二氯甲烷等溶媒，配位子為液狀的情況下亦能夠於無溶媒下實施。反應溫度並無特別限制，通常於0℃～200℃的範圍內進行。The typical reaction conditions represented by the following formula [B] will be described. The binuclear complex of the first stage can be synthesized in the same manner as the formula [A]. In the second stage, the activity of the 1,3-diketone compound can be extracted by combining the binuclear complex with 1 equivalent or more of acetone-like 1,3-diketone compound and 1 equivalent or more of sodium carbonate. The basic hydrogen compound reacts and transforms into a mononuclear complex coordinated by 1,3-diketone ligands. Usually, a solvent such as ethoxyethanol or methylene chloride that can dissolve the binuclear complex as a raw material is used, and it can be carried out without a solvent even when the ligand is liquid. The reaction temperature is not particularly limited, and it is usually carried out within the range of 0°C to 200°C.

[化20]

[化20]

第三階段中，使第二配位子反應1當量以上。溶媒的種類與量並無特別限制，當第二配位子於反應溫度下為液狀時亦可為無溶媒。反應溫度亦無特別限制，但由於反應性略有不足，因此大多於100℃～300℃的較高溫度下進行反應。因此，可較佳地使用甘油等高沸點的溶媒。最終反應後，為了除去未反應原料、反應副產物及溶媒而進行精製。可應用通常的有機合成化學中的精製操作，但如所述非專利文獻記載般，主要藉由順相的矽膠管柱層析法進行精製。展開液可使用己烷、庚烷、二氯甲烷、氯仿、乙酸乙酯、甲苯、甲基乙基酮、甲醇的單一或混合液。精製亦可改變條件進行多次。可根據需要而實施其他層析技術，例如反相矽膠層析法、尺寸排除層析法、紙層析法或分液清洗、再沈澱、再結晶、粉體的懸浮清洗、減壓乾燥等精製操作。In the third stage, 1 equivalent or more of the second ligand is reacted. The type and amount of the solvent are not particularly limited. When the second ligand is liquid at the reaction temperature, it can also be solvent-free. The reaction temperature is also not particularly limited, but since the reactivity is slightly insufficient, the reaction is usually carried out at a relatively high temperature of 100°C to 300°C. Therefore, a solvent with a high boiling point such as glycerin can be preferably used. After the final reaction, purification is performed to remove unreacted raw materials, reaction by-products, and solvents. The refining operations in general organic synthetic chemistry can be applied, but as described in the non-patent literature, the refining is mainly performed by the phase-phase silica gel column chromatography method. The developing solution can be a single or mixed solution of hexane, heptane, dichloromethane, chloroform, ethyl acetate, toluene, methyl ethyl ketone, and methanol. Refining can also be carried out many times under changing conditions. Other chromatographic techniques can be implemented as needed, such as reversed-phase silica gel chromatography, size exclusion chromatography, paper chromatography or liquid separation cleaning, reprecipitation, recrystallization, powder suspension cleaning, vacuum drying, etc. operating.

[溶媒、組成比] 本實施形態的有機電場發光元件用組成物中包含溶媒。有機電場發光元件用組成物通常用於藉由濕式成膜法來形成層或膜，特別是較佳為用於形成有機電場發光元件的發光層。有機電場發光元件用組成物中的發光摻雜劑的含量通常為0.01質量%以上，較佳為0.1質量%以上，另外通常為20質量%以下，較佳為10質量%以下。藉由使發光摻雜劑的含量為該範圍，於將該組成物用於有機電場發光元件用途的情況下，激發能向鄰接的層、例如電洞傳輸層或電洞阻擋層移動的情況少，另外，由於激子彼此的相互作用而消光的情況少，因此可提高發光效率。再者，發光摻雜劑的含量是式（1）所表示的化合物的合計含量。[Solvent, composition ratio] The composition for an organic electroluminescent element of this embodiment contains a solvent. The composition for an organic electroluminescent device is generally used to form a layer or film by a wet film forming method, and is particularly preferably used to form a light-emitting layer of an organic electroluminescent device. The content of the light-emitting dopant in the composition for an organic electroluminescence element is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 20% by mass or less, preferably 10% by mass or less. By setting the content of the light-emitting dopant within this range, when the composition is used in an organic electroluminescent device, the excitation energy is less likely to move to an adjacent layer, such as a hole transport layer or a hole blocking layer In addition, there is less extinction due to the interaction of excitons, so the luminous efficiency can be improved. In addition, the content of the light-emitting dopant is the total content of the compound represented by formula (1).

有機電場發光元件用組成物中的輔助摻雜劑的含量通常為0.005質量%以上，較佳為0.05質量%以上，另外通常為10質量%以下，較佳為5質量%以下。藉由使輔助摻雜劑的含量為該範圍，於將該組成物用於有機電場發光元件用途的情況下，可自鄰接的層、例如電洞傳輸層或電洞擋層層向發光層效率良好地注入電洞或電子，從而可降低驅動電壓。再者，輔助摻雜劑的含量是指式（2）所表示的化合物的合計含量。The content of the auxiliary dopant in the composition for an organic electroluminescence element is usually 0.005% by mass or more, preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. By setting the content of the auxiliary dopant within this range, when the composition is used in an organic electroluminescent device, it can be efficiently transferred from an adjacent layer, such as a hole transport layer or a hole blocking layer layer, to a light emitting layer. Inject holes or electrons well, so that the driving voltage can be reduced. In addition, the content of the auxiliary dopant refers to the total content of the compound represented by formula (2).

有機電場發光元件用組成物可僅含有一種式（2）所表示的成為輔助摻雜劑的化合物，亦可組合含有兩種以上。但是，於包含兩種以上的情況下，所有成為輔助摻雜劑的化合物的最大發光波長與式（1）所表示的成為發光摻雜劑的化合物的最大發光波長相比為短波。另外，於包含兩種以上式（1）所表示的成為發光摻雜劑的化合物的情況下，所有成為輔助摻雜劑的化合物的最大發光波長相較於所有成為發光摻雜劑的化合物的最大發光波長而為短波。The composition for an organic electroluminescence element may contain only one kind of compound that becomes an auxiliary dopant represented by formula (2), or may contain two or more kinds in combination. However, when two or more types are included, the maximum emission wavelength of all the compounds serving as auxiliary dopants is shorter than the maximum emission wavelength of the compound serving as the light emitting dopant represented by formula (1). In addition, in the case where two or more compounds represented by formula (1) that become luminescent dopants are included, the maximum emission wavelength of all compounds that become auxiliary dopants is compared with the maximum wavelength of all compounds that become luminescent dopants. The emission wavelength is shortwave.

有機電場發光元件用組成物中，成為發光摻雜劑的式（1）所表示的化合物的組成比（質量%）較佳為與成為輔助摻雜劑的式（2）所表示的化合物的組成比（質量%）相同或者比其大。藉由加大成為發光摻雜劑的化合物的組成比，於製成有機電場發光元件時，發光光譜的寬度變得更窄，得到鮮豔的發光，因此適合於顯示裝置用途。再者，於包含兩種以上成為輔助摻雜劑的化合物的情況下，成為發光摻雜劑的化合物的組成比（質量%）的合計較佳為大於所有成為輔助摻雜劑的化合物的組成比（質量%）的合計。In the composition for an organic electroluminescence element, the composition ratio (mass %) of the compound represented by formula (1) as the light-emitting dopant is preferably the same as the composition of the compound represented by formula (2) as the auxiliary dopant The ratio (mass %) is the same or greater. By increasing the composition ratio of the compound that becomes the light-emitting dopant, when the organic electroluminescent device is made, the width of the light-emitting spectrum becomes narrower, and bright light-emitting is obtained, so it is suitable for display device applications. Furthermore, when two or more compounds that become auxiliary dopants are included, the total composition ratio (mass %) of the compounds that become luminescent dopants is preferably greater than the composition ratio of all the compounds that become auxiliary dopants (Mass%) total.

所述成為發光摻雜劑的化合物進而佳為相對於所述成為輔助摻雜劑的化合物，於質量份換算中具有1倍～3倍。藉此，來自輔助摻雜劑的能量更有效率地向發光摻雜劑轉移，因此得到更高的發光效率。特佳為具有1倍～2倍。就獲得更鮮豔的發光的方面而言，成為發光摻雜劑的化合物的組成比（質量%）更佳為比成為輔助摻雜劑的化合物的組成比（質量%）大2倍以上。另一方面，就可降低元件的驅動電壓的方面而言，成為發光摻雜劑的化合物的組成比（質量%）較佳為不足成為輔助摻雜劑的化合物的組成比（質量%）的2倍。The compound used as a light-emitting dopant is more preferably 1 to 3 times in terms of parts by mass with respect to the compound used as an auxiliary dopant. Thereby, the energy from the auxiliary dopant is more efficiently transferred to the light-emitting dopant, thereby obtaining higher light-emitting efficiency. It is particularly preferable to have 1 to 2 times. In terms of obtaining more vivid light emission, the composition ratio (mass %) of the compound serving as the light-emitting dopant is more preferably two times or more larger than the composition ratio (mass %) of the compound serving as the auxiliary dopant. On the other hand, in terms of reducing the driving voltage of the device, the composition ratio (mass %) of the compound that becomes the light-emitting dopant is preferably less than 2% of the composition ratio (mass %) of the compound that becomes the auxiliary dopant. Times.

有機電場發光元件用組成物中所含有的溶媒是用於藉由濕式成膜來形成包含輔助摻雜劑及發光摻雜劑的層的具有揮發性的液體成分。The solvent contained in the composition for an organic electroluminescence element is a volatile liquid component for forming a layer containing an auxiliary dopant and a light-emitting dopant by wet film formation.

該溶媒只要是作為溶質的成為輔助摻雜劑的化合物、及成為發光摻雜劑的化合物良好地溶解的溶媒，則無特別限定。另外，較佳為溶解後述的電荷傳輸性化合物的溶媒。作為較佳的溶媒，例如可列舉：正癸烷、環己烷、乙基環己烷、十氫萘、雙環己烷等烷烴類；甲苯、二甲苯、均三甲苯、苯基環己烷、四氫萘等芳香族烴類；氯苯、二氯苯、三氯苯等鹵化芳香族烴類；1,2-二甲氧基苯、1,3-二甲氧基苯、苯甲醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基苯甲醚、2,4-二甲基苯甲醚、二苯醚等芳香族醚類；乙酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯類；環己酮、環辛酮、葑酮（fenchone）等脂環族酮類；環己醇、環辛醇等脂環族醇類；甲基乙基酮、二丁基酮等脂肪族酮類；丁醇、己醇等脂肪族醇類；乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚乙酸酯（propylene glycol-1-monomethyl ether acetate，PGMEA）等脂肪族醚類等。其中更佳為烷烴類或芳香族烴類，特別是苯基環己烷於濕式成膜製程中具有較佳的黏度及沸點，因此更進而佳。The solvent is not particularly limited as long as it is a solvent in which a compound that serves as an auxiliary dopant as a solute and a compound that serves as a light-emitting dopant dissolve well. In addition, it is preferably a solvent that dissolves the charge-transporting compound described later. Preferred solvents include, for example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, and bicyclohexane; toluene, xylene, mesitylene, phenylcyclohexane, Aromatic hydrocarbons such as tetralin; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, Phenyl ether, 2-methoxy toluene, 3-methoxy toluene, 4-methoxy toluene, 2,3-dimethyl anisole, 2,4-dimethyl anisole, diphenyl ether, etc. Aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate and other aromatic esters; cyclohexanone, cyclooctanone, fenchone (Fenchone) and other alicyclic ketones; alicyclic alcohols such as cyclohexanol and cyclooctanol; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; aliphatic alcohols such as butanol and hexanol ; Aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), etc. Among them, alkanes or aromatic hydrocarbons are more preferred, especially phenylcyclohexane has better viscosity and boiling point in the wet film forming process, so it is even more preferred.

該些溶媒可單獨使用一種，另外亦可以任意的組合及比率使用兩種以上。溶媒的沸點通常為80℃以上，較佳為100℃以上，更佳為150℃以上，特佳為200℃以上。藉由設為該範圍，於濕式成膜時，可抑制由於溶媒自有機電場發光元件用組成物蒸發而使成膜穩定性下降。另外，通常沸點為270℃以下，較佳為250℃以下，更佳為240℃以下。One kind of these solvents may be used alone, or two or more kinds may be used in any combination and ratio. The boiling point of the solvent is usually 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher, and particularly preferably 200°C or higher. By setting it in this range, during wet film formation, it is possible to suppress a decrease in film formation stability due to evaporation of the solvent from the composition for an organic electroluminescent element. In addition, the boiling point is usually 270°C or lower, preferably 250°C or lower, and more preferably 240°C or lower.

相對於有機電場發光元件用組成物100質量份，溶媒的含量較佳為10質量份以上，更佳為50質量份以上，特佳為80質量份以上，另外較佳為99.95質量份以下，更佳為99.9質量份以下，特佳為99.8質量份以下。藉由有機電場發光元件用組成物來形成有機電場發光元件的發光層時的厚度通常為3 nm～200 nm左右，藉由將溶媒的含量設為所述下限以上，可防止組成物的黏性變得過高而成膜作業性下降。另一方面，藉由設為所述上限以下，成膜後除去溶媒而得到的膜可得到一定以上的厚度，成膜性良好。The content of the solvent relative to 100 parts by mass of the composition for an organic electroluminescent element is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and more preferably 99.95 parts by mass or less. It is preferably 99.9 parts by mass or less, particularly preferably 99.8 parts by mass or less. The thickness of the light-emitting layer of an organic electroluminescence element when the composition for an organic electroluminescence element is used is usually about 3 nm to 200 nm. By setting the content of the solvent to be above the lower limit, the composition can be prevented from sticking. When it becomes too high, the workability of film formation decreases. On the other hand, by setting it to the upper limit or less, the film obtained by removing the solvent after the film formation can have a thickness of a certain level or more, and the film formability is good.

[電荷傳輸性化合物] 本實施形態的有機電場發光元件用組成物較佳為更包含電荷傳輸性化合物。作為電荷傳輸性化合物，可使用先前用作有機電場發光元件用材料者。例如可列舉三芳基胺、雙咔唑、三芳基三嗪、三芳基嘧啶及該些的衍生物、芳基胺基或咔唑基經取代的萘、苝、芘、蒽、䓛、稠四苯、菲、蔻（coronene）、螢蒽（fluoranthene）、苯並菲、芴、乙醯萘並螢蒽等縮合芳香族環化合物。[Charge Transport Compound] The composition for an organic electroluminescent device of this embodiment preferably further contains a charge-transporting compound. As the charge-transporting compound, those previously used as materials for organic electroluminescent devices can be used. For example, triarylamine, biscarbazole, triaryltriazine, triarylpyrimidine and their derivatives, arylamine or carbazolyl substituted naphthalene, perylene, pyrene, anthracene, tetraphenylene, pyrene , Phenanthrene, coronene, fluoranthene, triphenanthrene, fluorene, acetylnaphthofluoranthene and other condensed aromatic ring compounds.

另外，電荷傳輸性化合物可為高分子，作為高分子的電荷傳輸性化合物，可列舉聚(9,9-二辛基芴-2,7-二基)、聚[(9,9-二辛基芴-2,7-二基)-co-(4,4'-(N-(4-第二丁基苯基))二苯基胺)]、聚[(9,9-二辛基芴-2,7-二基)-co-(1,4-苯並-2{2,1'-3}-***)]等聚芴系材料、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-伸苯伸乙烯]等聚伸苯伸乙烯系材料等。該些電荷傳輸性化合物可單獨使用一種，亦可以任意的組合及比率使用兩種以上。In addition, the charge-transporting compound may be a polymer. Examples of the charge-transporting compound of the polymer include poly(9,9-dioctylfluorene-2,7-diyl), poly[(9,9-dioctyl) Fluorene-2,7-diyl)-co-(4,4'-(N-(4-second butylphenyl))diphenylamine)], poly[(9,9-dioctyl Fluorene-2,7-diyl)-co-(1,4-benzo-2{2,1'-3}-triazole)] and other polyfluorene-based materials, poly[2-methoxy-5- (2-ethylhexyloxy)-1,4-styrene ethylene] and other polystyrene-based materials. These charge-transporting compounds may be used singly, or two or more of them may be used in any combination and ratio.

