TW201341359A - Benzofluorene compound, material for lumious layer using the compound, organic electroluminescence element, display device and illuminating device - Google Patents

Benzofluorene compound, material for lumious layer using the compound, organic electroluminescence element, display device and illuminating device Download PDF

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TW201341359A
TW201341359A TW101138465A TW101138465A TW201341359A TW 201341359 A TW201341359 A TW 201341359A TW 101138465 A TW101138465 A TW 101138465A TW 101138465 A TW101138465 A TW 101138465A TW 201341359 A TW201341359 A TW 201341359A
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Yohei Ono
Kazushi Shiren
Akiko Kageyama
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Jnc Corp
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Abstract

The invention provides a benzofluorene compound such as one that is applied to an organic electroluminescence element for brining out excellent properties of the organic electroluminescence element. As a material for a luminous layer of the organic electroluminescence element, the benzofluorene compound is used to form an element having excellent color purity and prolong an operating life, wherein a condensed benzene ring is substituted by a diphenylamino group and a carbazolyl group on a five-membered ring.

Description

苯并茀化合物、使用該化合物的發光層用材料以及有機電場發光元件 Benzofluorene compound, material for light-emitting layer using the same, and organic electroluminescent element

本發明是有關於一種苯并茀化合物、使用該化合物的發光層用材料以及有機電場發光元件。 The present invention relates to a benzofluorene compound, a material for a light-emitting layer using the compound, and an organic electroluminescent device.

有機電場發光元件是自發光型的發光元件，其作為顯示用或照明用的發光元件而受到期待。先前，使用進行電場發光的發光元件的顯示裝置因可實現省電力化或薄型化而得到各種研究，進而，包含有機材料的有機電場發光元件因易於輕量化或大型化而得到積極研究。尤其，關於具有以作為光的三原色之一的藍色為首的發光特性的有機材料的開發，及具備電洞、電子等的電荷傳輸能力(有可能成為半導體或超導體)的有機材料的開發，迄今為止，不論高分子化合物、低分子化合物均得到積極研究。 The organic electroluminescence element is a self-luminous type of light-emitting element, and is expected as a light-emitting element for display or illumination. Conventionally, a display device using a light-emitting element that emits electric field has been subjected to various studies for saving power and thinning, and further, an organic electric field light-emitting element including an organic material has been actively studied because of its ease of weight reduction and enlargement. In particular, the development of organic materials having light-emitting characteristics including blue, which is one of the three primary colors of light, and the development of organic materials having charge transporting ability (possible as a semiconductor or a superconductor) such as holes and electrons have hitherto been Up to now, both polymer compounds and low molecular compounds have been actively studied.

有機電場發光元件具有如下的構造，該構造包括：包含陽極及陰極的一對電極，及配置於該一對電極間、且包含有機化合物的一層或多層。於包含有機化合物的層中，有發光層，或者傳輸或注入電洞、電子等電荷的電荷傳輸/注入層，作為該有機化合物，已開發有各種有機材料(例如，參照國際公開第2004/061047號手冊、國際公開第2004/061048號手冊(日本專利特表2006-512395號公報)、國際公開第2005/056633號手冊：專利文獻1、專利文獻2及專利文獻3)。 The organic electroluminescent device has a structure including a pair of electrodes including an anode and a cathode, and one or more layers disposed between the pair of electrodes and containing an organic compound. In the layer containing an organic compound, there is a light-emitting layer, or a charge transport/injection layer that transports or injects a charge such as a hole or an electron. As the organic compound, various organic materials have been developed (for example, refer to International Publication No. 2004/061047 No. 2004/061048 (Japanese Patent Publication No. 2006-512395), and International Publication No. 2005/056633: Patent Document 1, Patent Document 2, and Patent Document 3).

但是，於該些專利文獻的實例中，僅揭示有苯并茀的 高分子化合物。另外，例如於國際公開第2003/051092號手冊(日本專利特表2005-513713號公報)中，揭示有具有芳基取代胺基的二苯并茀化合物(參照專利文獻4)。但是，於該文獻中僅揭示有其結構式，未報告其具體的特性。 However, in the examples of these patent documents, only benzopyrene is disclosed. Polymer compound. In addition, a dibenzofluorene compound having an aryl-substituted amine group (see Patent Document 4) is disclosed in, for example, Japanese Laid-Open Patent Publication No. 2005-513713. However, only the structural formula is disclosed in this document, and its specific characteristics are not reported.

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

[專利文獻1]國際公開第2004/061047號手冊 [Patent Document 1] International Publication No. 2004/061047

[專利文獻2]國際公開第2004/061048號手冊(日本專利特表2006-512395號公報) [Patent Document 2] International Publication No. 2004/061048 (Japanese Patent Laid-Open Publication No. 2006-512395)

[專利文獻3]國際公開第2005/056633號手冊 [Patent Document 3] International Publication No. 2005/056633

[專利文獻4]國際公開第2003/051092號手冊(日本專利特表2005-513713號公報) [Patent Document 4] International Publication No. 2003/051092 (Japanese Patent Laid-Open Publication No. 2005-513713)

但是，即便使用上述有機材料，仍未獲得於元件壽命等方面具有充分的性能的有機電場發光元件。進而，為了提昇美國國家電視系統委員會(National Television System Committee，NTSC)比，而需要可獲得色純度更高的藍色發光的構成的材料。於此種狀況下，期望開發一種於元件壽命或色純度等方面性能更佳的有機電場發光元件，即，期望開發一種可獲得該元件的化合物。 However, even if the above organic material is used, an organic electroluminescent element having sufficient performance in terms of element life and the like is not obtained. Further, in order to increase the ratio of the National Television System Committee (NTSC), it is necessary to obtain a material having a blue color luminescence with higher color purity. Under such circumstances, it is desired to develop an organic electroluminescent element having better performance in terms of element life or color purity, etc., that is, it is desired to develop a compound which can obtain the element.

本發明者為了解決上述課題而努力研究的結果，發現了由下述通式(1)所表示的苯并茀化合物，進而發現了由下述通式(1'-1)或下述通式(1'-2)所表示的苯并茀化合物，並成功地製造出上述苯并茀化合物。另外，發現藉由 將含有該苯并茀化合物的層配置於一對電極間來構成有機電場發光元件，可獲得於元件壽命等方面得到改善的有機電場發光元件，從而完成了本發明。即，本發明提供如下的苯并茀化合物。 As a result of intensive studies to solve the above problems, the present inventors have found that a benzofluorene compound represented by the following formula (1) has been found to have a general formula (1'-1) or a general formula The benzofluorene compound represented by (1'-2), and the above-described benzofluorene compound was successfully produced. In addition, it was discovered by The organic electroluminescent device is formed by disposing a layer containing the benzofluorene compound between a pair of electrodes, and an organic electroluminescence device having improved life of the device and the like can be obtained, and the present invention has been completed. That is, the present invention provides the following benzofluorene compound.

[1]一種苯并茀化合物，其由下述通式(1)表示。 [1] A benzofluorene compound represented by the following formula (1).

式中，R分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、可由碳數為1~4的烷基取代的碳數為6~24的芳基、或可由碳數為1~4的烷基取代的碳數為5~24的雜芳基，A及B的任一者為9-咔唑基，另一者為二芳基胺基，9-咔唑基及二芳基胺基的芳基分別獨立，可由選自由碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、及由碳數為1~4的烷基取代的矽烷基所組成的組群中的至少1種基取代，當2個以上的基鄰接並進行取代時，該些可鍵結而形成脂肪族環或苯環，且由式(1)所表示的化合物中的至少1個氫可由重氫取代。 In the formula, R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 24 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms, Or a heteroaryl group having a carbon number of 5 to 24 substituted with an alkyl group having 1 to 4 carbon atoms, and any of A and B is a 9-carbazolyl group, and the other is a diarylamine group, 9- The aryl group of the carbazolyl group and the diarylamino group are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and At least one group in the group consisting of an alkyl group substituted with an alkyl group having 1 to 4 carbon atoms is substituted, and when two or more groups are adjacent to each other and substituted, the groups may bond to form an aliphatic ring or A benzene ring, and at least one hydrogen in the compound represented by the formula (1) may be substituted with a heavy hydrogen.

[2]如上述[1]所述之苯并茀化合物，其由下述式(1-1)表示。 [2] The benzofluorene compound according to the above [1], which is represented by the following formula (1-1).

式中，R分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、或可由碳數為1~4的烷基取代的碳數為6~12的芳基，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 In the formula, R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms. R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The alkyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, and n is independently An integer of 0 to 5, when two or more R 1 are adjacent to each other and substituted on one benzene ring, these may be bonded to form a cyclohexane ring or a benzene ring.

[3]如上述[1]所述之苯并茀化合物，其由下述式(1-2)表示。 [3] The benzofluorene compound according to the above [1], which is represented by the following formula (1-2).

式中，R分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、或可由碳數為1~4的烷基取代的碳數為6~12的芳基， R1分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 In the formula, R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms. , R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms; The alkyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, and n is independently An integer of 0 to 5, when two or more R 1 are adjacent to each other and substituted on one benzene ring, these may be bonded to form a cyclohexane ring or a benzene ring.

[4]如上述[2]或[3]所述之苯并茀化合物，其中R分別獨立為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、環己基、苯基或萘基，R1分別獨立為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、環己基、苯基、萘基、三甲基矽烷基、三乙基矽烷基或二甲基單第三丁基矽烷基，且m分別獨立為0~2的整數，n分別獨立為0~2的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成苯環。 [4] The benzofluorene compound according to the above [2] or [3] wherein R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and third. Butyl, cyclohexyl, phenyl or naphthyl, R 1 each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl, cyclohexyl, phenyl , naphthyl, trimethyldecyl, triethyldecyl or dimethyl mono-tert-butylalkyl, and m is independently an integer of 0 to 2, and n is independently an integer of 0 to 2, when 2 When more than one R 1 is adjacent to and substituted on one benzene ring, the bonds may be bonded to form a benzene ring.

[5]如上述[2]或[3]所述之苯并茀化合物，其中R分別獨立為甲基、乙基、異丙基、第二丁基、第三丁基、或苯基，R1分別獨立為甲基、乙基、異丙基、第三丁基、環己 基、苯基或三甲基矽烷基，m及n分別獨立為0~2的整數。 [5] The benzofluorene compound according to the above [2] or [3] wherein R is independently methyl, ethyl, isopropyl, t-butyl, t-butyl or phenyl, R 1 is independently methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl or trimethyldecyl, and m and n are each independently an integer of 0-2.

[6]如上述[1]所述之苯并茀化合物，其由下述式(1-1-24)、式(1-1-54)或式(1-1-84)表示。 [6] The benzofluorene compound according to the above [1], which is represented by the following formula (1-1-24), formula (1-1-54) or formula (1-1-84).

[7]如上述[1]所述之苯并茀化合物，其由下述式(1-1-1)、式(1-1-10)、式(1-1-70)、式(1-1-101)、式(1-1-113)、式(1-2-24)、式(1-2-84)或式(1-2-85)表示。 [7] The benzofluorene compound according to the above [1], which is represented by the following formula (1-1-1), formula (1-1-10), formula (1-1-70), and formula (1) -1-101), formula (1-1-113), formula (1-2-24), formula (1-2-84) or formula (1-2-85).