[有機電場發光元件] 本實施形態的有機電場發光元件包括使用所述有機電場發光元件用組成物，較佳為藉由濕式成膜法而形成的層。有機電場發光元件較佳為於基板上至少具有陽極、陰極以及於陽極與陰極之間的至少一層有機層，且所述有機層中的至少一層為使用本實施形態的有機電場發光元件用組成物而形成的層。所述層更佳為藉由濕式成膜法而形成。另外，所述有機層包括發光層，但更佳為該發光層為使用本實施形態的有機電場發光元件用組成物而形成的層。[Organic electroluminescent element] The organic electroluminescence element of the present embodiment includes the use of the composition for the organic electroluminescence element, and is preferably a layer formed by a wet film formation method. The organic electroluminescence element preferably has at least an anode, a cathode, and at least one organic layer between the anode and the cathode on the substrate, and at least one of the organic layers is the composition for the organic electroluminescence element of this embodiment And the layers formed. The layer is more preferably formed by a wet film forming method. In addition, the organic layer includes a light-emitting layer, but it is more preferable that the light-emitting layer is a layer formed using the composition for an organic electroluminescence element of this embodiment.

本說明書中，所謂濕式成膜法，是指採用例如旋塗法、浸塗法、模塗法、棒塗法、刮塗法、輥塗法、噴塗法、毛細管塗佈法、噴墨法、噴嘴印刷法、網版印刷法、凹版印刷法、柔版印刷法等以濕式來成膜的方法作為成膜方法即塗佈方法，並使藉由該些方法而成膜的膜乾燥來進行膜形成的方法。In this specification, the so-called wet film forming method refers to the use of, for example, spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, and inkjet methods. , Nozzle printing method, screen printing method, gravure printing method, flexographic printing method, etc., use wet method to form a film as a film forming method, that is, a coating method, and dry the film formed by these methods The method of film formation.

圖1是表示作為本發明的有機電場發光元件10而較佳的結構例的剖面的示意圖。圖1中，符號1表示基板、符號2表示陽極、符號3表示電洞注入層、符號4表示電洞傳輸層、符號5表示發光層、符號6表示電洞阻擋層、符號7表示電子傳輸層、符號8表示電子注入層、符號9表示陰極。應用於該些結構的材料可應用公知的材料，並無特別限制，以下記載關於各層的代表性材料或製法作為一例。以下，於引用公報或論文等的情況下，可於本領域技術人員的常識範圍內適當適用、應用相應內容。FIG. 1 is a schematic diagram showing a cross-section of a preferred configuration example of the organic electroluminescent element 10 of the present invention. In Figure 1, the symbol 1 indicates the substrate, the symbol 2 indicates the anode, the symbol 3 indicates the hole injection layer, the symbol 4 indicates the hole transport layer, the symbol 5 indicates the light-emitting layer, the symbol 6 indicates the hole blocking layer, and the symbol 7 indicates the electron transport layer , Symbol 8 indicates an electron injection layer, and symbol 9 indicates a cathode. As the materials applied to these structures, well-known materials can be used, and there is no particular limitation. The following describes representative materials or manufacturing methods for each layer as an example. Hereinafter, in the case of citing publications or papers, etc., the corresponding content can be appropriately adapted and applied within the scope of the common sense of those skilled in the art.

＜基板1＞基板1為有機電場發光元件的支撐體，通常使用石英或玻璃的板、金屬板、金屬箔、或者合成樹脂即塑膠的膜或片材等。該些中，較佳為玻璃板、或聚酯、聚甲基丙烯酸酯、聚碳酸酯、聚碸等透明的合成樹脂的膜。就不易發生外部氣體引起的有機電場發光元件的劣化的方面而言，基板1較佳為採用阻氣性高的材質。特別是於使用合成樹脂製的基板等般阻氣性低的材質的情況下，較佳為於基板1的至少一個面設置緻密的矽氧化膜等來提高阻氣性。＜Board 1＞ The substrate 1 is a support for an organic electroluminescence element, and usually a quartz or glass plate, a metal plate, a metal foil, or a synthetic resin, ie, a plastic film or sheet, or the like is used. Among these, a glass plate, or a film of transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polycure is preferred. In terms of preventing deterioration of the organic electroluminescence element caused by external air, the substrate 1 is preferably made of a material with high gas barrier properties. In particular, when using a material with low gas barrier properties such as a synthetic resin substrate, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate 1 to improve the gas barrier properties.

＜陽極2＞陽極2承擔對發光層側的層注入電洞的功能。陽極2通常包含：鋁、金、銀、鎳、鈀、鉑等金屬；銦及/或錫的氧化物等金屬氧化物；碘化銅等鹵化金屬；碳黑或者聚(3-甲基噻吩)、聚吡咯、聚苯胺等導電性高分子等。＜Anode 2＞ The anode 2 has a function of injecting holes into the layer on the light-emitting layer side. The anode 2 usually contains: metals such as aluminum, gold, silver, nickel, palladium, and platinum; metal oxides such as indium and/or tin oxides; halogenated metals such as copper iodide; carbon black or poly(3-methylthiophene) , Polypyrrole, polyaniline and other conductive polymers.

陽極2的形成通常大多藉由濺鍍法、真空蒸鍍法等乾式法來進行。於使用銀等金屬微粒子、碘化銅等微粒子、碳黑、導電性的金屬氧化物微粒子、導電性高分子微粉末等來形成陽極2的情況下，亦可藉由分散於適當的黏合劑樹脂溶液並塗佈至基板1上來形成。於導電性高分子的情況下，亦可藉由電解聚合直接於基板上形成薄膜、或於基板上塗佈導電性高分子來形成陽極2（應用物理快訊（Appl. Phys. Lett.），60卷，2711頁，1992年）。The formation of the anode 2 is usually performed by a dry method such as a sputtering method or a vacuum vapor deposition method. When the anode 2 is formed using metal particles such as silver, copper iodide particles, carbon black, conductive metal oxide particles, conductive polymer fine powder, etc., it can also be dispersed in an appropriate binder resin The solution is applied to the substrate 1 to be formed. In the case of conductive polymer, it is also possible to directly form a thin film on the substrate by electrolytic polymerization, or coat a conductive polymer on the substrate to form the anode 2 (Appl. Phys. Lett.), 60 Vol. 2711, 1992).

陽極2通常為單層結構，但亦可適當採用積層結構。於陽極2為積層結構的情況下，亦可於第一層的陽極上積層不同的導電材料。陽極2的厚度根據所需的透明性及材質等來決定即可。特別是於需要高的透明性的情況下，較佳為使可見光的透射率成為60%以上的厚度，進而佳為成為80%以上的厚度。陽極2的厚度通常為5 nm以上，較佳為10 nm以上，通常為1000 nm以下，較佳為500 nm以下。The anode 2 usually has a single-layer structure, but a layered structure may be appropriately adopted. When the anode 2 has a laminated structure, different conductive materials may be laminated on the anode of the first layer. The thickness of the anode 2 may be determined according to the required transparency, material, and the like. In particular, when high transparency is required, it is preferable to make the visible light transmittance a thickness of 60% or more, and more preferably to have a thickness of 80% or more. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, usually 1000 nm or less, preferably 500 nm or less.

於不需要透明性的情況下，陽極2的厚度根據所需的強度等設為任意的厚度即可，於該情況下，陽極2亦可與基板1為相同的厚度。於形成陽極2後，繼而於其表面進行以下的層的成膜的情況下，較佳為於成膜前實施紫外線+臭氧、氧電漿、氬電漿等處理，藉此除去陽極上的雜質並且調整其離子化電位而使電洞注入性提高。In the case where transparency is not required, the thickness of the anode 2 may be any thickness depending on the required strength or the like. In this case, the anode 2 may have the same thickness as the substrate 1. After the anode 2 is formed, when the following layers are formed on the surface, it is preferable to perform treatments such as ultraviolet + ozone, oxygen plasma, argon plasma, etc. before the film formation to remove impurities on the anode And adjust its ionization potential to improve hole injection.

＜電洞注入層3＞承擔自陽極2側向發光層5側傳輸電洞的功能的層通常被稱為電洞注入傳輸層或電洞傳輸層。於承擔自陽極2側向發光層5側傳輸電洞的功能的層存在兩層以上的情況下，有時將更靠近陽極2側的層稱為電洞注入層3。以下，對電洞注入層3進行說明，對於承擔傳輸電洞的功能的層為一層時的電洞注入傳輸層或電洞傳輸層，亦同樣地作為電洞注入層3來進行說明。即，後述的電洞傳輸層4不同於承擔傳輸電洞的功能的層為一層時的電洞傳輸層，是所述層為兩層以上時接近發光層5側的層的名稱且是任意的層。就強化自陽極2向發光層5側傳輸電洞的功能的方面而言，較佳為使用電洞注入層3。於使用電洞注入層3的情況下，通常電洞注入層3形成於陽極2上。＜Hole injection layer 3＞ The layer that performs the function of transporting holes from the anode 2 side to the light emitting layer 5 side is generally called a hole injection transport layer or a hole transport layer. When there are two or more layers that perform the function of transporting holes from the anode 2 side to the light emitting layer 5 side, the layer closer to the anode 2 side may be referred to as the hole injection layer 3. Hereinafter, the hole injection layer 3 will be described, and the hole injection transport layer or the hole transport layer when the layer that performs the function of transmitting holes is one layer is also described as the hole injection layer 3 in the same manner. That is, the hole transport layer 4 described later is different from the hole transport layer when the layer that is responsible for the function of transporting holes is one layer, and is the name of the layer close to the light-emitting layer 5 when the layer is two or more layers, and it is arbitrary. Floor. In terms of enhancing the function of transporting holes from the anode 2 to the light-emitting layer 5 side, it is preferable to use the hole injection layer 3. When the hole injection layer 3 is used, the hole injection layer 3 is usually formed on the anode 2.

電洞注入層3的膜厚通常為1 nm以上，較佳為5 nm以上，通常為1000 nm以下，較佳為500 nm以下。電洞注入層3的形成方法可為真空蒸鍍法，亦可為濕式成膜法。就成膜性優異的方面而言，較佳為藉由濕式成膜法來形成。電洞注入層3較佳為包含電洞傳輸性化合物，更佳為包含電洞傳輸性化合物及受電子性化合物。進而，較佳為於電洞注入層3中包含陽離子自由基化合物，特佳為包含陽離子自由基化合物及電洞傳輸性化合物。The thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, usually 1000 nm or less, preferably 500 nm or less. The method for forming the hole injection layer 3 may be a vacuum evaporation method or a wet film forming method. In terms of excellent film-forming properties, it is preferably formed by a wet film-forming method. The hole injection layer 3 preferably includes a hole-transporting compound, and more preferably includes a hole-transporting compound and an electron-accepting compound. Furthermore, it is preferable to include a cationic radical compound in the hole injection layer 3, and it is particularly preferable to include a cationic radical compound and a hole transporting compound.

（電洞傳輸性化合物）電洞注入層形成用組成物通常含有成為電洞注入層3的電洞傳輸性化合物。於濕式成膜法的情況下，通常亦更含有溶劑。電洞注入層形成用組成物較佳為電洞傳輸性高、可效率良好地傳輸所注入的電洞。因此，較佳為電洞遷移率大、製造時或使用時等不易產生成為陷阱的雜質。另外，較佳為穩定性優異、離子化電位小、對可見光的透明性高。特別是於電洞注入層3與發光層5相接的情況下，即承擔自陽極2側向發光層5側傳輸電洞的功能的層為電洞注入層3的一層的情況下較佳為不對來自發光層5的發光進行消光者或與發光層5形成激發錯合體（exciplex）而不會使發光效率降低者。(Hole-transporting compound) The composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. In the case of the wet film forming method, it usually contains a solvent. The composition for forming the hole injection layer preferably has high hole transport properties and can efficiently transport the injected holes. Therefore, it is preferable that the hole mobility is high, and impurities that become traps are not easily generated during manufacturing or use. In addition, it is preferably excellent in stability, low in ionization potential, and high in transparency to visible light. Especially in the case where the hole injection layer 3 is in contact with the light emitting layer 5, that is, when the layer that performs the function of transporting holes from the anode 2 side to the light emitting layer 5 side is a layer of the hole injection layer 3, it is preferably Those who do not extinct the light emitted from the light-emitting layer 5 or form an exciplex with the light-emitting layer 5 without reducing the luminous efficiency.

作為電洞傳輸性化合物，就自陽極2向電洞注入層3的電荷注入阻礙的觀點而言，較佳為具有4.5 eV～6.0 eV的離子化電位的化合物。作為電洞傳輸性化合物的例子，可列舉芳香族胺系化合物、酞青系化合物、卟啉系化合物、低聚噻吩系化合物、聚噻吩系化合物、苄基苯基系化合物、以芴基將三級胺連結而成的化合物、腙系化合物、矽氮烷系化合物、喹吖啶酮系化合物等。As the hole-transporting compound, from the viewpoint of inhibiting charge injection from the anode 2 to the hole injection layer 3, a compound having an ionization potential of 4.5 eV to 6.0 eV is preferred. Examples of hole-transporting compounds include aromatic amine-based compounds, phthalocyanine-based compounds, porphyrin-based compounds, oligothiophene-based compounds, polythiophene-based compounds, benzylphenyl-based compounds, and fluorenyl-based compounds. Compounds formed by linking graded amines, hydrazone-based compounds, silazane-based compounds, quinacridone-based compounds, etc.

所述例示化合物中，就非晶質性及可見光透射性的方面而言，較佳為芳香族胺化合物，特佳為芳香族三級胺化合物。所謂芳香族三級胺化合物，亦包含具有芳香族三級胺結構且具有源自芳香族三級胺的基的化合物。芳香族三級胺化合物的種類並無特別限制，就藉由表面平滑化效果而容易獲得均勻的發光的方面而言，較佳為使用重量平均分子量為1000以上且1000000以下的高分子化合物（重複單元相連的聚合型化合物）。作為芳香族三級胺高分子化合物的較佳例，可列舉具有下述式（I）所表示的重複單元的高分子化合物等。Among the exemplified compounds, in terms of amorphous properties and visible light transmittance, aromatic amine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred. The aromatic tertiary amine compound also includes a compound having an aromatic tertiary amine structure and having a group derived from an aromatic tertiary amine. The type of aromatic tertiary amine compound is not particularly limited. In terms of easily obtaining uniform light emission due to the surface smoothing effect, it is preferable to use a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (repeat Polymeric compounds with connected units). As a preferable example of the aromatic tertiary amine polymer compound, a polymer compound having a repeating unit represented by the following formula (I) and the like can be cited.

[化21]

[化21]

式（I）中，Ar¹ 及Ar² 分別獨立地表示可具有取代基的一價的芳香族基或可具有取代基的一價的雜芳香族基。Ar³ ～Ar⁵ 分別獨立地表示可具有取代基的二價的芳香族基或可具有取代基的二價的雜芳香族基。Q表示選自下述的連結基群中的連結基。另外，Ar¹ ～Ar⁵ 中，鍵結於同一N原子的兩個基可相互鍵結而形成環。以下示出連結基。In formula (I), Ar ¹ and Ar ² each independently represent a monovalent aromatic group which may have a substituent or a monovalent heteroaromatic group which may have a substituent. Ar ³ to Ar ⁵ each independently represent a divalent aromatic group which may have a substituent or a divalent heteroaromatic group which may have a substituent. Q represents a linking group selected from the following linking group group. In addition, among Ar ¹ to Ar ⁵ , two groups bonded to the same N atom may be bonded to each other to form a ring. The linking base is shown below.

[化22]

[化22]

（所述各式中，Ar⁶ ～Ar¹⁶ 分別獨立地表示可具有取代基的芳香族基或可具有取代基的雜芳香族基；R^a 及R^b 分別獨立地表示氫原子或任意的取代基）(In the formulas, Ar ⁶ ~ Ar ¹⁶ each independently represents an aromatic group may have a substituent or a hetero aromatic substituent; R ^a and R ^b each independently represent a hydrogen atom or an optionally substituted base)

作為Ar¹ ～Ar¹⁶ 的芳香族基及雜芳香族基，就高分子化合物的溶解性、耐熱性、電洞注入傳輸性的方面而言，較佳為源自苯環、萘環、菲環、噻吩環、吡啶環的基，進而佳為源自苯環、萘環的基。作為具有式（I）所表示的重複單元的芳香族三級胺高分子化合物的具體例，可列舉國際公開第2005/089024號中記載的化合物等。The aromatic group and heteroaromatic group of Ar ¹ to Ar ¹⁶ are preferably derived from a benzene ring, a naphthalene ring, and a phenanthrene ring in terms of the solubility, heat resistance, and hole injection and transport properties of the polymer compound. The group of thiophene ring and pyridine ring is more preferably a group derived from a benzene ring or a naphthalene ring. Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by formula (I) include the compounds described in International Publication No. 2005/089024.

（受電子性化合物）電洞注入層3藉由電洞傳輸性化合物的氧化可提高電洞注入層3的導電率，因此較佳為含有受電子性化合物。作為受電子性化合物，較佳為具有氧化能力且具有自所述電洞傳輸性化合物接受單電子的能力的化合物。具體而言更佳為電子親和力為4 eV以上的化合物，進而佳為電子親和力為5 eV以上的化合物。(Electron-accepting compound) The hole injection layer 3 can increase the conductivity of the hole injection layer 3 by oxidation of the hole-transporting compound, and therefore preferably contains an electron-accepting compound. The electron-accepting compound is preferably a compound having an oxidizing ability and an ability to accept a single electron from the hole transporting compound. Specifically, a compound having an electron affinity of 4 eV or more is more preferable, and a compound having an electron affinity of 5 eV or more is still more preferable.

作為此種受電子性化合物，例如可列舉選自由三芳基硼化合物、鹵化金屬、路易斯酸、有機酸、鎓鹽、芳基胺與鹵化金屬的鹽、及芳基胺與路易斯酸的鹽所組成的群組中的一種或兩種以上的化合物等。具體而言，可列舉：4-異丙基-4'-甲基二苯基錪四(五氟苯基)硼酸鹽、三苯基鋶四氟硼酸鹽等有機基進行了取代的鎓鹽（國際公開第2005/089024號）；氯化鐵（III）（日本專利特開平11-251067號公報）、過氧二硫酸銨等高原子價的無機化合物；四氰基乙烯等氰基化合物；三(五氟苯基)硼烷（日本專利特開2003-31365號公報）等芳香族硼化合物；富勒烯衍生物及碘等。Examples of such electron-accepting compounds include triaryl boron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. One or two or more compounds in the group. Specifically, examples include onium salts substituted with organic groups such as 4-isopropyl-4'-methyldiphenyl iodotetrakis (pentafluorophenyl) borate and triphenyl sulfonium tetrafluoroborate ( International Publication No. 2005/089024); iron(III) chloride (Japanese Patent Laid-Open No. 11-251067), high valence inorganic compounds such as ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene; three (Pentafluorophenyl)borane (Japanese Patent Laid-Open No. 2003-31365) and other aromatic boron compounds; fullerene derivatives, iodine, etc.

（陽離子自由基化合物）作為陽離子自由基化合物，較佳為包含作為自電洞傳輸性化合物去除了一個電子的化學種的陽離子自由基、及抗衡陰離子的離子化合物。於陽離子自由基源自電洞傳輸性的高分子化合物的情況下，陽離子自由基成為自高分子化合物的重複單元去除了一個電子的結構。(Cation free radical compound) The cationic radical compound is preferably an ionic compound containing a cationic radical which is a chemical species in which one electron is removed from the hole transporting compound, and a counter anion. When the cationic radical is derived from a hole-transporting polymer compound, the cationic radical has a structure in which one electron is removed from the repeating unit of the polymer compound.

作為陽離子自由基，就非晶質性、可見光的透射率、耐熱性及溶解性等方面而言，較佳為自上文中作為電洞傳輸性化合物而敘述的化合物去除了一個電子的化學種。陽離子自由基化合物可藉由混合所述電洞傳輸性化合物與受電子性化合物來生成。藉由混合所述電洞傳輸性化合物與受電子性化合物，而發生自電洞傳輸性化合物向受電子性化合物的電子移動，生成包含電洞傳輸性化合物的陽離子自由基與抗衡陰離子的陽離子自由基化合物。As the cationic radical, in terms of amorphousness, visible light transmittance, heat resistance, and solubility, it is preferably a chemical species in which one electron has been removed from the compound described above as the hole-transporting compound. The cationic radical compound can be produced by mixing the hole-transporting compound and the electron-accepting compound. By mixing the hole-transporting compound and the electron-accepting compound, electrons move from the hole-transporting compound to the electron-accepting compound, and cation radicals including the hole-transporting compound and the counter anion are generated. Base compound.

作為陽離子自由基化合物，例如摻雜有聚(4-苯乙烯磺酸)的聚(3,4-乙烯二氧基噻吩)（PEDOT/PSS）（先進材料（Adv. Mater.），2000年，12卷，481頁）或苯胺綠（emeraldine）鹽酸鹽（物理化學雜誌（J. Phys. Chem.），1990年，94卷，7716頁）等源自高分子化合物的陽離子自由基化合物亦可藉由氧化聚合（脫氫聚合）來生成。此處所提及的氧化聚合是將單體在酸性溶液中，使用過氧二硫酸鹽等化學性地或電氣化學性地氧化。於該氧化聚合（脫氫聚合）的情況下，將單體藉由氧化而高分子化，並且生成將源自酸性溶液的陰離子作為抗衡陰離子的、自高分子的重複單元去除了一個電子的陽離子自由基。As a cationic radical compound, for example, poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonic acid) (PEDOT/PSS) (Adv. Mater.), 2000, Vol. 12, page 481) or emeraldine hydrochloride (J. Phys. Chem., 1990, Vol. 94, page 7716) and other cationic radical compounds derived from polymer compounds can also be used It is produced by oxidative polymerization (dehydrogenation polymerization). The oxidative polymerization mentioned here is to chemically or electrochemically oxidize the monomer in an acid solution using peroxodisulfate or the like. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is polymerized by oxidation, and an anion derived from an acidic solution is used as a counter anion, and a cation with one electron removed from the repeating unit of the polymer is generated Free radicals.

（利用濕式成膜法的電洞注入層3的形成）於藉由濕式成膜法來形成電洞注入層3的情況下，通常將成為電洞注入層3的材料與可溶的溶劑（電洞注入層用溶劑）混合來製備成膜用的組成物（電洞注入層形成用組成物），將此電洞注入層形成用組成物藉由濕式成膜法成膜於相當於電洞注入層3的下層的層通常為陽極2上，並使其乾燥，藉此來形成。成膜的膜的乾燥可與利用濕式成膜法的發光層5的形成中的乾燥方法同樣地進行。(Formation of hole injection layer 3 by wet film forming method) In the case of forming the hole injection layer 3 by a wet film formation method, the material for the hole injection layer 3 is usually mixed with a soluble solvent (solvent for the hole injection layer) to prepare a composition for film formation (A composition for forming a hole injection layer), the composition for forming a hole injection layer is formed by a wet film forming method on a layer corresponding to the lower layer of the hole injection layer 3, usually on the anode 2, and Let it dry to form it. The drying of the formed film can be performed in the same manner as the drying method in the formation of the light-emitting layer 5 by the wet film formation method.

只要不明顯損及本發明的效果，則電洞注入層形成用組成物中的電洞傳輸性化合物的濃度為任意，就膜厚的均勻性的方面而言，較佳為低，就電洞注入層3中不易產生缺陷的方面而言，較佳為高。電洞注入層形成用組成物中的電洞傳輸性化合物的濃度較佳為0.01質量%以上，進而佳為0.1質量%以上，特佳為0.5質量%以上，另外，較佳為70質量%以下，進而佳為60質量%以下，特佳為50質量%以下。As long as the effect of the present invention is not significantly impaired, the concentration of the hole-transporting compound in the composition for forming a hole injection layer is arbitrary. In terms of uniformity of the film thickness, it is preferably low. It is preferable that it is high in the point which is less prone to produce defects in the injection layer 3. The concentration of the hole-transporting compound in the composition for forming a hole injection layer is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and more preferably 70% by mass or less , More preferably 60% by mass or less, particularly preferably 50% by mass or less.

作為溶劑，例如可列舉醚系溶劑、酯系溶劑、芳香族烴系溶劑、醯胺系溶劑等。作為醚系溶劑，例如可列舉：乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚乙酸酯（PGMEA）等脂肪族醚及1,2-二甲氧基苯、1,3-二甲氧基苯、苯甲醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基苯甲醚、2,4-二甲基苯甲醚等芳香族醚等。Examples of the solvent include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, and amide-based solvents. As ether solvents, for example, aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), and 1,2-dimethoxybenzene, 1,3-Dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2 , 4-dimethyl anisole and other aromatic ethers.

作為酯系溶劑，例如可列舉：乙酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯等。Examples of ester-based solvents include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.

作為芳香族烴系溶劑，例如可列舉：甲苯、二甲苯、環己基苯、3-異丙基聯苯、1,2,3,4-四甲基苯、1,4-二異丙基苯、甲基萘等。Examples of aromatic hydrocarbon solvents include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, and 1,4-diisopropylbenzene , Methyl naphthalene and so on.

作為醯胺系溶劑，例如可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等。該些之外，亦可使用二甲基亞碸等。Examples of amide-based solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and the like. In addition to these, dimethyl sulfoxide and the like can also be used.

利用濕式成膜法的電洞注入層3的形成通常是藉由在製備電洞注入層形成用組成物後，將其塗佈成膜至相當於電洞注入層3的下層的層通常為陽極2上並進行乾燥來進行。電洞注入層3通常是於成膜後藉由加熱或減壓乾燥等來使塗佈膜乾燥。The formation of the hole injection layer 3 by the wet film formation method is usually by preparing the composition for forming the hole injection layer, and then coating it to form a film to a layer corresponding to the lower layer of the hole injection layer 3 is usually The anode 2 is applied and dried to proceed. The hole injection layer 3 is usually dried by heating or drying under reduced pressure after forming the film.

（利用真空蒸鍍法的電洞注入層3的形成）於藉由真空蒸鍍法來形成電洞注入層3的情況下，通常將電洞注入層3的構成材料即前述的電洞傳輸性化合物、受電子性化合物等的一種或兩種以上放入至設置於真空容器內的坩堝中。此時，於使用兩種以上的材料的情況下，通常分別放入至不同的坩堝中。其後，利用真空泵將真空容器內排氣至10^-4 Pa左右後，加熱坩堝，一邊控制坩堝內的材料的蒸發量一邊使其蒸發。於使用兩種以上的材料的情況下，通常對各個坩堝進行加熱，分別獨立地一邊控制蒸發量一邊使其蒸發。藉由所述操作，使電洞注入層3形成於面向坩堝放置的基板上的陽極2上。於使用兩種以上的材料的情況下，亦可將該些作為混合物而放入至坩堝中，加熱使其蒸發來形成電洞注入層3。(Formation of the hole injection layer 3 by the vacuum evaporation method) In the case of forming the hole injection layer 3 by the vacuum evaporation method, the constituent material of the hole injection layer 3 is usually the aforementioned hole transportability One or two or more of compounds, electron-accepting compounds, etc. are put in a crucible set in a vacuum container. At this time, when two or more materials are used, they are usually put into different crucibles. After that, the inside of the vacuum container was evacuated to about 10 ^-4 Pa with a vacuum pump, and the crucible was heated to evaporate the material in the crucible while controlling the evaporation amount of the material in the crucible. When two or more kinds of materials are used, each crucible is usually heated, and each crucible is evaporated while independently controlling the amount of evaporation. Through the operation, the hole injection layer 3 is formed on the anode 2 on the substrate placed facing the crucible. When two or more kinds of materials are used, these can be put into a crucible as a mixture, and heated and evaporated to form the hole injection layer 3.

只要不明顯損及本發明的效果，則蒸鍍時的真空度並無特別限定，通常為0.1×10^-6 Torr（0.13×10^-4 Pa）以上且9.0×10^-6 Torr（12.0×10^-4 Pa）以下。只要不明顯損及本發明的效果，則蒸鍍速度並無限定，通常為0.1 Å/秒以上且5.0 Å/秒以下。只要不明顯損及本發明的效果，則蒸鍍時的成膜溫度並無限定，較佳為於10℃以上且50℃以下進行。As long as the effect of the present invention is not significantly impaired, the degree of vacuum during vapor deposition is not particularly limited, and it is usually 0.1×10 ^-6 Torr (0.13×10 ^-4 Pa) or more and 9.0×10 ^-6 Torr (12.0×10 ^-4 Pa) or less. As long as the effect of the present invention is not significantly impaired, the vapor deposition rate is not limited, and it is usually 0.1 Å/sec or more and 5.0 Å/sec or less. As long as the effect of the present invention is not significantly impaired, the film formation temperature during vapor deposition is not limited, and it is preferably performed at 10°C or higher and 50°C or lower.

＜電洞傳輸層4＞電洞傳輸層4是承擔自陽極2側向發光層5側傳輸電洞的功能的層。電洞傳輸層4對於本實施形態的有機電場發光元件而言並非必需的層，但就強化自陽極2向發光層5傳輸電洞的功能的方面而言，較佳為設置。於設置電洞傳輸層4的情況下，通常電洞傳輸層4形成於陽極2與發光層5之間。於存在電洞注入層3的情況下，電洞傳輸層4形成於電洞注入層3與發光層5之間。＜Hole transport layer 4＞ The hole transport layer 4 is a layer that performs the function of transporting holes from the anode 2 side to the light emitting layer 5 side. The hole transport layer 4 is not an essential layer for the organic electroluminescent element of this embodiment, but it is preferably provided in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. When the hole transport layer 4 is provided, the hole transport layer 4 is usually formed between the anode 2 and the light-emitting layer 5. When the hole injection layer 3 is present, the hole transport layer 4 is formed between the hole injection layer 3 and the light-emitting layer 5.

電洞傳輸層4的膜厚通常為5 nm以上，較佳為10 nm以上，通常為300 nm以下，較佳為100 nm以下。電洞傳輸層4的形成方法可為真空蒸鍍法，亦可為濕式成膜法。就成膜性優異的方面而言，較佳為藉由濕式成膜法來形成。The thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, usually 300 nm or less, preferably 100 nm or less. The method of forming the hole transport layer 4 may be a vacuum evaporation method or a wet film forming method. In terms of excellent film-forming properties, it is preferably formed by a wet film-forming method.

電洞傳輸層4通常含有形成電洞傳輸層4的電洞傳輸性化合物。作為電洞傳輸層4中所含的電洞傳輸性化合物，特別是可列舉：4,4'-雙[N-(1-萘基)-N-苯基胺基]聯苯所代表的含有兩個以上的三級胺且兩個以上的縮合芳香族環取代為氮原子的芳香族二胺（日本專利特開平5-234681號公報）、4,4',4''-三(1-萘基苯基胺基)三苯基胺等具有星爆（Starburst）結構的芳香族胺化合物（發光學報（J. Lumin.），72-74卷，985頁，1997年）、包含三苯基胺的四聚體的芳香族胺化合物（化學通訊（Chem. Commun.），2175頁，1996年）、2,2',7,7'-四-(二苯基胺基)-9,9'-螺二芴等螺環化合物（合成金屬（Synth. Metals），91卷，209頁，1997年）、4,4'-N,N'-二咔唑聯苯等咔唑衍生物等。亦可較佳地使用包含聚乙烯基咔唑、聚乙烯基三苯基胺（日本專利特開平7-53953號公報）、含有四苯基聯苯胺的聚伸芳基醚碸（先進技術用聚合物（Polym. Adv. Tech.），7卷，33頁，1996年）等。The hole transport layer 4 usually contains a hole transport compound that forms the hole transport layer 4. Examples of the hole-transporting compound contained in the hole-transporting layer 4 include, in particular, those represented by 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl Two or more tertiary amines and an aromatic diamine in which two or more condensed aromatic rings are substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4',4''-tri(1- Naphthylphenylamino) triphenylamine and other aromatic amine compounds with a Starburst structure (J. Lumin., Volume 72-74, Page 985, 1997), containing triphenylamine Aromatic amine compound of amine tetramer (Chem. Commun., 2175 page, 1996), 2,2',7,7'-tetra-(diphenylamino)-9,9 Spiro compounds such as'-spirobifluorene (Synth. Metals, Volume 91, page 209, 1997), carbazole derivatives such as 4,4'-N,N'-dicarbazole biphenyl, etc. It is also preferable to use polyvinyl carbazole, polyvinyl triphenylamine (Japanese Patent Laid-Open No. 7-53953), and poly(arylene ether) containing tetraphenyl benzidine (advanced technology for polymerization (Polym. Adv. Tech.), Volume 7, 33 pages, 1996) and so on.