[8]如上述[1]所述之苯并茀化合物，其由下述式(1-1-140)、式(1-2-121)或式(1-2-174)表示。 [8] The benzofluorene compound according to the above [1], which is represented by the following formula (1-1-140), formula (1-2-121) or formula (1-2-174).

[9]如上述[1]所述之苯并茀化合物，其由下述式(1-1-61)、式(1-1-76)、式(1-1-103)、式(1-1-123)或式(1-1-154)表示。 [9] The benzofluorene compound according to the above [1], which is represented by the following formula (1-1-61), formula (1-1-76), formula (1-1-103), and formula (1) -1-123) or formula (1-1-154).

[10]一種苯并茀化合物，其由下述式(1'-1)表示。 [10] A benzofluorene compound represented by the following formula (1'-1).

式中，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環 烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 In the formula, R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The substituted decyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, respectively. An integer of 0 to 5 is independently independent. When two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring.

[11]一種苯并茀化合物，其由下述式(1'-2)表示。 [11] A benzofluorene compound represented by the following formula (1'-2).

式中，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 In the formula, R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The substituted decyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, respectively. An integer of 0 to 5 is independently independent. When two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring.

[12]如上述[10]或[11]所述之苯并茀化合物，其中R1分別獨立為甲基、乙基、正丙基、異丙基、正丁基、第二 丁基、第三丁基、環己基、苯基、萘基、三甲基矽烷基、三乙基矽烷基或二甲基單第三丁基矽烷基，且m分別獨立為0~2的整數，n分別獨立為0~2的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成苯環。 [12] The benzofluorene compound according to the above [10] or [11] wherein R 1 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or Tributyl, cyclohexyl, phenyl, naphthyl, trimethyldecyl, triethyldecyl or dimethyl mono-tert-butylalkyl, and m is independently an integer from 0 to 2, and n is independently An integer of 0 to 2, when two or more R 1 are adjacent to each other and substituted on one benzene ring, these may be bonded to form a benzene ring.

[13]如上述[10]或[11]所述之苯并茀化合物，其中R1分別獨立為甲基、乙基、異丙基、第三丁基、環己基、苯基或三甲基矽烷基，m及n分別獨立為0~2的整數。 [13] The benzofluorene compound according to the above [10] or [11] wherein R 1 is independently methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl or trimethyl. The alkyl group, m and n are each independently an integer of 0-2.

[14]一種發光層用材料，其是發光元件的發光層用材料，其含有如上述[1]至[13]中任一項所述之苯并茀化合物。 [14] A material for a light-emitting layer, which is a material for a light-emitting layer of a light-emitting element, which contains the benzofluorene compound according to any one of the above [1] to [13].

[15]一種有機電場發光元件，其包括：一對電極，包含陽極及陰極；以及發光層，配置於該一對電極間、且含有如上述[14]所述之發光層用材料。 [15] An organic electroluminescence device comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes and containing the material for a light-emitting layer according to [14] above.

[16]如上述[15]所述之有機電場發光元件，其更包括配置於上述陰極與上述發光層之間的電子傳輸層及/或電子注入層，上述電子傳輸層及上述電子注入層的至少1層含有選自由羥基喹啉系金屬錯合物、吡啶衍生物、啡啉衍生物、硼烷衍生物及苯并咪唑衍生物所組成的組群中的至少1種。 [16] The organic electroluminescence device according to the above [15], further comprising an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, the electron transport layer and the electron injection layer At least one layer contains at least one selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.

[17]如上述[16]所述之有機電場發光元件，其中上述電子傳輸層及/或上述電子注入層進而含有選自由鹼金屬、鹼土金屬、稀土金屬、鹼金屬的氧化物、鹼金屬的鹵化物、鹼土金屬的氧化物、鹼土金屬的鹵化物、稀土金屬 的氧化物、稀土金屬的鹵化物、鹼金屬的有機錯合物、鹼土金屬的有機錯合物及稀土金屬的有機錯合物所組成的組群中的至少1種。 [17] The organic electroluminescence device according to the above [16], wherein the electron transport layer and/or the electron injecting layer further contains an oxide selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal, and an alkali metal. Halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal At least one of the group consisting of an oxide, a rare earth metal halide, an alkali metal organic complex, an alkaline earth metal organic complex, and an organic complex of a rare earth metal.

[18]一種顯示裝置，其包括如上述[15]至[17]中任一項所述之有機電場發光元件。 [18] A display device comprising the organic electroluminescence element according to any one of [15] to [17] above.

[19]一種照明裝置，其包括如上述[15]至[17]中任一項所述之有機電場發光元件。 [19] An illumination device comprising the organic electroluminescence element according to any one of [15] to [17] above.

根據本發明的較佳的形態，可提供一種例如作為發光層用材料具有優異的特性的苯并茀化合物。另外，可提供一種顯示優異的色純度、且元件壽命等特性得到改善的有機電場發光元件。 According to a preferred embodiment of the present invention, for example, a benzofluorene compound having excellent properties as a material for a light-emitting layer can be provided. Further, it is possible to provide an organic electroluminescence device which exhibits excellent color purity and improved characteristics such as device life.