（利用濕式成膜法的電洞傳輸層4的形成）於利用濕式成膜法形成電洞傳輸層4的情況下，通常與所述利用濕式成膜法形成電洞注入層3時同樣地，使用電洞傳輸層形成用組成物來代替電洞注入層形成用組成物而形成。於利用濕式成膜法來形成電洞傳輸層4的情況下，通常電洞傳輸層形成用組成物更含有溶劑。電洞傳輸層形成用組成物中所使用的溶劑可使用與所述電洞注入層形成用組成物中所使用的溶劑同樣的溶劑。(Formation of hole transport layer 4 by wet film formation method) In the case of forming the hole transport layer 4 by a wet film formation method, generally, the same as when the hole injection layer 3 is formed by the wet film formation method, a composition for forming a hole transport layer is used instead of the holes. The injection layer forming composition is formed. In the case of forming the hole transport layer 4 by a wet film formation method, the composition for forming the hole transport layer generally contains a solvent. The solvent used in the composition for forming a hole transport layer can be the same as the solvent used in the composition for forming a hole injection layer.

電洞傳輸層形成用組成物中的電洞傳輸性化合物的濃度可設為與電洞注入層形成用組成物中的電洞傳輸性化合物的濃度同樣的範圍。利用濕式成膜法的電洞傳輸層4的形成可與所述電洞注入層3的成膜法同樣地進行。The concentration of the hole transporting compound in the composition for forming a hole transport layer can be set to the same range as the concentration of the hole transporting compound in the composition for forming a hole injection layer. The formation of the hole transport layer 4 by the wet film formation method can be performed in the same manner as the film formation method of the hole injection layer 3 described above.

（利用真空蒸鍍法的電洞傳輸層4的形成）於利用真空蒸鍍法形成電洞傳輸層4的情況下，亦通常與所述利用濕式成膜法形成電洞注入層3時同樣地，可使用電洞傳輸層4的構成材料來代替電洞注入層3的構成材料而形成。關於蒸鍍時的真空度、蒸鍍速度及溫度等成膜條件等，可利用與電洞注入層3的真空蒸鍍時同樣的條件來進行成膜。(Formation of hole transport layer 4 by vacuum evaporation method) In the case of forming the hole transport layer 4 by a vacuum vapor deposition method, it is usually the same as when the hole injection layer 3 is formed by the wet film formation method, and the constituent material of the hole transport layer 4 can be used instead of the electricity. The hole is formed by injecting the constituent material of the layer 3. Regarding the film forming conditions such as the degree of vacuum during the vapor deposition, the vapor deposition rate, and the temperature, the film can be formed under the same conditions as those during the vacuum vapor deposition of the hole injection layer 3.

＜發光層5＞發光層5是承擔於一對電極間被賦予電場時，藉由自陽極2注入的電洞與自陰極9注入的電子再結合而被激發，從而發光的功能的層。發光層5是形成於陽極2與陰極9之間的層。關於發光層5，於在陽極2之上存在電洞注入層3的情況下，形成於電洞注入層3與陰極9之間，於在陽極2之上存在電洞傳輸層4的情況下，形成於電洞傳輸層4與陰極9之間。＜Light-emitting layer 5＞ The light-emitting layer 5 is a layer that performs the function of being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 to emit light when an electric field is applied between a pair of electrodes. The light-emitting layer 5 is a layer formed between the anode 2 and the cathode 9. Regarding the light-emitting layer 5, when the hole injection layer 3 exists on the anode 2, it is formed between the hole injection layer 3 and the cathode 9, and when the hole transport layer 4 exists on the anode 2, It is formed between the hole transport layer 4 and the cathode 9.

只要不明顯損及本發明的效果，則發光層5的膜厚為任意，但就膜不易產生缺陷的方面而言，以厚為佳，另一方面，就容易實現低驅動電壓的方面而言以薄為佳。發光層5的膜厚較佳為3 nm以上，進而佳為5 nm以上，另外，通常較佳為200 nm以下，進而佳為100 nm以下。發光層5較佳為使用本實施形態的有機電場發光元件用組成物來形成，更佳為藉由濕式塗佈法來形成。除了使用本實施形態的有機電場發光元件用組成物並藉由濕式塗佈法而形成的發光層以外，有機電場發光元件亦可包括其他發光材料及電荷傳輸性材料，以下對其他發光材料及電荷傳輸性材料進行詳細敘述。As long as the effect of the present invention is not significantly impaired, the film thickness of the light-emitting layer 5 is arbitrary, but in terms of the film’s resistance to defects, the thickness is preferred. On the other hand, it is easier to achieve a low driving voltage. Thin is better. The thickness of the light-emitting layer 5 is preferably 3 nm or more, more preferably 5 nm or more, and is generally preferably 200 nm or less, and more preferably 100 nm or less. The light-emitting layer 5 is preferably formed using the composition for an organic electroluminescence element of this embodiment, and more preferably formed by a wet coating method. In addition to the light-emitting layer formed by the wet coating method using the composition for the organic electroluminescent element of this embodiment, the organic electroluminescent element may also include other light-emitting materials and charge-transporting materials. The charge transport material will be described in detail.

（發光材料）發光材料以所期望的發光波長發光，只要不損及本發明的效果，則並無特別限制，能夠應用公知的發光材料。發光材料可為螢光發光材料，亦可為磷光發光材料，但較佳為發光效率良好的材料，就內部量子效率的觀點而言，較佳為磷光發光材料。(Luminescent material) The luminescent material emits light at a desired emission wavelength, and as long as the effect of the present invention is not impaired, there is no particular limitation, and a known luminescent material can be applied. The luminescent material may be a fluorescent luminescent material or a phosphorescent luminescent material, but it is preferably a material with good luminous efficiency, and from the viewpoint of internal quantum efficiency, it is preferably a phosphorescent luminescent material.

作為螢光發光材料，例如可列舉以下材料。作為提供藍色發光的螢光發光材料（藍色螢光發光材料），例如可列舉萘、苝、芘、蒽、香豆素、䓛、對雙(2-苯基乙烯基)苯及該些的衍生物等。作為提供綠色發光的螢光發光材料（綠色螢光發光材料），例如可列舉喹吖啶酮衍生物、香豆素衍生物、Al(C₉ H₆ NO)₃ 等鋁錯合物等。Examples of the fluorescent material include the following materials. As the fluorescent light emitting material (blue fluorescent light emitting material) that provides blue light emission, for example, naphthalene, perylene, pyrene, anthracene, coumarin, cha, p-bis(2-phenylvinyl)benzene and these Derivatives and so on. Examples of fluorescent materials that provide green light emission (green fluorescent light-emitting materials) include quinacridone derivatives, coumarin derivatives, aluminum complexes such as _{Al(C 9} H ₆ NO) _{3, and the like.}

作為提供黃色發光的螢光發光材料（黃色螢光發光材料），例如可列舉紅螢烯、萘嘧啶酮（perimidone）衍生物等。作為提供紅色發光的螢光發光材料（紅色螢光發光材料），例如可列舉DCM（4-(二氰基亞甲基)-2-甲基-6-(對二甲基胺基苯乙烯基)-4H-吡喃）系化合物、苯並吡喃衍生物、玫瑰紅衍生物、苯並噻噸衍生物、氮雜苯並噻噸等。As a fluorescent light emitting material (yellow fluorescent light emitting material) that provides yellow light emission, for example, fluorescein, perimidone derivatives, and the like can be cited. As the fluorescent light-emitting material (red fluorescent light-emitting material) that provides red light emission, for example, DCM (4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl) )-4H-pyran) compounds, benzopyran derivatives, rose bengal derivatives, benzothioxanthone derivatives, azabenzothioxanthones, etc.

作為磷光發光材料，例如可列舉含有選自長週期型週期表（以下只要並無特別說明則於稱為「週期表」的情況下，是指長週期型週期表）的第7族～第11族中的金屬的有機金屬錯合物等。作為選自週期表的第7族～第11族中的金屬，較佳可列舉釕、銠、鈀、銀、錸、鋨、銥、鉑、金等。Examples of phosphorescent materials include Groups 7 to 11 selected from the long-period periodic table (hereinafter referred to as the "periodic table" unless otherwise specified). Organometallic complexes of metals in the group. Preferred examples of metals selected from Group 7 to Group 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold, and the like.

作為有機金屬錯合物的配位子，較佳為（雜）芳基吡啶配位子、（雜）芳基吡唑配位子等（雜）芳基與吡啶、吡唑、啡啉等連結而成的配位子，特別是較佳為苯基吡啶配位子、苯基吡唑配位子。此處，（雜）芳基表示芳基及雜芳基中的至少一者。As the ligands of the organometallic complexes, (hetero)arylpyridine ligands, (hetero)arylpyrazole ligands and other (hetero)aryl groups are preferably linked to pyridine, pyrazole, phenanthroline, etc. The ligands formed are particularly preferably phenylpyridine ligands and phenylpyrazole ligands. Here, the (hetero)aryl group means at least one of an aryl group and a heteroaryl group.

作為較佳的磷光發光材料，具體而言可列舉：三(2-苯基吡啶)銥、三(2-苯基吡啶)釕、三(2-苯基吡啶)鈀、雙(2-苯基吡啶)鉑、三(2-苯基吡啶)鋨、三(2-苯基吡啶)錸等苯基吡啶錯合物及八乙基鉑卟啉、八苯基鉑卟啉、八乙基鈀卟啉、八苯基鈀卟啉等卟啉錯合物等。As preferred phosphorescent luminescent materials, specific examples include: tris(2-phenylpyridine)iridium, tris(2-phenylpyridine)ruthenium, tris(2-phenylpyridine)palladium, bis(2-phenylpyridine) Pyridine)platinum, tris(2-phenylpyridine)osmium, tris(2-phenylpyridine)rhenium and other phenylpyridine complexes and octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin Porphyrin complexes such as phyrin, octaphenyl palladium porphyrin, etc.

作為高分子系發光材料，可列舉：聚(9,9-二辛基芴-2,7-二基)、聚[(9,9-二辛基芴-2,7-二基)-co-(4,4'-(N-(4-第二丁基苯基))二苯基胺)]、聚[(9,9-二辛基芴-2,7-二基)-co-(1,4-苯並-2{2,1'-3}-***)]等聚芴系材料、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-伸苯伸乙烯]等聚伸苯伸乙烯系材料。Examples of polymer-based light-emitting materials include poly(9,9-dioctylfluorene-2,7-diyl), poly[(9,9-dioctylfluorene-2,7-diyl)-co -(4,4'-(N-(4-Second-butylphenyl))diphenylamine)], poly[(9,9-dioctylfluorene-2,7-diyl)-co- (1,4-benzo-2{2,1'-3}-triazole)] and other polyfluorene-based materials, poly[2-methoxy-5-(2-ethylhexyloxy)-1, 4-styrene ethylene] and other polystyrene ethylene-based materials.

（電荷傳輸性材料）電荷傳輸性材料為具有正電荷（電洞）或負電荷（電子）傳輸性的材料，只要不損及本發明的效果，則並無特別限制，能夠應用公知的材料。電荷傳輸性材料可使用先前用於有機電場發光元件的發光層5的化合物等，特別是較佳為用作發光層5的主體材料的化合物。(Charge transport material) The charge-transporting material is a material having positive charge (hole) or negative charge (electron) transport properties. As long as the effect of the present invention is not impaired, it is not particularly limited, and known materials can be applied. The charge-transporting material can be a compound used in the light-emitting layer 5 of an organic electroluminescent element, and the like, and a compound used as a host material of the light-emitting layer 5 is particularly preferable.

作為電荷傳輸性材料，具體而言可列舉：芳香族胺系化合物、酞青系化合物、卟啉系化合物、低聚噻吩系化合物、聚噻吩系化合物、苄基苯基系化合物、利用芴基連結三級胺而成的化合物、腙系化合物、矽氮烷系化合物、矽烷胺系化合物、磷醯胺系化合物、喹吖啶酮系化合物等作為電洞注入層3的電洞傳輸性化合物而例示的化合物等，此外，亦可列舉蒽系化合物、芘系化合物、咔唑系化合物、吡啶系化合物、啡啉系化合物、噁二唑系化合物、噻咯系化合物等電子傳輸性化合物等。Specific examples of charge-transporting materials include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzyl phenyl compounds, and fluorenyl connection Compounds made of tertiary amines, hydrazone-based compounds, silazane-based compounds, silanamine-based compounds, phosphamide-based compounds, quinacridone-based compounds, etc. are exemplified as hole-transporting compounds in the hole injection layer 3 In addition, electron-transporting compounds such as anthracene-based compounds, pyrene-based compounds, carbazole-based compounds, pyridine-based compounds, phenanthroline-based compounds, oxadiazole-based compounds, and silole-based compounds can also be cited.

作為電荷傳輸性材料，亦可較佳地使用：4,4'-雙[N-(1-萘基)-N-苯基胺基]聯苯所代表的含有兩個以上的三級胺且兩個以上的縮合芳香族環取代為氮原子的芳香族二胺（日本專利特開平5-234681號公報）、4,4',4''-三(1-萘基苯基胺基)三苯基胺等具有星爆結構的芳香族胺系化合物（發光學報（J. Lumin.），72-74卷，985頁，1997年）、包含三苯基胺的四聚體的芳香族胺系化合物（化學通訊（Chem. Commun.），2175頁，1996年）、2,2',7,7'-四-(二苯基胺基)-9,9'-螺二芴等芴系化合物（合成材料（Synth. Metals），91卷，209頁，1997年）、4,4'-N,N'-二咔唑聯苯等咔唑系化合物等作為電洞傳輸層4的電洞傳輸性化合物而例示的化合物等。此外，亦可列舉：2-(4-聯苯基)-5-(對第三丁基苯基)-1,3,4-噁二唑（tBu-PBD）、2,5-雙(1-萘基)-1,3,4-噁二唑（BND）等噁二唑系化合物；2,5-雙(6'-(2',2''-聯吡啶基))-1,1-二甲基-3,4-二苯基噻咯（PyPySPyPy）等噻咯系化合物；4,7-二苯基-1,10-啡啉（bathophenanthroline，BPhen）、2,9-二甲基-4,7-二苯基-1,10-啡啉（bathocuproin，BCP）等啡啉系化合物等。As a charge-transporting material, it can also be preferably used: 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl containing two or more tertiary amines and Aromatic diamines in which two or more condensed aromatic rings are substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4',4''-tris(1-naphthylphenylamino) three Aromatic amine compounds with starburst structure such as phenylamine (J. Lumin., Volume 72-74, Page 985, 1997), aromatic amines containing tetramers of triphenylamine Compounds (Chem. Commun.), 2175 pages, 1996), 2,2',7,7'-tetra-(diphenylamino)-9,9'-spirobifluorene and other fluorene compounds (Synth. Metals, Vol. 91, p. 209, 1997), 4,4'-N,N'-dicarbazole biphenyl and other carbazole-based compounds as hole transport in the hole transport layer 4 Exemplified compounds and the like. In addition, you can also cite: 2-(4-biphenyl)-5-(p-tertiary butylphenyl)-1,3,4-oxadiazole (tBu-PBD), 2,5-bis(1 -Naphthyl)-1,3,4-oxadiazole (BND) and other oxadiazole compounds; 2,5-bis(6'-(2',2''-bipyridyl))-1,1 -Dimethyl-3,4-diphenylsilole (PyPySPyPy) and other silole compounds; 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline, BPhen), 2,9-dimethyl -4,7-Diphenyl-1,10-phenanthroline (bathocuproin, BCP) and other phenanthroline compounds, etc.