1.由通式(1)所表示的苯并茀化合物 1. A benzofluorene compound represented by the general formula (1)

對本發明的苯并茀化合物進行詳細說明。本發明的苯并茀化合物是由上述通式(1)所表示的苯并茀化合物。再者，由上述通式(1-1)及通式(1-2)所表示的苯并茀化合物是由上述通式(1)所表示的苯并茀化合物的1種形態，各個式中的R彼此相對應，針對式(1)中的9-咔唑基及二芳基胺基的芳基的取代基相當於式(1-1)及式(1-2)中的R1。 The benzofluorene compound of the present invention will be described in detail. The benzofluorene compound of the present invention is a benzofluorene compound represented by the above formula (1). In addition, the benzofluorene compound represented by the above formula (1-1) and the formula (1-2) is one form of the benzofluorene compound represented by the above formula (1), and each of the formulae The R of the formula (1) corresponds to R 1 in the formula (1-1) and the formula (1-2), and the substituent of the aryl group of the 9-carbazolyl group and the diarylamino group in the formula (1).

作為通式(1)的R中的「碳數為1~6的烷基」，可為直鏈及支鏈的任一種(碳數為1~6的直鏈烷基或碳數為3~6的支鏈烷基)。較佳為碳數為1~4的烷基(碳數為3 ~4的支鏈烷基)。 The "alkyl group having 1 to 6 carbon atoms" in R in the general formula (1) may be either a straight chain or a branched chain (a linear alkyl group having 1 to 6 carbon atoms or a carbon number of 3 to 3). a branched alkyl group of 6). Preferred is an alkyl group having a carbon number of 1 to 4 (carbon number 3) ~4 branched alkyl).

作為具體的「烷基」，可列舉：甲基(Me)、乙基(Et)、正丙基、異丙基(i-Pr)、正丁基、異丁基、第二丁基、第三丁基(t-Bu)、正戊基、異戊基、新戊基、第三戊基、正己基、1-甲基戊基、4-甲基-2-戊基、3,3-二甲基丁基、2-乙基丁基等。 Specific examples of the "alkyl group" include methyl (Me), ethyl (Et), n-propyl, isopropyl (i-Pr), n-butyl, isobutyl, second butyl, and Tributyl (t-Bu), n-pentyl, isopentyl, neopentyl, third amyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3- Dimethyl butyl, 2-ethyl butyl and the like.

作為通式(1)的R中的「碳數為3~6的環烷基」，可列舉：環丙基、環丁基、環戊基、環己基、甲基環戊基、或環庚基等。 Examples of the "cycloalkyl group having 3 to 6 carbon atoms" in R in the formula (1) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, or a cycloheptane. Base.

作為通式(1)的R中的「碳數為6~24的芳基」，較佳為碳數為6~16的芳基，更佳為碳數為6~12的芳基。 The "aryl group having 6 to 24 carbon atoms" in R in the general formula (1) is preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms.

作為具體的「芳基」，可列舉：作為單環系芳基的苯基、(鄰,間,對)甲苯基、(2,3-,2,4-,2,5-,2,6-,3,4-,3,5-)二甲苯基、2,4,6-三甲苯基(mesityl)、(鄰,間,對)枯基，作為二環系芳基的(2-,3-,4-)聯苯基，作為縮合二環系芳基的(1-,2-)萘基，作為三環系芳基的聯三苯基(間聯三苯-2'-基、間聯三苯-4'-基、間聯三苯-5'-基、鄰聯三苯-3'-基、鄰聯三苯-4'-基、對聯三苯-2'-基、間聯三苯-2-基、間聯三苯-3-基、間聯三苯-4-基、鄰聯三苯-2-基、鄰聯三苯-3-基、鄰聯三苯-4-基、對聯三苯-2-基、對聯三苯-3-基、對聯三苯-4-基)，作為縮合三環系芳基的苊-(1-,3-,4-,5-)基、茀-(1-,2-,3-,4-,9-)基、萉-(1-,2-)基、(1-,2-,3-,4-,9-)菲基，作為四環系芳基的聯四苯基(5'-苯基-間聯三苯-2-基、5'-苯基-間聯三苯-3-基、5'-苯基-間聯三苯-4-基、間聯四苯)，作為縮合四環系芳基的聯 伸三苯-(1-,2-)基、芘-(1-,2-,4-)基、稠四苯-(1-,2-,5-)基，作為縮合五環系芳基的苝-(1-,2-,3-)基、稠五苯-(1-,2-,5-,6-)基等。 Specific examples of the "aryl group" include a phenyl group as a monocyclic aryl group, (o-, m-, p-tolyl), (2, 3-, 2, 4-, 2, 5-, 2, 6). -, 3,4-,3,5-)dimethylphenyl, 2,4,6-trimethylphenyl (mesityl), (o, m, p) cumyl, as a bicyclic aryl (2-, 3-, 4-) biphenyl, as a (1-, 2-)naphthyl group of a condensed bicyclic aryl group, as a tricyclic aryl group, a triphenyl (m-triphenyl-2'-yl group, Cross-linked triphenyl-4'-yl, m-triphenyl-5'-yl, ortho-triphenyl-3'-yl, ortho-triphenyl-4'-yl, p-triphenyl-2'-yl, inter Biphenyl-2-yl, m-triphenyl-3-yl, m-triphenyl-4-yl, o-triphenyl-2-yl, o-triphenyl-3-yl, o-triphenyl-4 -yl, p-triphenyl-2-yl, p-triphenyl-3-yl, p-triphenyl-4-yl), as a condensed tricyclic aryl 苊-(1-, 3-, 4-, 5- ), 茀-(1-, 2-, 3-, 4-, 9-)yl, 萉-(1-,2-)yl, (1-, 2-, 3-, 4-, 9-) Phenylidene, tetraphenylene (5'-phenyl-m-triphenyl-2-yl, 5'-phenyl-m-triphenyl-3-yl, 5'-phenyl) as a tetracyclic aryl group -inter-triphenyl-4-yl, meta-tetraphenyl), as a condensed tetracyclic aryl group a triphenyl-(1-,2-)yl, fluorenyl-(1-,2-,4-)yl, fused tetraphenyl-(1-,2-,5-)yl group as a condensed pentacyclic aryl group苝-(1-,2-,3-)yl, fused pentabenzene-(1-,2-,5-,6-)yl and the like.