（利用濕式成膜法的發光層5的形成）有機電場發光元件較佳為具有使用本實施形態的有機電場發光元件用組成物並藉由濕式成膜法而形成的發光層。作為發光層5，除了使用本實施形態的有機電場發光元件用組成物而形成的發光層以外，亦可具有發光層。該些發光層的形成方法可為真空蒸鍍法，亦可為濕式成膜法，但就成膜性優異而言，較佳為濕式成膜法。(Formation of light-emitting layer 5 by wet film forming method) The organic electroluminescence element preferably has a light-emitting layer formed by a wet film formation method using the composition for an organic electroluminescence element of this embodiment. As the light-emitting layer 5, in addition to the light-emitting layer formed using the composition for an organic electroluminescent element of this embodiment, it may have a light-emitting layer. The formation method of these light-emitting layers may be a vacuum deposition method or a wet film formation method, but in terms of excellent film formation properties, the wet film formation method is preferred.

於藉由濕式成膜法形成發光層5的情況下，通常與所述利用濕式成膜法形成電洞注入層3時同樣地，使用將形成發光層5的材料與可溶的溶劑（發光層用溶劑）混合而製備的發光層形成用組成物來代替電洞注入層形成用組成物而形成。作為溶劑，例如除了針對電洞注入層3的形成而列舉的醚系溶劑、酯系溶劑、芳香族烴系溶劑、醯胺系溶劑以外，亦可列舉烷烴系溶劑、鹵化芳香族烴系溶劑、脂肪族醇系溶劑、脂環族醇系溶劑、脂肪族酮系溶劑及脂環族酮系溶劑等。所使用的溶劑如亦作為本實施形態的含銥錯合物化合物的組成物的溶劑所例示般。以下列舉溶劑的具體例，但只要不損及本發明的效果，則並不限定於該些。In the case of forming the light-emitting layer 5 by a wet film formation method, generally, as in the case of forming the hole injection layer 3 by the wet film formation method, the material for forming the light-emitting layer 5 and a soluble solvent are used ( The light-emitting layer forming composition prepared by mixing the solvent for the light-emitting layer is formed instead of the hole injection layer forming composition. As the solvent, for example, in addition to the ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, and amide-based solvents listed for the formation of the hole injection layer 3, alkane-based solvents, halogenated aromatic hydrocarbon-based solvents, Aliphatic alcohol solvents, alicyclic alcohol solvents, aliphatic ketone solvents, alicyclic ketone solvents, etc. The solvent used is also exemplified as the solvent of the composition of the iridium-containing complex compound of the present embodiment. Specific examples of solvents are listed below, but they are not limited to these as long as the effects of the present invention are not impaired.

例如可列舉：乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚乙酸酯（PGMEA）等脂肪族醚系溶劑；1,2-二甲氧基苯、1,3-二甲氧基苯、苯甲醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基苯甲醚、2,4-二甲基苯甲醚、二苯基醚等芳香族醚系溶劑；乙酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯系溶劑；甲苯、二甲苯、均三甲苯、環己基苯、四氫萘、3-異丙基聯苯、1,2,3,4-四甲基苯、1,4-二異丙基苯、甲基萘等芳香族烴系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺系溶劑；正癸烷、環己烷、乙基環己烷、十氫萘、雙環己烷（bicyclohexane）等烷烴系溶劑；氯苯、二氯苯、三氯苯等鹵化芳香族烴系溶劑；丁醇、己醇等脂肪族醇系溶劑；環己醇、環辛醇等脂環族醇系溶劑；甲基乙基酮、二丁基酮等脂肪族酮系溶劑；環己酮、環辛酮、葑酮等脂環族酮系溶劑等。該些中，特佳為烷烴系溶劑及芳香族烴系溶劑。For example, aliphatic ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3 -Dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4- Aromatic ether solvents such as dimethyl anisole and diphenyl ether; aromatics such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate, etc. Ester solvents; toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropyl Aromatic hydrocarbon solvents such as benzene and methylnaphthalene; amine solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; n-decane, cyclohexane, ethyl ring Alkane solvents such as hexane, decahydronaphthalene, and bicyclohexane; halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; aliphatic alcohol solvents such as butanol and hexanol; cyclohexane Alicyclic alcohol-based solvents such as alcohol and cyclooctanol; aliphatic ketone-based solvents such as methyl ethyl ketone and dibutyl ketone; alicyclic ketone-based solvents such as cyclohexanone, cyclooctanone, and fenone. Among these, particularly preferred are an alkane-based solvent and an aromatic hydrocarbon-based solvent.

為了獲得更均勻的膜，較佳為溶劑以適當的速度自剛剛成膜後的液膜蒸發。因此，所使用的溶劑的沸點如上所述，通常為80℃以上，較佳為100℃以上，更佳為120℃以上，通常為270℃以下，較佳為250℃以下，更佳為230℃以下。只要不明顯損及本發明的效果，則溶劑的使用量為任意，但就因低黏性而容易進行成膜作業的方面而言，發光層形成用組成物、即含銥錯合物化合物的組成物中的合計含量以多為佳，就容易以厚膜成膜的方面而言以低為佳。如上所述，溶劑的含量於含銥錯合物化合物的組成物中較佳為1質量%以上，更佳為10質量%以上，特佳為50質量%以上，較佳為99.99質量%以下，更佳為99.9質量%以下，特佳為99質量%以下。In order to obtain a more uniform film, it is preferable that the solvent evaporate from the liquid film immediately after film formation at an appropriate rate. Therefore, the boiling point of the solvent used is as described above, usually 80°C or higher, preferably 100°C or higher, more preferably 120°C or higher, usually 270°C or lower, preferably 250°C or lower, more preferably 230°C the following. The amount of solvent used is arbitrary as long as the effect of the present invention is not significantly impaired. However, in terms of easy film formation due to low viscosity, the composition for forming a light-emitting layer, that is, a compound containing an iridium complex compound The total content in the composition is preferably large, and it is preferably low in terms of easy formation of a thick film. As described above, the content of the solvent in the composition containing the iridium complex compound is preferably 1% by mass or more, more preferably 10% by mass or more, particularly preferably 50% by mass or more, and preferably 99.99% by mass or less, It is more preferably 99.9% by mass or less, and particularly preferably 99% by mass or less.

作為濕式成膜後的溶劑除去方法，可採用加熱或減壓。作為加熱方法中使用的加熱手段，就對膜整體均等地提供熱而言，較佳為清潔烘箱、加熱板。只要不明顯損及本發明的效果，則加熱步驟中的加熱溫度為任意，但就縮短乾燥時間的方面而言，較佳為溫度高，就對材料的損傷少的方面而言，以低為佳。加溫溫度的上限通常為250℃以下，較佳為200℃以下，進而佳為150℃以下。加溫溫度的下限通常為30℃以上，較佳為50℃以上，進而佳為80℃以上。藉由設為所述上限以下，成為較通常所使用的電荷傳輸性材料或磷光發光材料的耐熱性低的溫度，從而可抑制分解或結晶化。藉由使加熱溫度為所述下限以上，可避免溶劑的去除中的長時間化。加熱步驟中的加熱時間可根據發光層形成用組成物中的溶劑的沸點、或蒸氣壓、材料的耐熱性及加熱條件而適當決定。As a solvent removal method after wet film formation, heating or reduced pressure can be used. As the heating means used in the heating method, in terms of uniformly supplying heat to the entire film, it is preferable to clean an oven or a hot plate. As long as the effect of the present invention is not significantly impaired, the heating temperature in the heating step is arbitrary, but in terms of shortening the drying time, the temperature is preferably high, and in terms of less damage to the material, low is good. The upper limit of the heating temperature is usually 250°C or lower, preferably 200°C or lower, and more preferably 150°C or lower. The lower limit of the heating temperature is usually 30°C or higher, preferably 50°C or higher, and more preferably 80°C or higher. By setting it to the upper limit or less, it becomes a temperature lower than the heat resistance of the charge transport material or phosphorescent material used normally, and can suppress decomposition or crystallization. By setting the heating temperature to be equal to or higher than the above lower limit, it is possible to avoid prolonged time in solvent removal. The heating time in the heating step can be appropriately determined according to the boiling point or vapor pressure of the solvent in the composition for forming a light-emitting layer, the heat resistance of the material, and the heating conditions.

（利用真空蒸鍍法的發光層5的形成）於藉由真空蒸鍍法形成發光層5的情況下，通常將發光層5的構成材料，即所述發光材料、電荷傳輸性化合物等的一種或兩種以上放入至設置於真空容器內的坩堝中。此時於使用兩種以上的材料的情況下，通常分別放入至不同的坩堝中。其後，利用真空泵將真空容器內排氣至10^-4 Pa左右後，加熱坩堝，一邊控制坩堝內的材料的蒸發量一邊使其蒸發。於使用兩種以上的材料的情況下，通常對各個坩堝進行加熱，分別獨立地一邊控制蒸發量一邊使其蒸發。藉由所述操作，使發光層5形成於面向坩堝放置的電洞注入層3或電洞傳輸層4之上。於使用兩種以上的材料的情況下，亦可將該些作為混合物而放入至坩堝中，加熱使其蒸發來形成發光層5。(Formation of the light-emitting layer 5 by the vacuum evaporation method) When the light-emitting layer 5 is formed by the vacuum evaporation method, the constituent material of the light-emitting layer 5, that is, one of the light-emitting materials, charge-transporting compounds, etc. Or two or more are put into the crucible set in the vacuum container. At this time, when two or more materials are used, they are usually put into different crucibles. After that, the inside of the vacuum container was evacuated to about 10 ^-4 Pa with a vacuum pump, and the crucible was heated to evaporate the material in the crucible while controlling the evaporation amount of the material in the crucible. When two or more kinds of materials are used, each crucible is usually heated, and each crucible is evaporated while independently controlling the amount of evaporation. Through the above operation, the light-emitting layer 5 is formed on the hole injection layer 3 or the hole transport layer 4 placed facing the crucible. When two or more kinds of materials are used, they may be put into a crucible as a mixture, and heated and evaporated to form the light-emitting layer 5.

只要不明顯損及本發明的效果，則蒸鍍時的真空度並無限定，通常為0.1×10^-6 Torr（0.13×10^-4 Pa）以上且9.0×10^-6 Torr（12.0×10^-4 Pa）以下。只要不明顯損及本發明的效果，則蒸鍍速度並無限定，通常為0.1 Å/秒以上且5.0 Å/秒以下。只要不明顯損及本發明的效果，則蒸鍍時的成膜溫度並無限定，較佳為於10℃以上且50℃以下進行。That does not significantly impair the effects of the present invention, the degree of vacuum during the deposition is not limited, but is usually ^{0.1 × 10 -6 Torr (0.13 ×} 10 -4 Pa) or more and ^{9.0 × 10 -6 Torr (12.0 ×} 10 - ⁴ Pa) or less. As long as the effect of the present invention is not significantly impaired, the vapor deposition rate is not limited, and it is usually 0.1 Å/sec or more and 5.0 Å/sec or less. As long as the effect of the present invention is not significantly impaired, the film formation temperature during vapor deposition is not limited, and it is preferably performed at 10°C or higher and 50°C or lower.

＜電洞阻擋層6＞亦可於發光層5與後述的電子注入層8之間設置電洞阻擋層6。電洞阻擋層6是於發光層5之上以與發光層5的陰極9側的界面相接的方式積層的層。電洞阻擋層6具有阻擋自陽極2移動而來的電洞到達陰極9的作用及將自陰極9注入的電子效率良好地傳輸至發光層5的方向的作用。作為對構成電洞阻擋層6的材料所要求的物性，可列舉電子遷移率高且電洞遷移率低、能隙即HOMO與LUMO之差大、及激發三重態能階（T1）高。＜Hole barrier layer 6＞ A hole blocking layer 6 may be provided between the light-emitting layer 5 and the electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light-emitting layer 5 so as to be in contact with the interface on the cathode 9 side of the light-emitting layer 5. The hole blocking layer 6 has a function of blocking holes moved from the anode 2 from reaching the cathode 9 and a function of efficiently transporting electrons injected from the cathode 9 to the direction of the light-emitting layer 5. The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, large energy gap, which is the difference between HOMO and LUMO, and high excited triplet energy level (T1).

作為滿足此種條件的電洞阻擋層6的材料，例如可列舉：雙(2-甲基-8-羥基喹啉)(苯酚)鋁、雙(2-甲基-8-羥基喹啉)(三苯基矽醇)鋁（bis(2-methyl-8-quinolinolato)(triphenyl silanolato)aluminum）等混合配位子錯合物、雙(2-甲基-8-羥基喹啉)鋁-μ-氧代-雙-(2-甲基-8-羥基喹啉)鋁二核金屬錯合物等金屬錯合物、二苯乙烯基聯苯衍生物等苯乙烯基化合物（日本專利特開平11-242996號公報）、3-(4-聯苯基)-4-苯基-5-(4-第三丁基苯基)-1,2,4-***等***衍生物（日本專利特開平7-41759號公報）、浴銅靈（bathocuproin）等啡啉衍生物（日本專利特開平10-79297號公報）等。國際公開第2005/022962號中所記載的具有至少一個2,4,6位經取代的吡啶環的化合物亦作為電洞阻擋層6的材料較佳。As a material of the hole blocking layer 6 that satisfies such conditions, for example, bis(2-methyl-8-hydroxyquinoline) (phenol)aluminum, bis(2-methyl-8-hydroxyquinoline) ( Triphenylsilanol) aluminum (bis(2-methyl-8-quinolinolato)(triphenyl silanolato)aluminum) and other mixed ligand complexes, bis(2-methyl-8-quinolinolato)aluminum-μ- Metal complexes such as oxo-bis-(2-methyl-8-hydroxyquinoline) aluminum dinuclear metal complexes, and styryl compounds such as stilbene biphenyl derivatives (Japanese Patent Laid-Open No. 11- 242996), 3-(4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole and other triazole derivatives (Japanese Patent Special Kaihei 7-41759), phenanthroline derivatives such as bathocuproin (Japanese Patent Laid-open No. 10-79297), etc. The compounds described in International Publication No. 2005/022962 having at least one substituted pyridine ring at positions 2, 4, and 6 are also preferable as the material of the hole blocking layer 6.

電洞阻擋層6的形成方法並無限制，可與所述發光層5的形成方法同樣地形成。只要不明顯損及本發明的效果，則電洞阻擋層6的膜厚為任意，通常為0.3 nm以上，較佳為0.5 nm以上，通常為100 nm以下，較佳為50 nm以下。The method of forming the hole blocking layer 6 is not limited, and it can be formed in the same manner as the method of forming the light-emitting layer 5 described above. As long as the effect of the present invention is not significantly impaired, the film thickness of the hole blocking layer 6 is arbitrary, and is usually 0.3 nm or more, preferably 0.5 nm or more, usually 100 nm or less, preferably 50 nm or less.

＜電子傳輸層7＞出於進一步提高元件的電流效率的目的，電子傳輸層7設於發光層5或電洞阻擋層6與電子注入層8之間。電子傳輸層7由可於被賦予電場的電極間將自陰極9注入的電子效率良好地傳輸至發光層5的方向的化合物形成。作為電子傳輸層7中所使用的電子傳輸性化合物，需要為自陰極9或電子注入層8的電子注入效率高、且具有高的電子遷移率並可效率良好地傳輸所注入的電子的化合物。＜Electron transport layer 7＞ For the purpose of further improving the current efficiency of the device, the electron transport layer 7 is provided between the light emitting layer 5 or the hole blocking layer 6 and the electron injection layer 8. The electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 9 to the direction of the light emitting layer 5 between electrodes to which an electric field is applied. The electron-transporting compound used in the electron-transporting layer 7 needs to be a compound that has high electron injection efficiency from the cathode 9 or the electron injection layer 8 and has high electron mobility and can efficiently transport the injected electrons.