R中的「芳基」可由碳數為1~4的烷基取代，作為此時的取代基，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基，較佳為甲基。取代基的數量例如為最大可取代的數量，較佳為1個~3個，更佳為1個~2個，進而更佳為1個，但較佳為無「取代基」。 The "aryl group" in R may be substituted by an alkyl group having 1 to 4 carbon atoms, and examples of the substituent at this time include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. The second butyl group, the third butyl group, is preferably a methyl group. The number of the substituents is, for example, the maximum substitutable amount, preferably from 1 to 3, more preferably from 1 to 2, still more preferably one, but preferably no "substituent".

作為通式(1)的R中的「碳數為5~24的雜芳基」，較佳為碳數為2~20的雜芳基，更佳為碳數為2~15的雜芳基，特佳為碳數為2~10的雜芳基。另外，作為「雜芳基」，例如可列舉如下的雜環基等，即除碳以外，含有1個至5個選自氧、硫及氮中的雜原子作為環構成原子，例如可列舉芳香族雜環基等。 The "heteroaryl group having 5 to 24 carbon atoms" in R of the formula (1) is preferably a heteroaryl group having 2 to 20 carbon atoms, more preferably a heteroaryl group having 2 to 15 carbon atoms. Particularly preferred is a heteroaryl group having a carbon number of 2 to 10. In addition, examples of the "heteroaryl group" include a heterocyclic group or the like which contains, in addition to carbon, one or five hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen as a ring-constituting atom, and examples thereof include aroma. A heterocyclic group or the like.

作為「雜環基」，例如可列舉吡咯基、噁唑基、異噁唑基、噻唑基、異噻唑基、咪唑基、噁二唑基、噻二唑基、***基、四唑基、吡唑基、吡啶基、嘧啶基、噠嗪基、吡嗪基、三嗪基、吲哚基、異吲哚基、1H-吲唑基、苯并咪唑基、苯并噁唑基、苯并噻唑基、1H-苯并***基、喹啉基、異喹啉基、噌啉基、喹唑啉基、喹噁啉基、呔嗪基、萘啶基、嘌呤基、喋啶基、咔唑基、吖啶基、啡噁嗪基、啡噻嗪基、啡嗪基、吲嗪基等，較佳為咪唑基、吡啶基、咔唑基等。 Examples of the "heterocyclic group" include a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, and a tetrazolyl group. Pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, fluorenyl, isodecyl, 1H-carbazolyl, benzimidazolyl, benzoxazolyl, benzo Thiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolinyl, porphyrinyl, quinazolinyl, quinoxalinyl, pyridazinyl, naphthyridinyl, indolyl, acridinyl, anthracene The azole group, acridinyl group, phenoxazinyl group, phenothiazine group, cyanozinyl group, pyridazinyl group and the like are preferably an imidazolyl group, a pyridyl group or a carbazolyl group.

作為「芳香族雜環基」，例如可列舉呋喃基、噻吩基、 吡咯基、噁唑基、異噁唑基、噻唑基、異噻唑基、咪唑基、吡唑基、噁二唑基、呋吖基、噻二唑基、***基、四唑基、吡啶基、嘧啶基、噠嗪基、吡嗪基、三嗪基、苯并呋喃基、異苯并呋喃基、苯并[b]噻吩基、吲哚基、異吲哚基、1H-吲唑基、苯并咪唑基、苯并噁唑基、苯并噻唑基、1H-苯并***基、喹啉基、異喹啉基、噌啉基、喹唑啉基、喹噁啉基、呔嗪基(phthalazinyl)、萘啶基、嘌呤基、喋啶基、咔唑基、吖啶基、啡噁嗪基、啡噻嗪基、啡嗪基、啡噁噻基、噻嗯基、吲嗪基等，較佳為噻吩基、咪唑基、吡啶基、咔唑基等。 Examples of the "aromatic heterocyclic group" include a furyl group and a thienyl group. Pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl , pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo[b]thienyl, indolyl, isodecyl, 1H-carbazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolinyl, porphyrinyl, quinazolinyl, quinoxalinyl, pyridazinyl (phthalazinyl), naphthyridinyl, fluorenyl, acridinyl, oxazolyl, acridinyl, phenoxazinyl, phenothiazine, cyanoazinyl, morphothionyl, thiophene, pyridazinyl, etc. Preferred are thienyl, imidazolyl, pyridyl, oxazolyl and the like.

通式(1)中的A及B的任一者為9-咔唑基，另一者為二芳基胺基。作為二芳基胺基的芳基，可列舉與上述芳基相同者。9-咔唑基及二芳基胺基的芳基分別獨立，可由選自由碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、及由碳數為1~4的烷基取代的矽烷基所組成的組群中的至少1種基取代，關於該些基中的「烷基」、「環烷基」、「芳基」，可列舉與上述「烷基」、「環烷基」、「芳基」相同者。另外，該些取代基針對9-咔唑基及二芳基胺基的芳基的取代位置並無特別限定，例如當二芳基胺基為二苯基胺基時，若於該苯基的對位(以N的鍵結位置為基準)上存在取代基，則具有可抑制其後的「苯并茀化合物的製造方法」中所說明的流程2及流程3中的鹵化步驟中的副反應的優點。 Any one of A and B in the formula (1) is a 9-carbazolyl group, and the other is a diarylamine group. The aryl group as the diarylamine group may be the same as the above aryl group. The aryl group of the 9-carbazolyl group and the diarylamine group are each independently and may be selected from an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. And at least one group in the group consisting of a decyl group substituted with an alkyl group having 1 to 4 carbon atoms, and "alkyl group", "cycloalkyl group", and "aryl group" in the group. The same as the above-mentioned "alkyl group", "cycloalkyl group", and "aryl group" are mentioned. Further, the positions at which the substituents are substituted for the aryl group of the 9-carbazolyl group and the diarylamine group are not particularly limited, and, for example, when the diarylamino group is a diphenylamino group, When a substituent is present on the alignment (based on the bonding position of N), the side reaction in the halogenation step in Scheme 2 and Scheme 3 described in the "Method for Producing Benzofluorene Compound" which can be suppressed later is suppressed. The advantages.