作為滿足此種條件的電子傳輸性化合物，例如可列舉：8-羥基喹啉（8-hydroxyquinoline）的鋁錯合物等金屬錯合物（日本專利特開昭59-194393號公報）、10-羥基苯並[h]喹啉的金屬錯合物、噁二唑衍生物、二苯乙烯基聯苯衍生物、噻咯（silole）衍生物、3-羥基黃酮金屬錯合物、5-羥基黃酮金屬錯合物、苯並噁唑金屬錯合物、苯並噻唑金屬錯合物、三苯並咪唑基苯（美國專利第5645948號說明書）、喹噁啉化合物（日本專利特開平6-207169號公報）、啡啉衍生物（日本專利特開平5-331459號公報）、2-第三丁基-9,10-N,N'-二氰基蒽醌二亞胺、n型氫化非晶質碳化矽、n型硫化鋅、n型硒化鋅等。Examples of electron-transporting compounds satisfying such conditions include: 8-hydroxyquinoline (8-hydroxyquinoline) aluminum complexes and other metal complexes (Japanese Patent Laid-Open No. 59-194393), 10- Metal complexes of hydroxybenzo[h]quinoline, oxadiazole derivatives, stilbene biphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone Metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, tribenzimidazolylbenzene (U.S. Patent No. 5645948 specification), quinoxaline compounds (Japanese Patent Laid-Open No. 6-207169) Bulletin), phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459), 2-tert-butyl-9,10-N,N'-dicyanoanthraquinone diimide, n-type hydrogenated amorphous Silicon carbide, n-type zinc sulfide, n-type zinc selenide, etc.

電子傳輸層7的膜厚通常為1 nm以上，較佳為5 nm以上，通常為300 nm以下，較佳為100 nm以下。電子傳輸層7與與發光層5同樣地，藉由濕式成膜法或者真空蒸鍍法在發光層5或電洞阻擋層6上進行積層來形成。通常多使用真空蒸鍍法。The thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, usually 300 nm or less, preferably 100 nm or less. The electron transport layer 7 is formed by laminating the light emitting layer 5 or the hole blocking layer 6 by a wet film formation method or a vacuum vapor deposition method similarly to the light emitting layer 5. Usually, the vacuum evaporation method is often used.

＜電子注入層8＞電子注入層8發揮以下作用：將自陰極9注入的電子效率良好地注入至電子傳輸層7或發光層5。為了效率良好地進行電子注入，較佳為於形成電子注入層8的材料中使用功函數低的金屬。作為例子，可使用鈉或銫等鹼金屬、鋇或鈣等鹼土金屬等。＜Electron injection layer 8＞ The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the electron transport layer 7 or the light-emitting layer 5. In order to perform electron injection efficiently, it is preferable to use a metal with a low work function in the material forming the electron injection layer 8. As examples, alkali metals such as sodium or cesium, alkaline earth metals such as barium or calcium, and the like can be used.

電子注入層8的膜厚較佳為0.1 nm～5 nm。於陰極9與電子傳輸層7的界面***LiF、MgF₂ 、Li₂ O、Cs₂ CO₃ 等膜厚為0.1 nm～5 nm左右的極薄絕緣膜作為電子注入層8亦是提高元件的效率的有效方法（應用物理快報（Appl. Phys. Lett.），70卷，152頁，1997年；日本專利特開平10-74586號公報；電子設備IEEE會報（IEEETrans. Electron. Devices），44卷，1245頁，1997年；國際訊息顯示學會（Society for Information Display，SID）04 摘要（Digest），2004年，154頁）。The thickness of the electron injection layer 8 is preferably 0.1 nm to 5 nm. _{Inserting LiF, MgF 2} , Li ₂ O, Cs ₂ CO ₃ and other very thin insulating films with a thickness of about 0.1 nm to 5 nm at the interface between the cathode 9 and the electron transport layer 7 as the electron injection layer 8 also improves the efficiency of the device Phys. Lett. (Appl. Phys. Lett.), Volume 70, 152 pages, 1997; Japanese Patent Laid-Open No. 10-74586; IEEE Trans. Electron. Devices, Volume 44, 1245 pages, 1997; Society for Information Display (SID) 04 Digest, 2004, 154 pages).

進而，藉由對4,7-二苯基-1,10-啡啉（bathophenanthroline）等含氮雜環化合物或8-羥基喹啉的鋁錯合物等金屬錯合物所代表的有機電子傳輸材料摻雜鈉、鉀、銫、鋰、銣等鹼金屬（日本專利特開平10-270171號公報、日本專利特開2002-100478號公報、日本專利特開2002-100482號公報等中記載），能夠兼具電子注入性、傳輸性提升的優異的膜質，因此較佳。該情況下的膜厚通常為5 nm以上，較佳為10 nm以上，通常為200 nm以下，較佳為100 nm以下。電子注入層8與發光層5同樣地藉由利用濕式成膜法或者真空蒸鍍法積層於發光層5或其上的電洞阻擋層6或電子傳輸層7上而形成。濕式成膜法的情況下的詳細情況與所述發光層5的情況相同。Furthermore, organic electron transport represented by nitrogen-containing heterocyclic compounds such as 4,7-diphenyl-1,10-phenanthroline or metal complexes such as aluminum complexes of 8-hydroxyquinoline The material is doped with alkali metals such as sodium, potassium, cesium, lithium, rubidium (described in Japanese Patent Laid-Open No. 10-270171, Japanese Patent Laid-Open No. 2002-100478, Japanese Patent Laid-Open No. 2002-100482, etc.), It is preferable because it has excellent film quality with improved electron injection properties and improved transport properties. The film thickness in this case is usually 5 nm or more, preferably 10 nm or more, usually 200 nm or less, and preferably 100 nm or less. The electron injection layer 8 is formed by laminating the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 on the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 similarly to the light emitting layer 5 by a wet film formation method or a vacuum evaporation method. The details in the case of the wet film formation method are the same as in the case of the light-emitting layer 5 described above.

＜陰極9＞陰極9發揮將電子注入至電子注入層8或發光層5等發光層5側的層的作用。作為陰極9的材料，能夠使用所述陽極2中所使用的材料，但就效率良好地進行電子注入的方面而言，較佳為使用功函數低的金屬，例如可使用錫、鎂、銦、鈣、鋁、銀等金屬或者該些的合金等。作為陰極9的材料，例如可列舉鎂-銀合金、鎂-銦合金、鋁-鋰合金等低功函數的合金電極等。＜Cathode 9＞ The cathode 9 plays a role of injecting electrons into a layer on the light-emitting layer 5 side such as the electron injection layer 8 or the light-emitting layer 5. As the material of the cathode 9, the material used in the anode 2 can be used, but in terms of efficient electron injection, it is preferable to use a metal with a low work function. For example, tin, magnesium, indium, etc. can be used. Metals such as calcium, aluminum, and silver, or alloys of these. Examples of the material of the cathode 9 include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

就元件的穩定性的方面而言，較佳為於陰極9之上積層功函數高、相對於大氣穩定的金屬層，來保護包含低功函數的金屬的陰極9。作為積層的金屬，例如可列舉鋁、銀、銅、鎳、鉻、金、鉑等金屬。陰極的膜厚通常與陽極2相同。In terms of device stability, it is preferable to laminate a metal layer with a high work function and stable with respect to the atmosphere on the cathode 9 to protect the cathode 9 containing a metal with a low work function. Examples of the laminated metal include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum. The film thickness of the cathode is usually the same as that of the anode 2.

＜其他構成層＞以上，以圖1所示的層構成的元件為中心進行了說明，但於本實施形態的有機電場發光元件的陽極2及陰極9與發光層5之間，只要不損及其性能，則除了上述說明中的層以外，亦可具有任意的層，另外，亦可省略發光層5以外的任意的層。＜Other constituent layers＞ The above description is centered on the element with the layer structure shown in FIG. 1. However, the organic electroluminescent element of the present embodiment between the anode 2 and cathode 9 and the light-emitting layer 5, as long as its performance is not impaired, except Any layer other than the layer in the above description may be provided, and any layer other than the light-emitting layer 5 may be omitted.

例如，出於與電洞阻擋層6同樣的目的，於電洞傳輸層4與發光層5之間設置電子阻擋層亦有效。電子阻擋層有如下作用：藉由阻擋自發光層5移動來的電子到達電洞傳輸層4，而增加發光層5內與電洞的再結合概率，將生成的激子封閉於發光層5內的作用；及將自電洞傳輸層4注入的電洞效率良好地向發光層5的方向傳輸的作用。For example, for the same purpose as the hole blocking layer 6, it is also effective to provide an electron blocking layer between the hole transport layer 4 and the light-emitting layer 5. The electron blocking layer has the following function: by blocking the electrons moving from the light-emitting layer 5 from reaching the hole transport layer 4, the probability of recombination with holes in the light-emitting layer 5 is increased, and the generated excitons are enclosed in the light-emitting layer 5 The role of; and the role of efficiently transporting holes injected from the hole transport layer 4 in the direction of the light emitting layer 5.

作為對電子阻擋層所要求的特性，可列舉電洞傳輸性高、能隙即HOMO與LUMO之差大、激發三重態能級（T1）高。於利用濕式成膜法形成發光層5的情況下，電子阻擋層亦利用濕式成膜法形成會使元件製造變得容易，因此較佳。因此，電子阻擋層亦較佳為具有濕式成膜適應性，作為此種電子阻擋層中所使用的材料，可列舉以F8-TFB為代表的二辛基芴與三苯基胺的共聚物（國際公開第2004/084260號）等。The characteristics required for the electron blocking layer include high hole transportability, a large energy gap, that is, a large difference between HOMO and LUMO, and a high excited triplet energy level (T1). In the case where the light-emitting layer 5 is formed by a wet film formation method, the electron blocking layer is also formed by a wet film formation method, which facilitates device manufacturing, which is therefore preferable. Therefore, the electron blocking layer is also preferably suitable for wet film formation. As the material used in this type of electron blocking layer, a copolymer of dioctylfluorene and triphenylamine represented by F8-TFB can be cited. (International Publication No. 2004/084260) and so on.

亦可為與圖1相反的結構，即，在基板1上依序積層陰極9、電子注入層8、電子傳輸層7、電洞阻擋層6、發光層5、電洞傳輸層4、電洞注入層3、陽極2。另外，亦能夠於至少一者的透明性高的兩片基板之間設置本實施形態的有機電場發光元件。亦能夠設為積層有多級圖1所示的層構成的結構即積層有多個發光單元的結構。此時，若將例如V₂ O₅ 等用作電荷產生層來代替級間即發光單元間的界面層，則級間的障壁變少，就發光效率、驅動電壓的觀點而言更佳。界面層於例如陽極為氧化銦錫（indium tin oxide，ITO），陰極為Al的情況下是指該兩層。本發明於有機電場發光元件為單個元件、具有呈陣列狀配置的結構的元件、陽極與陰極呈X-Y矩陣狀配置的結構中的任一種中均可應用。It may also have a structure opposite to that of FIG. 1, that is, a cathode 9, an electron injection layer 8, an electron transport layer 7, a hole blocking layer 6, a light emitting layer 5, a hole transport layer 4, and a hole are sequentially laminated on the substrate 1. Injection layer 3, anode 2. In addition, the organic electroluminescent element of this embodiment can also be provided between at least one of two highly transparent substrates. It is also possible to have a structure in which the layer configuration shown in FIG. 1 is laminated in multiple stages, that is, a structure in which a plurality of light-emitting units are laminated. At this time, if, for example, V ₂ O _{5 is} used as the charge generation layer instead of the interface layer between the stages, that is, between the light-emitting units, the barriers between the stages are reduced, which is more preferable from the viewpoint of luminous efficiency and driving voltage. For example, the interface layer refers to the two layers when the anode is indium tin oxide (ITO) and the cathode is Al. The present invention can be applied to any of the organic electroluminescence element is a single element, the element has a structure arranged in an array, and the anode and the cathode are arranged in an XY matrix.

[顯示裝置] 本實施形態的顯示裝置及照明裝置具有如上所述的有機電場發光元件。對於顯示裝置的形式或結構無特別限制，可使用本實施形態的有機電場發光元件並依照常法進行組裝。[Display device] The display device and the lighting device of this embodiment have the organic electroluminescence element as described above. There is no particular limitation on the form or structure of the display device, and the organic electroluminescent element of this embodiment can be used and assembled in accordance with a conventional method.

例如，可利用「有機EL顯示器」（歐姆社（Ohmsha），2004年8月20日發行，時任靜士、安達千波矢、村田英幸著）中所記載般的方法，來形成本實施形態的顯示裝置。實施例以下，示出實施例來對本發明進行更具體的說明。本發明並不限定於以下實施例，只要不脫離本發明的主旨，則可任意地變更來實施本發明。For example, the display of this embodiment can be formed by using the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, by Shishi Shi, Chinami Adachi, Hideyuki Murata). Device. Example Hereinafter, examples are shown to explain the present invention more specifically. The present invention is not limited to the following examples, and can be arbitrarily modified and implemented as long as it does not deviate from the gist of the present invention.

[實施例1] 利用以下的方法製作了有機電場發光元件。針對於玻璃基板上將銦/錫氧化物（ITO）的透明導電膜堆積為50 nm的厚度而成者（三容真空公司製造，濺鍍成膜品），使用通常的光微影技術與鹽酸蝕刻，圖案化為2 mm寬的條紋而形成陽極。將如此進行了ITO的圖案形成的基板按照基於界面活性劑水溶液的超音波清洗、基於超純水的水洗、基於超純水的超音波清洗、基於超純水的水洗的順序進行清洗後，利用壓縮空氣使其乾燥，最後進行紫外線臭氧清洗。[Example 1] The organic electroluminescent element was produced by the following method. For those made by depositing a transparent conductive film of indium/tin oxide (ITO) to a thickness of 50 nm on a glass substrate (manufactured by Sanyo Vacuum Co., Ltd., sputtered film product), the usual photolithography technology and hydrochloric acid are used Etched and patterned into 2 mm wide stripes to form the anode. The substrate patterned with ITO is cleaned in the order of ultrasonic cleaning with surfactant aqueous solution, ultrapure water, ultrasonic cleaning with ultrapure water, and water cleaning with ultrapure water. Compressed air is used to dry it, and finally it is cleaned with ultraviolet ozone.

作為電洞注入層形成用組成物，製備使具有下述式（P-1）所表示的重複結構的電洞傳輸性高分子化合物3.0質量%與下述式（HI-1）所表示的氧化劑0.6質量%溶解於苯甲酸乙酯中而成的組成物。將該溶液於大氣中旋塗於所述基板上，於大氣中利用加熱板於240℃下乾燥30分鐘，形成膜厚40 nm的均勻的薄膜，作為電洞注入層。As a composition for forming a hole injection layer, an oxidizing agent represented by the following formula (HI-1) and 3.0% by mass of a hole-transporting polymer compound having a repeating structure represented by the following formula (P-1) was prepared A composition made by dissolving 0.6% by mass in ethyl benzoate. The solution was spin-coated on the substrate in the atmosphere, and dried in the atmosphere on a hot plate at 240° C. for 30 minutes to form a uniform thin film with a thickness of 40 nm as a hole injection layer.

[化23]

[化23]

接著，使具有下述式（HT-1）所表示的結構的電荷傳輸性高分子化合物100質量份溶解於環己基苯中，製備3.0質量%的溶液。將該溶液於氮手套箱中旋塗於塗佈成膜有所述電洞注入層的基板上，利用氮手套箱中的加熱板於230℃下乾燥30分鐘，形成膜厚40 nm的均勻的薄膜，作為電洞傳輸層。Next, 100 parts by mass of a charge-transporting polymer compound having a structure represented by the following formula (HT-1) was dissolved in cyclohexylbenzene to prepare a 3.0% by mass solution. The solution was spin-coated in a nitrogen glove box on a substrate coated with the hole injection layer, and dried on a heating plate in a nitrogen glove box at 230°C for 30 minutes to form a uniform film with a thickness of 40 nm. Thin film, as a hole transport layer.

[化24]

[化24]

繼而，秤量下述式（H-1）所表示的化合物60質量份、下述式（H-2）所表示的化合物40質量份、下述式（D-1）所表示的成為紅色發光摻雜劑的化合物15質量份及下述式（D-2）所表示的成為輔助摻雜劑的化合物15質量份作為發光層的材料，使其溶解於環己基苯中製備7.8質量%的溶液。Then, weigh 60 parts by mass of the compound represented by the following formula (H-1), 40 parts by mass of the compound represented by the following formula (H-2), and the compound represented by the following formula (D-1) as a red luminescent dopant. 15 parts by mass of the compound of the dopant and 15 parts by mass of the compound as an auxiliary dopant represented by the following formula (D-2) were used as the material of the light-emitting layer, and were dissolved in cyclohexylbenzene to prepare a 7.8% by mass solution.

[化25]

[化25]

將該溶液於氮手套箱中旋塗於塗佈成膜有所述電洞傳輸層的基板上，利用氮手套箱中的加熱板於120℃下乾燥20分鐘，形成膜厚80 nm的均勻的薄膜，作為發光層。再者，式（D-1）所表示的化合物是以波長613 nm、式（D-2）所表示的化合物是以波長555 nm為最大發光波長的摻雜劑。The solution was spin-coated in a nitrogen glove box on the substrate coated with the hole transport layer, and dried on a heating plate in a nitrogen glove box at 120°C for 20 minutes to form a uniform film with a thickness of 80 nm. Thin film, as the light-emitting layer. In addition, the compound represented by formula (D-1) is a dopant whose wavelength is 613 nm, and the compound represented by formula (D-2) is a dopant whose wavelength is 555 nm as the maximum emission wavelength.

將至成膜有發光層的基板設置於真空蒸鍍裝置，將裝置內排氣至成為2×10^-4 Pa以下。接著，藉由真空蒸鍍法將下述式（HB-1）所表示的化合物及8-羥基喹啉鋰以成為2:3的膜厚比的方式以1 Å/秒的速度共蒸鍍於發光層上，形成膜厚30 nm的電洞阻擋層。The substrate on which the light-emitting layer has been formed is set in a vacuum vapor deposition apparatus, and the inside of the apparatus is exhausted to 2×10 ^-4 Pa or less. Next, the compound represented by the following formula (HB-1) and lithium 8-quinolinolate were co-evaporated at a rate of 1 Å/sec at a film thickness ratio of 2:3 by a vacuum vapor deposition method. On the light-emitting layer, a hole blocking layer with a thickness of 30 nm is formed.

[化26]

[化26]

繼而，作為陰極蒸鍍用的遮罩，將2 mm寬的條紋狀陰影遮罩（shadow mask）以與陽極的ITO條紋正交的方式密接於基板，設置於其他真空蒸鍍裝置內。然後，藉由鉬舟對鋁進行加熱，以蒸鍍速度1 Å/秒～8.6 Å/秒形成膜厚80 nm的鋁層，形成陰極。藉由如上所述般進行操作，得到具有2 mm×2 mm的尺寸的發光面積部分的有機電場發光元件。當對所得到的有機電場發光元件施加電壓時，觀測到源自式（D-1）所表示的化合物的紅色發光。Then, as a mask for cathode vapor deposition, a 2 mm wide striped shadow mask was closely attached to the substrate so as to be orthogonal to the ITO stripes of the anode, and set in another vacuum vapor deposition apparatus. Then, the aluminum is heated by the molybdenum boat to form an aluminum layer with a thickness of 80 nm at a deposition rate of 1 Å/sec to 8.6 Å/sec to form a cathode. By performing the operation as described above, an organic electroluminescent element having a light-emitting area portion having a size of 2 mm×2 mm was obtained. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-1) was observed.

[實施例2] 除了將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-1）：（D-3）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。以下示出式（D-3）所表示的化合物的結構式。再者，式（D-3）所表示的化合物是以波長560 nm為最大發光波長的摻雜劑。[Example 2] Except that the composition of the light-emitting layer is set as the mass ratio of the compound represented by each formula (H-1): (H-2): (D-1): (D-3)=60:40:15:15 In the same manner as in Example 1, an organic electroluminescent element was produced. The structural formula of the compound represented by formula (D-3) is shown below. Furthermore, the compound represented by the formula (D-3) is a dopant whose wavelength is 560 nm as the maximum emission wavelength.

[化27]

[化27]

[實施例3] 除了將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-1）：（D-4）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。以下示出式（D-4）所表示的化合物的結構式。再者，式（D-4）所表示的化合物是以波長558 nm為最大發光波長的摻雜劑。[Example 3] Except that the composition of the light-emitting layer is set as the mass ratio of the compound represented by each formula (H-1): (H-2): (D-1): (D-4)=60:40:15:15 In the same manner as in Example 1, an organic electroluminescent element was produced. The structural formula of the compound represented by formula (D-4) is shown below. Furthermore, the compound represented by formula (D-4) is a dopant whose wavelength is 558 nm as the maximum emission wavelength.

[化28]

[化28]

[比較例1] 除了使用式（D-5）所表示的化合物作為紅色發光摻雜劑，並將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-5）：（D-2）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。以下示出式（D-5）所表示的化合物的結構式。當對所得到的有機電場發光元件施加電壓時，觀測到源自式（D-5）所表示的化合物的紅色發光。[Comparative Example 1] In addition to using the compound represented by the formula (D-5) as the red light-emitting dopant, the composition of the light-emitting layer is set to the mass ratio of the compound represented by each formula (H-1): (H-2): ( D-5): Except for (D-2)=60:40:15:15, an organic electroluminescent element was produced in the same manner as in Example 1. The structural formula of the compound represented by formula (D-5) is shown below. When a voltage was applied to the obtained organic electroluminescent element, red light emission derived from the compound represented by formula (D-5) was observed.

[化29]

[化29]

[比較例2] 除了使用式（D-5）所表示的化合物作為紅色發光摻雜劑，並將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-5）：（D-3）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。當對所得到的有機電場發光元件施加電壓時，觀測到源自式（D-5）所表示的化合物的紅色發光。[Comparative Example 2] In addition to using the compound represented by the formula (D-5) as the red light-emitting dopant, the composition of the light-emitting layer is set to the mass ratio of the compound represented by each formula (H-1): (H-2): ( D-5): Except for (D-3)=60:40:15:15, an organic electroluminescent element was produced in the same manner as in Example 1. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-5) was observed.

[比較例3] 除了使用式（D-5）所表示的化合物作為紅色發光摻雜劑，並將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-5）：（D-4）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。當對所得到的有機電場發光元件施加電壓時，觀測到源自式（D-5）所表示的化合物的紅色發光。[Comparative Example 3] In addition to using the compound represented by the formula (D-5) as the red light-emitting dopant, the composition of the light-emitting layer is set to the mass ratio of the compound represented by each formula (H-1): (H-2): ( D-5): Except for (D-4)=60:40:15:15, an organic electroluminescent element was produced in the same manner as in Example 1. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-5) was observed.

[元件的評價] 對於所得到的實施例1～實施例3及比較例1～比較例3的有機電場發光元件，測定以亮度1000 cd/m² 發光時的電流發光效率（cd/A）及外部量子效率EQE（%）。分別算出將比較例n（n為1～3）的電流發光效率設為1時的、實施例n（n為1～3）的電流發光效率之比，並作為相對發光效率而記載於表1。另外，將自實施例n（n為1～3）的EQE分別減去比較例n（n為1～3）的EQE而得到的△EQE=EQE（實施例n）-EQE（比較例n）的值一併記載於下述的表1。如表1的結果所示，可知：本實施形態的將式（D-1）所表示的化合物作為發光摻雜劑而用於發光層材料的有機電場發光元件與使用式（D-5）所表示的化合物的有機電場發光元件相比，效率提高，而與成為輔助摻雜劑的化合物的結構無關。[Evaluation of the device] For the obtained organic electroluminescent devices of Examples 1 to 3 and Comparative Examples 1 to 3, the current luminous efficiency (cd/A) and the current luminous efficiency (cd/A) when emitting light at a ^{luminance of 1000 cd/m 2 were measured} External quantum efficiency EQE (%). The ratio of the current luminous efficiency of Example n (n is 1 to 3) when the current luminous efficiency of Comparative Example n (n is 1 to 3) is calculated as 1, and is described in Table 1 as the relative luminous efficiency . In addition, ΔEQE = EQE (Example n)-EQE (Comparative Example n) obtained by subtracting the EQE of Comparative Example n (n is 1 to 3) from the EQE of Example n (n is 1 to 3). The values of is also described in Table 1 below. As shown in the results in Table 1, it can be seen that the compound represented by formula (D-1) in this embodiment is used as a light-emitting dopant for the light-emitting layer material of the organic electroluminescent element and the formula (D-5) is used. Compared with the organic electroluminescence element of the compound shown, the efficiency is improved regardless of the structure of the compound serving as the auxiliary dopant.

[表1] 發光摻雜劑輔助摻雜劑相對發光效率 ⊿EQE 實施例1 D-1 D-2 2.7 +2.6 比較例1 D-5 D-2 1 - 實施例2 D-1 D-3 2.7 +2.0 比較例2 D-5 D-3 1 - 實施例3 D-1 D-4 2.6 +2.4 比較例3 D-5 D-4 1 - [Table 1] Luminescent dopant Auxiliary dopant Relative luminous efficiency ⊿EQE Example 1 D-1 D-2 2.7 +2.6 Comparative example 1 D-5 D-2 1 - Example 2 D-1 D-3 2.7 +2.0 Comparative example 2 D-5 D-3 1 - Example 3 D-1 D-4 2.6 +2.4 Comparative example 3 D-5 D-4 1 -

[比較例4] 除了不使用成為輔助摻雜劑的式（D-2）所表示的化合物，並將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-1）=60：40：15以外，與實施例1同樣地製作有機電場發光元件。當對所獲得的有機電場發光元件施加電壓時，觀測到源自式（D-1）所表示的化合物的紅色發光。[Comparative Example 4] Except that the compound represented by the formula (D-2) which becomes the auxiliary dopant is not used, the composition of the light-emitting layer is set to the mass ratio of the compound represented by each formula (H-1): (H-2): Except for (D-1)=60:40:15, an organic electroluminescent element was produced in the same manner as in Example 1. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-1) was observed.

[比較例5] 除了使用式（D-5）所表示的化合物作為紅色發光摻雜劑，而不使用成為輔助摻雜劑的式（D-2）所表示的化合物，並將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-5）=60：40：15以外，與實施例1同樣地製作有機電場發光元件。當對所獲得的有機電場發光元件施加電壓時，觀測到源自式（D-5）表示的化合物的紅色發光。[Comparative Example 5] Except for using the compound represented by the formula (D-5) as the red light-emitting dopant, the compound represented by the formula (D-2) which becomes the auxiliary dopant is not used, and the composition of the light-emitting layer is set to the formula Except that the mass ratio of the compound shown is (H-1): (H-2): (D-5)=60:40:15, an organic electroluminescent element was produced in the same manner as in Example 1. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-5) was observed.

[元件的評價] 對於所得到的實施例1、比較例1、比較例4及比較例5的有機電場發光元件，測定以亮度1000 cd/m² 發光時的外部量子效率EQE。相對於不含成為輔助摻雜劑的化合物的有機電場發光元件（比較例4或比較例5）的EQE，將包含成為輔助摻雜劑的化合物的有機電場發光元件（實施例1或比較例1）的EQE的變化幅度設為△EQE，記載於下述表2或表3。如表2及表3的結果所示，可知：本實施形態的將式（D-1）所表示的化合物作為發光摻雜劑而用於發光層材料的有機電場發光元件（實施例1）與使用式（D-5）所表示的化合物的有機電場發光元件（比較例1）相比，添加了成為輔助摻雜劑的化合物時的外部量子效率的變化幅度大。[Evaluation of Element] For the obtained organic electroluminescent elements of Example 1, Comparative Example 1, Comparative Example 4, and Comparative Example 5, the external quantum efficiency EQE when emitting light at a ^{luminance of 1000 cd/m 2 was measured.} Compared with the EQE of the organic electroluminescence element (Comparative Example 4 or Comparative Example 5) that does not contain the compound that becomes the auxiliary dopant, the organic electroluminescence element (Example 1 or Comparative Example 1) that contains the compound that becomes the auxiliary dopant ) The change range of EQE is △EQE, which is described in Table 2 or Table 3 below. As shown in the results of Table 2 and Table 3, it can be seen that the organic electroluminescent element (Example 1) of the present embodiment using the compound represented by formula (D-1) as a light-emitting dopant as a light-emitting layer material (Example 1) and Compared with the organic electroluminescent element (Comparative Example 1) using the compound represented by the formula (D-5), the external quantum efficiency of the device when the compound used as the auxiliary dopant is added has a large change in the external quantum efficiency.

[表2] 發光摻雜劑輔助摻雜劑 ⊿EQE 實施例1 D-1 D-2 +2.3 比較例4 D-1 無 - [Table 2] Luminescent dopant Auxiliary dopant ⊿EQE Example 1 D-1 D-2 +2.3 Comparative example 4 D-1 no -

[表3] 發光摻雜劑輔助摻雜劑 ⊿EQE 比較例1 D-5 D-2 +2.1 比較例5 D-5 無 - [table 3] Luminescent dopant Auxiliary dopant ⊿EQE Comparative example 1 D-5 D-2 +2.1 Comparative example 5 D-5 no -

[實施例4] 除了使用式（D-6）所表示的化合物作為紅色發光摻雜劑，並將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-6）：（D-2）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。再者，式（D-6）所表示的化合物是以波長627 nm為最大發光波長的摻雜劑。當對所獲得的有機電場發光元件施加電壓時，觀測到源自式（D-6）所表示的化合物的紅色發光。[Example 4] In addition to using the compound represented by the formula (D-6) as the red light-emitting dopant, the composition of the light-emitting layer is set as the mass ratio of the compound represented by each formula (H-1): (H-2): ( D-6): Except for (D-2)=60:40:15:15, an organic electroluminescent element was produced in the same manner as in Example 1. In addition, the compound represented by formula (D-6) is a dopant whose wavelength is 627 nm as the maximum emission wavelength. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-6) was observed.

[化30]

[化30]

[實施例5] 除了將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-6）：（D-7）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。再者，式（D-7）所表示的化合物是以波長605 nm為最大發光波長的摻雜劑。當對所獲得的有機電場發光元件施加電壓時，觀測到源自式（D-6）所表示的化合物的紅色發光。[Example 5] Except that the composition of the light-emitting layer is set as the mass ratio of the compound represented by each formula (H-1): (H-2): (D-6): (D-7)=60:40:15:15 In the same manner as in Example 1, an organic electroluminescent element was produced. Furthermore, the compound represented by formula (D-7) is a dopant whose wavelength is 605 nm as the maximum emission wavelength. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-6) was observed.

[化31]

[化31]

[比較例6] 除了將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-6）=60：40：15以外，與實施例1同樣地製作有機電場發光元件。當對所獲得的有機電場發光元件施加電壓時，觀測到源自式（D-6）所表示的化合物的紅色發光。[Comparative Example 6] It was produced in the same manner as in Example 1 except that the composition of the light-emitting layer was set as the mass ratio of the compound represented by each formula (H-1): (H-2): (D-6)=60:40:15 Organic electroluminescent element. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-6) was observed.

[比較例7] 除了將發光層組成設為以各式所表示的化合物的質量比計（H-1）：（H-2）：（D-5）：（D-7）=60：40：15：15以外，與實施例1同樣地製作有機電場發光元件。當對所獲得的有機電場發光元件施加電壓時，觀測到源自式（D-5）所表示的化合物的紅色發光。[Comparative Example 7] Except that the composition of the light-emitting layer is set as the mass ratio of the compound represented by each formula (H-1): (H-2): (D-5): (D-7) = 60:40:15:15 In the same manner as in Example 1, an organic electroluminescent element was produced. When a voltage was applied to the obtained organic electroluminescence element, red light emission derived from the compound represented by formula (D-5) was observed.