作為可取代於9-咔唑基及二芳基胺基的芳基上的「由 碳數為1~4的烷基取代的矽烷基」，可列舉矽烷基中的3個氫分別獨立地由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等取代者。 As an aryl group which can be substituted for 9-carbazolyl and diarylamine groups An alkyl-substituted fluorenyl group having 1 to 4 carbon atoms, wherein three hydrogens in the fluorenyl group are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. , third butyl and other substitutions.

作為具體的「取代矽烷基」，可列舉：三甲基矽烷基(Trimethylsilyl，TMS)、三乙基矽烷基、三丙基矽烷基、三異丙基矽烷基、三丁基矽烷基、三第二丁基矽烷基、三第三丁基矽烷基、乙基二甲基矽烷基、丙基二甲基矽烷基、異丙基二甲基矽烷基、丁基二甲基矽烷基、第二丁基二甲基矽烷基、第三丁基二甲基矽烷基、甲基二乙基矽烷基、丙基二乙基矽烷基、異丙基二乙基矽烷基、丁基二乙基矽烷基、第二丁基二乙基矽烷基、第三丁基二乙基矽烷基、甲基二丙基矽烷基、乙基二丙基矽烷基、丁基二丙基矽烷基、第二丁基二丙基矽烷基、第三丁基二丙基矽烷基、甲基二異丙基矽烷基、乙基二異丙基矽烷基、丁基二異丙基矽烷基、第二丁基二異丙基矽烷基、第三丁基二異丙基矽烷基等。 Specific examples of the "substituted decyl group" include trimethylsilyl (TMS), triethyl decyl, tripropyl decyl, triisopropyl decyl, tributyl decyl, and tris. Dibutyl decyl, tri-tert-butyl fluorenyl, ethyl dimethyl decyl, propyl dimethyl decyl, isopropyl dimethyl decyl, butyl dimethyl decyl, second Dimethyl decyl, tert-butyl dimethyl decyl, methyl diethyl decyl, propyl diethyl decyl, isopropyl diethyl decyl, butyl diethyl decyl, Second butyldiethyldecyl, tert-butyldiethyldecyl, methyldipropyldecyl,ethyldipropyldecyl,butyldipropyldecyl,second butyldipropyl Base alkyl, tert-butyldipropyldecyl, methyldiisopropyldecyl, ethyldiisopropyldecyl, butyldiisopropyldecyl, tert-butyldiisopropyldecane Base, tert-butyldiisopropyldecylalkyl, and the like.

另外，關於取代於9-咔唑基及二芳基胺基的芳基上的取代基，當2個以上的基鄰接並進行取代時，該些可鍵結而形成脂肪族環或苯環，作為所形成的脂肪族環，具體而言，可列舉環丁烷、環戊烷、環己烷等。另外，例如當取代於二苯基胺基的苯基上的取代基彼此形成苯環時，在該苯基上形成縮合而成的苯環(即萘基)，可為1-萘基的形態，亦可為2-萘基的形態。 Further, when a substituent on an aryl group substituted with a 9-carbazolyl group and a diarylamine group is adjacent to and substituted, two or more groups may be bonded to each other to form an aliphatic ring or a benzene ring. Specific examples of the aliphatic ring to be formed include cyclobutane, cyclopentane, and cyclohexane. Further, for example, when a substituent on a phenyl group substituted with a diphenylamino group forms a benzene ring, a benzene ring (i.e., a naphthyl group) formed by condensation on the phenyl group may be in the form of a 1-naphthyl group. It can also be in the form of 2-naphthyl.

式(1-1)及式(1-2)中的n分別獨立為0~5的整數， 較佳的n為0~3的整數，更佳的n為0~2的整數，進而更佳的n為0。另外，m分別獨立為0~4的整數，較佳的m為0~2的整數，更佳的m為0~1的整數，進而更佳的m為0。 n in the formula (1-1) and the formula (1-2) is independently an integer of 0 to 5, Preferably, n is an integer from 0 to 3, more preferably n is an integer from 0 to 2, and more preferably n is zero. Further, m is independently an integer of 0 to 4, preferably m is an integer of 0 to 2, more preferably m is an integer of 0 to 1, and more preferably m is 0.

另外，構成由通式(1)所表示的化合物的苯并茀環上的氫原子、取代於苯并環上的R基、9-咔唑基、二芳基胺基、進而針對該些基的取代基中的氫原子的全部或一部分亦可為重氫。 Further, a hydrogen atom on the benzofluorene ring constituting the compound represented by the general formula (1) is substituted with benzo All or a part of the R group, the 9-carbazolyl group, the diarylamine group, and further the hydrogen atom in the substituent of the group may be a heavy hydrogen.

再者，於由式(1)或式(1-1)及式(1-2)所表示的苯并茀化合物中，2個R亦可鍵結而形成茀環。當於式(1-1)或式(1-2)中2個R鍵結而形成茀環時，相當於由上述通式(1'-1)或上述通式(1'-2)所表示的化合物。關於由式(1'-1)或式(1'-2)所表示的化合物中的R1、n及m，可引用式(1)或式(1-1)及式(1-2)中的說明。 Further, in the benzofluorene compound represented by the formula (1) or the formula (1-1) and the formula (1-2), two R groups may be bonded to each other to form an anthracene ring. When two R bonds are bonded in the formula (1-1) or the formula (1-2) to form an anthracene ring, it corresponds to the above formula (1'-1) or the above formula (1'-2). The compound represented. With respect to R 1 , n and m in the compound represented by the formula (1'-1) or the formula (1'-2), the formula (1) or the formula (1-1) and the formula (1-2) can be referred to. In the description.

作為由上述通式(1)所表示的化合物的具體例，例如可列舉由下述式(1-1-1)~式(1-1-120)、下述式(1-1-121)~式(1-1-175)、下述式(1-2-1)~式(1-2-120)、及下述式(1-2-121)~式(1-2-180)所表示的化合物。另外，作為由通式(1'-1)所表示的化合物的具體例，例如可列舉由下述式(1'-1-1)~式(1'-1-15)所表示的化合物，作為由通式(1'-2)所表示的化合物的具體例，例如可列舉由下述式(1'-2-1)~式(1'-2-15)所表示的化合物。 Specific examples of the compound represented by the above formula (1) include, for example, the following formula (1-1-1) to formula (1-1-120) and the following formula (1-1-121). ~Formula (1-1-175), the following formula (1-2-1)~Formula (1-2-120), and the following formula (1-2-121)~Formula (1-2-180) The compound represented. In addition, specific examples of the compound represented by the formula (1'-1) include compounds represented by the following formula (1'-1-1) to formula (1'-1-15). Specific examples of the compound represented by the formula (1'-2) include a compound represented by the following formula (1'-2-1) to the formula (1'-2-15).

由上述式(1-1-1)~式(1-1-120)或上述式(1-2-1)~式(1-2-120)所表示的化合物之中，特佳為式(1-1-1)~式(1-1-3)、式(1-1-7)~式(1-1-11)、式(1-1-16)~式(1-1-33)、式(1-1-37)~式(1-1-41)、式(1-1-46)~式(1-1-63)、式(1-1-67)~式(1-1-71)、式(1-1-76)~式(1-1-90)、式(1-1-91)、式(1-1-93)、式(1-1-95)、式(1-1-97)、式(1-1-99)、式(1-1-101)、式(1-1-103)、式(1-1-105)、式(1-1-107)、式(1-1-109)、式(1-1-111)、式(1-1-113)、式(1-1-115)、式(1-1-117)、式(1-2-1)~式(1-2-3)、式(1-2-7)~式(1-2-11)、式(1-2-16) ~式(1-2-33)、式(1-2-37)~式(1-2-41)、式(1-2-46)~式(1-2-63)、式(1-2-67)~式(1-2-71)、式(1-2-76)~式(1-2-90)、式(1-2-91)、式(1-2-93)、式(1-2-95)、式(1-2-97)、式(1-2-99)、式(1-2-101)、式(1-2-103)、式(1-2-105)、式(1-2-107)、式(1-2-109)、式(1-2-111)、式(1-2-113)、式(1-2-115)、式(1-2-116)、式(1-2-117)及式(1-2-119)。 Among the compounds represented by the above formula (1-1-1) to formula (1-1-120) or the above formula (1-2-1) to formula (1-2-120), a particularly preferred formula ( 1-1-1)~Formula (1-1-3), Formula (1-1-7)~Formula (1-1-11), Formula (1-1-16)~Formula (1-1-33) ), Formula (1-1-37)~Formula (1-1-41), Formula (1-1-46)~Formula (1-1-63), Formula (1-1-67)~Formula (1) -1-71), formula (1-1-76)~form (1-1-90), formula (1-1-91), formula (1-1-93), formula (1-1-95) , formula (1-1-97), formula (1-1-99), formula (1-1-101), formula (1-1-103), formula (1-1-105), formula (1- 1-107), formula (1-1-109), formula (1-1-111), formula (1-1-113), formula (1-1-115), formula (1-1-117), Formula (1-2-1)~Formula (1-2-3), Formula (1-2-7)~Formula (1-2-11), Formula (1-2-16) ~Formula (1-2-33), Formula (1-2-37)~Formula (1-2-41), Formula (1-2-46)~Formula (1-2-63), Formula (1- 2-67)~Formula (1-2-71), Formula (1-2-76)~Formula (1-2-90), Formula (1-2-91), Formula (1-2-93), Formula (1-2-95), Formula (1-2-97), Formula (1-2-99), Formula (1-2-101), Formula (1-2-103), Formula (1-2) -105), Formula (1-2-107), Formula (1-2-109), Formula (1-2-111), Formula (1-2-113), Formula (1-2-115), Formula (1-2-116), formula (1-2-117) and formula (1-2-119).

另外，由上述式(1-1-121)~式(1-1-175)、上述式(1'-1-1)~式(1'-1-15)、上述式(1-2-121)~式(1-2-180)及上述式(1'-2-1)~式(1'-2-15)所表示的化合物之中，特佳為式(1-1-121)~式(1-1-133)、式(1-1-137)~式(1-1-142)、式(1-1-146)、式(1-1-160)、式(1-2-121)~式(1-2-124)、式(1-2-127)~式(1-2-131)、式(1-2-136)~式(1-2-150)、式(1-2-151)~式(1-2-153)、式(1-2-157)~式(1-2-161)及式(1-2-166)~式(1-2-180)。 Further, the above formula (1-1-121) to formula (1-1-175), the above formula (1'-1-1) to formula (1'-1-15), and the above formula (1-2- Among the compounds represented by the formula (1-2-180) and the above formula (1'-2-1) to the formula (1'-2-15), the formula (1-1-121) is particularly preferred. ~Formula (1-1-133), Formula (1-1-137)~Formula (1-1-142), Formula (1-1-146), Formula (1-1-160), Formula (1- 2-121)~(1-2-124), (1-2-127)~(1-2-131), (1-2-136)~(1-2-150), Formula (1-2-151)~Formula (1-2-153), Formula (1-2-157)~Formula (1-2-161) and Formula (1-2-166)~Formula (1-2 -180).