[元件的評價] 對於所得到的實施例4、實施例5、比較例6及比較例7的有機電場發光元件，測定以亮度1000 cd/m² 發光時的外部量子效率EQE，將與比較例6的EQE的差記作△EQE。另外，以60 mA/cm² 的電流密度使有機電場發光元件驅動，測定相對發光亮度成為80%的時間LT80，記下將比較例6的LT80設為100時的相對壽命。記載於下述表4。如表4的結果所示般，可知：本實施形態的將式（D-6）所表示的化合物作為發光摻雜劑，並與成為輔助摻雜劑的化合物組合地用於發光層的有機電場發光元件是效率高且驅動壽命亦長的元件。可知：其中，使用式（D-7）所表示的化合物作為成為輔助摻雜劑的化合物的有機電場發光元件是發光效率更高且驅動壽命亦長的元件。[Evaluation of the element] For the obtained organic electroluminescent elements of Example 4, Example 5, Comparative Example 6, and Comparative Example 7, the external quantum efficiency EQE when emitting light at a ^{luminance of 1000 cd/m 2 was measured and compared with the comparative example.} The difference of EQE of 6 is recorded as △EQE. In addition, the organic electroluminescent element was driven at a current density of 60 mA/cm ² , the time LT80 when the relative emission luminance became 80% was measured, and the relative lifetime when the LT80 of Comparative Example 6 was set to 100 was recorded. Recorded in Table 4 below. As shown in the results of Table 4, it can be seen that the compound represented by formula (D-6) in this embodiment is used as a light-emitting dopant in combination with a compound that becomes an auxiliary dopant for the organic electric field of the light-emitting layer The light-emitting element is an element with high efficiency and long driving life. It can be seen that among them, the organic electroluminescent element using the compound represented by formula (D-7) as the compound as the auxiliary dopant is an element with higher luminous efficiency and long driving life.

[表4] 發光摻雜劑輔助摻雜劑 ⊿EQE 相對壽命實施例4 D-6 D-2 +1.7 222 實施例5 D-6 D-7 +2.4 227 比較例6 D-6 無 - 100 比較例7 D-5 D-7 -0.7 166 [Table 4] Luminescent dopant Auxiliary dopant ⊿EQE Relative life Example 4 D-6 D-2 +1.7 222 Example 5 D-6 D-7 +2.4 227 Comparative example 6 D-6 no - 100 Comparative example 7 D-5 D-7 -0.7 166

雖已詳細並且參照特定的實施方式對本發明進行了說明，但對於本領域技術人員顯而易見的是，可在不脫離本發明的精神與範圍的情況下作出各種變更或修正。本申請案基於2019年5月20日提出申請的日本專利申請案（日本專利特願2019-094708），其內容作為參照而被引用至本文。Although the present invention has been described in detail and with reference to specific embodiments, it is obvious to those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2019-094708) filed on May 20, 2019, and the content is incorporated herein by reference.

1:基板 2:陽極 3:電洞注入層 4:電洞傳輸層 5:發光層 6:電洞阻擋層 7:電子傳輸層 8:電子注入層 9:陰極 10:有機電場發光元件1: substrate 2: anode 3: hole injection layer 4: hole transport layer 5: Light-emitting layer 6: Hole barrier 7: Electron transport layer 8: Electron injection layer 9: Cathode 10: Organic electroluminescent element

圖1是示意性表示本發明的有機電場發光元件的結構的一例的剖面圖。FIG. 1 is a cross-sectional view schematically showing an example of the structure of the organic electroluminescent element of the present invention.

1:基板 1: substrate

2:陽極 2: anode

3:電洞注入層 3: hole injection layer

4:電洞傳輸層 4: hole transport layer

5:發光層 5: Light-emitting layer

6:電洞阻擋層 6: Hole barrier

7:電子傳輸層 7: Electron transport layer

8:電子注入層 8: Electron injection layer

9:陰極 9: Cathode

10:有機電場發光元件 10: Organic electroluminescent element

Claims

一種有機電場發光元件用組成物，包含下述式（1）所表示的化合物、最大發光波長相較於所述式（1）所表示的化合物而為短波的下述式（2）所表示的化合物、及溶媒；

[所述式（1）中，R¹ 、R² 分別獨立地為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R¹ 、R² 的情況下，該些可分別相同亦可不同；於存在多個R¹ 的情況下，相鄰的R¹ 可彼此鍵結而形成環； a為0～4的整數，b為0～3的整數； R³ 、R⁴ 分別獨立地為氫原子、氟原子、氯原子、溴原子、碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數2～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～20的（雜）芳基；該些基亦可進而具有取代基；於存在多個R³ 、R⁴ 的情況下，該些可分別相同亦可不同； L¹ 表示有機配位子，m為1～3的整數]

[所述式（2）中，R⁵ 為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁵ 的情況下，該些可相同亦可不同； c為0～4的整數；環A為吡啶環、吡嗪環、嘧啶環、咪唑環、噁唑環、噻唑環、喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環、苯並噻唑環、苯並噁唑環中的任一者；環A可具有取代基，所述取代基為氟原子、氯原子、溴原子、碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數2～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～20的（雜）芳基；另外，鍵結於環A的相鄰的取代基彼此可鍵結而進而形成環；於存在多個環A的情況下，該些可相同亦可不同； L² 表示有機配位子，n為1～3的整數]。A composition for an organic electroluminescent element, comprising a compound represented by the following formula (1), and the maximum emission wavelength is shorter than the compound represented by the formula (1), represented by the following formula (2) Compound, and solvent;

[In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, (Hetero)aryloxy group with 3-20 carbons, alkylsilyl group with 1-20 carbons, arylsilyl group with 6-20 carbons, alkylcarbonyl group with 2-20 carbons, 7-20 carbons Arylcarbonyl group, alkylamino group having 1-20 carbon atoms, arylamino group having 6-20 carbon atoms, or (hetero)aryl group having 3-30 carbon atoms; these groups may further have substituents; When there are a plurality of R ¹ and R ² , these may be the same or different respectively; when there are a plurality of R ¹ , adjacent R ¹ may be bonded to each other to form a ring; a is 0-4 An integer of, b is an integer of 0 to 3; R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbons, and a (hetero) having 7 to 40 carbons. Aralkyl group, alkoxy group having 1 to 20 carbons, (hetero)aryloxy group having 3 to 20 carbons, alkylsilyl group having 1 to 20 carbons, arylsilyl group having 6 to 20 carbons, carbon Alkylcarbonyl with 2-20, arylcarbonyl with 7-20, alkylamino with 2-20, arylamino with 6-20, or (hetero) with 3-20 carbons ) Aryl; these groups may further have substituents; when there are multiple R ³ and R ⁴ , these may be the same or different respectively; L ¹ represents an organic ligand, and m is 1 to 3 Integer]

[In the above formula (2), R ⁵ is an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and an alkyl group having 3 to 20 carbons. (Hetero) aryloxy group, alkylsilyl group with 1-20 carbons, arylsilyl group with 6-20 carbons, alkylcarbonyl group with 2-20 carbons, arylcarbonyl group with 7-20 carbons, carbon Alkylamino groups having 1-20, arylamino groups having 6-20 carbons, or (hetero)aryl groups having 3-30 carbons; these groups may further have substituents; when there are multiple R ⁵ In the case of, these may be the same or different; c is an integer from 0 to 4; ring A is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, a quinoline ring, and an isoquinoline Any of a ring, a quinazoline ring, a quinoxaline ring, an azatriphenylene ring, a carboline ring, a benzothiazole ring, and a benzoxazole ring; ring A may have a substituent, and the substituent Fluorine atom, chlorine atom, bromine atom, C1-C20 alkyl group, C7-40 (hetero)aralkyl group, C1-C20 alkoxy group, C3-C20 (hetero) ) Aryloxy, C1-C20 alkylsilyl group, C6-C20 arylsilyl group, C2-C20 alkylcarbonyl group, C7-20 arylcarbonyl group, C2-C2 ~20 alkylamino groups, 6-20 arylamino groups, or 3-20 (hetero)aryl groups; in addition, adjacent substituents bonded to ring A may be bonded to each other. Furthermore, a ring is formed; when there are a plurality of rings A, these may be the same or different; L ² represents an organic ligand, and n is an integer of 1 to 3].

如請求項1所述的有機電場發光元件用組成物，其中所述式（1）所表示的化合物的組成比於質量份換算中為所述式（2）所表示的化合物的組成比以上。The composition for an organic electroluminescent element according to claim 1, wherein the composition ratio of the compound represented by the formula (1) is greater than or equal to the composition ratio of the compound represented by the formula (2) in terms of parts by mass.

如請求項1或請求項2所述的有機電場發光元件用組成物，其中所述式（1）所表示的化合物為下述式（1-1）所表示的化合物；

[所述式（1-1）中，R¹ 、R² 、a、b、L¹ 、m與所述式（1）中的R¹ 、R² 、a、b、L¹ 、m分別意義相同； R⁶ 、R⁷ 分別獨立地為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁶ 、R⁷ 的情況下，該些可分別相同亦可不同； d、e分別獨立地為0～5的整數]。The composition for an organic electroluminescent element according to claim 1 or 2, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1);

In [the formula ^{^{(1-1) R 1, R 2}} , a, b, L 1, m and (1) the formula R ^{^{1 R 2 a, b, L}} 1 m , respectively, meaning,,,, Same; R ⁶ and R ⁷ are each independently an alkyl group having 1 to 20 carbons, a (hetero)aralkyl group having 7 to 40 carbons, an alkoxy group having 1 to 20 carbons, and a (hetero)aralkyl group having 1 to 20 carbons ( Hetero) aryloxy group, alkylsilyl group having 1-20 carbons, arylsilyl group having 6-20 carbons, alkylcarbonyl group having 2-20 carbons, arylcarbonyl group having 7-20 carbons, carbon number Alkylamino groups having 1-20, arylamino groups having 6-20 carbons, or (hetero)aryl groups having 3-30 carbons; these groups may further have substituents; when there are multiple R ⁶ , in the case of R ^7, the plurality may be the same or different; d, e are independently an integer of 0 to 5].

如請求項1或請求項2所述的有機電場發光元件用組成物，其中所述式（1）所表示的化合物為下述式（1-2）所表示的化合物；

[所述式（1-2）中，R² ～R⁴ 、b、L¹ 、m與所述式（1）中的R² ～R⁴ 、b、L¹ 、m分別意義相同； R¹⁴ ～R¹⁶ 為取代基，於存在多個R¹⁴ ～R¹⁶ 的情況下，該些可分別相同亦可不同； i為0～4的整數]。The composition for an organic electroluminescent device according to claim 1 or 2, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-2);

In [the formula ^{(1-2), R 2 ~ R} 4, b, L 1, m and (1) of the formula R ^{^{2 ~ R 4, b, L}} 1, m are the same meaning; R ¹⁴ ~R ¹⁶ is a substituent, and when there are a plurality of R ¹⁴ to R ¹⁶ , these may be the same or different; i is an integer of 0 to 4].

如請求項3所述的有機電場發光元件用組成物，其中所述式（1-1）所表示的化合物為下述式（1-3）所表示的化合物；

[所述式（1-3）中，R² 、R⁶ 、R⁷ 、b、d、e、L¹ 、m與所述式（1-1）中的R² 、R⁶ 、R⁷ 、b、d、e、L¹ 、m分別意義相同； R¹⁴ ～R¹⁶ 為取代基，於存在多個R¹⁴ ～R¹⁶ 的情況下，該些可分別相同亦可不同； i為0～4的整數]。The composition for an organic electroluminescence element according to claim 3, wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-3);

[In the formula (1-3), R ² , R ⁶ , R ⁷ , b, d, e, L ¹ ^{, m and R 2} , R ⁶ , R ⁷ , and R in the formula (1-1) b, d, e, L ¹ and m respectively have the same meaning; R ¹⁴ to R ¹⁶ are substituents, and when there are multiple R ¹⁴ to R ¹⁶ , these may be the same or different; i is 0 to 4 Integer].

如請求項1至請求項5中任一項所述的有機電場發光元件用組成物，其中所述式（2）所表示的化合物為下述式（2-1）所表示的化合物；

[所述式（2-1）中，環A、L² 、n與所述式（2）中的環A、L² 、n分別意義相同； R⁸ 為碳數1～20的烷基、碳數7～40的（雜）芳烷基、碳數1～20的烷氧基、碳數3～20的（雜）芳氧基、碳數1～20的烷基矽烷基、碳數6～20的芳基矽烷基、碳數2～20的烷基羰基、碳數7～20的芳基羰基、碳數1～20的烷基胺基、碳數6～20的芳基胺基、或碳數3～30的（雜）芳基；該些基亦可進而具有取代基；於存在多個R⁸ 的情況下，該些可相同亦可不同； f為0～5的整數]。The composition for an organic electroluminescent element according to any one of claims 1 to 5, wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1);

[In the formula (2-1), ^{the ring A, L 2} and n have the same meaning as the ^{ring A, L 2} and n in the formula (2) ^{respectively; R 8} is an alkyl group having 1 to 20 carbons, (Hetero)aralkyl with 7-40 carbons, alkoxy with 1-20 carbons, (hetero)aryloxy with 3-20 carbons, alkylsilyl with 1-20 carbons, 6 carbons ~20 arylsilyl group, C2-20 alkylcarbonyl group, C7-20 arylcarbonyl group, C1-20 alkylamino group, C6-20 arylamino group, Or a (hetero)aryl group having 3 to 30 carbons; these groups may further have substituents; when there are a plurality of R ⁸ , these may be the same or different; f is an integer of 0 to 5].

如請求項1至請求項6中任一項所述的有機電場發光元件用組成物，其中所述式（1）中的m不足3，L¹ 具有選自由下述式（3）、式（4）及式（5）所組成的群組中的至少一種結構；

[所述式（3）～式（5）中，R⁹ 、R¹⁰ 與所述式（1）中的R¹ 意義相同，於存在多個R⁹ 、R¹⁰ 的情況下，該些可分別相同亦可不同； R¹¹ ～R¹³ 分別獨立地為氫原子、可經氟原子取代的碳數1～20的烷基、可經碳數1～20的烷基取代的苯基、或鹵素原子； g為0～4的整數；h為0～4的整數；環B為吡啶環、嘧啶環、咪唑環、喹啉環、異喹啉環、喹唑啉環、喹噁啉環、氮雜三伸苯環、咔啉環、苯並噻唑環或苯並噁唑環；環B亦可進而具有取代基]。The composition for an organic electroluminescent element according to any one of claims 1 to 6, wherein m in the formula (1) is less than 3, and L ¹ is selected from the following formulas (3) and ( 4) At least one structure in the group formed by formula (5);

[In the formulas (3) to (5), R ⁹ and R ¹⁰ have the same meaning as ^{R 1} in the formula (1). When ^{there are multiple R 9} and R ¹⁰ , these can be separated The same or different; R ¹¹ to R ¹³ are each independently a hydrogen atom, a C 1-20 alkyl group which may be substituted with a fluorine atom, a phenyl group which may be substituted with a C 1-20 alkyl group, or a halogen atom ; G is an integer from 0 to 4; h is an integer from 0 to 4; ring B is a pyridine ring, pyrimidine ring, imidazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, aza Terpenylene ring, carboline ring, benzothiazole ring or benzoxazole ring; ring B may further have a substituent].

如請求項1至請求項7中任一項所述的有機電場發光元件用組成物，其中所述式（1）中的a為1，或者所述式（1）中的a為2以上的整數且不具有相鄰的R¹ 相互鍵結而成的環。The composition for an organic electroluminescent element according to any one of claims 1 to 7, wherein a in the formula (1) is 1, or a in the formula (1) is 2 or more It is an integer and does not have a ring formed by bonding ^{adjacent R 1 to each other.}

一種有機電場發光元件的製造方法，包括使用如請求項1至請求項8中任一項所述的有機電場發光元件用組成物並藉由濕式成膜法來形成發光層的步驟。A method for manufacturing an organic electroluminescent element includes the step of using the composition for an organic electroluminescent element according to any one of claims 1 to 8 and forming a light-emitting layer by a wet film forming method.

一種有機電場發光元件，具有使用如請求項1至請求項8中任一項所述的有機電場發光元件用組成物而形成的發光層。An organic electroluminescence element having a light-emitting layer formed using the composition for an organic electroluminescence element according to any one of claims 1 to 8.

一種顯示裝置，具有如請求項10所述的有機電場發光元件。A display device having the organic electroluminescence element according to claim 10.