2.苯并茀化合物的製造方法 2. Method for producing benzopyrene compound

由通式(1)所表示的苯并茀化合物可利用布赫瓦爾德-哈特維希(Buchwald-Hartwig)反應、烏爾曼(Ullmaun)反應或芳香族親核取代反應等現有的反應來製造。但是，由通式(1)所表示的化合物是一定取代有1個經取代或未經取代的咔唑基的化合物，且為非對稱的化合物。因此，於製造時，較佳為利用反應性取代基的活性的不同而有選擇地應用反應、或利用精製分離技術等。 The benzofluorene compound represented by the general formula (1) can be subjected to an existing reaction such as a Buchwald-Hartwig reaction, a Ullmaun reaction or an aromatic nucleophilic substitution reaction. Manufacturing. However, the compound represented by the formula (1) is a compound which is substituted with one substituted or unsubstituted carbazolyl group, and is an asymmetric compound. Therefore, at the time of production, it is preferred to selectively apply the reaction or to use a purification separation technique or the like by utilizing the difference in the activity of the reactive substituent.

Buchwald-Hartwig反應是於鹼的存在下，使用鈀觸 媒，對芳香族鹵化物與一級芳香族胺、二級芳香族胺或咔唑進行偶合的方法。藉由該方法來獲得由通式(1)所表示的化合物的反應途徑的具體例如下所述(流程1~流程5)。作為一例，表示鍵結有咔唑基與二苯基胺基的類型，但當設為包含二苯基胺基的二芳基胺基時，亦可藉由相同的方法來合成。 The Buchwald-Hartwig reaction is carried out using palladium in the presence of a base. A method of coupling an aromatic halide to a primary aromatic amine, a secondary aromatic amine or a carbazole. Specific examples of the reaction route for obtaining the compound represented by the general formula (1) by this method are as follows (Scheme 1 to Scheme 5). As an example, a type in which a carbazolyl group and a diphenylamino group are bonded is shown, but when it is a diarylamine group containing a diphenylamino group, it can also synthesize by the same method.

流程1的第一階段所示的反應為鈴木偶合(Suzuki coupling)，以進行反應的2種化合物中的Y基與X1基選擇性地進行反應的方式，使X1基與X2基變成反應活性不同的基。若考慮原料的獲得容易性，則較佳為例如X1基為三氟甲磺酸酯、X2基為氯的化合物。另外，即便將進行反應的2種化合物中的X1基與Y基相互調換，亦可進行反應。於此情況下，使取代於苯甲酸酯上的Y基及X2基的反應活性變成Y基>X2基。進而，於該第一階段的反應中，亦可使用根岸偶合(Negishi coupling)而非鈴木偶合，於此情況下，作為具有Y基的化合物，使用氯化鋅錯合物來代替硼酸或硼酸酯。另外，於該根岸偶合的情況下，與上述同樣地，即便將X1基與Y基相互調換(即，使用苯甲酸酯的氯化鋅錯合物)，亦可進行反應。進而，流程1中，為了於偶合反應後形成五員環，使用事先使-COOR取代於苯環的進行偶合的碳的旁邊的原料，但亦可使用使-COOR取代於萘環的2位(進行偶合的碳的旁邊)上的原料。再者，關於流程1中所說明的芳香族鹵化物的合成方法，例如參考國際公開第2005/056633號手冊。 The reaction shown in the first stage of the scheme 1 is a Suzuki coupling, in which the Y group and the X 1 group in the two compounds in the reaction are selectively reacted, and the X 1 group and the X 2 group are changed. A group having a different reactivity. In view of easiness of obtaining a raw material, for example, a compound in which the X 1 group is a triflate and the X 2 group is chlorine is preferable. Further, the reaction can be carried out even if the X 1 group and the Y group in the two kinds of compounds to be reacted are exchanged with each other. In this case, the reactivity of the Y group and the X 2 group substituted on the benzoate is changed to a Y group>X 2 group. Further, in the first-stage reaction, a Negishi coupling may be used instead of Suzuki coupling, in which case, as a compound having a Y group, a zinc chloride complex is used instead of boric acid or boric acid. ester. Further, in the case of coupling to the root, in the same manner as described above, the reaction can be carried out even if the X 1 group and the Y group are exchanged with each other (that is, a zinc chloride complex of benzoate is used). Further, in the first scheme, in order to form a five-membered ring after the coupling reaction, a raw material in which the -COOR is substituted with the carbon to be coupled to the benzene ring in advance is used, but a 2-position in which -COOR is substituted for the naphthalene ring may be used. The raw material on the side of the coupled carbon is carried out. Further, regarding the method for synthesizing the aromatic halide described in the scheme 1, for example, refer to the International Publication No. 2005/056633.

藉由至流程1的第三階段為止的反應而獲得苯并茀的單鹵素體，可將其用於後述的流程2及流程3。另外，藉由進行至第四階段的鹵化反應為止而獲得苯并茀的二鹵素體，可將其用於後述的流程4及流程5。再者，如上所述X2基(例如氯)的反應活性低，因此根據向X3基中導入反應活性比X2基高的基的理由，作為第四階段中所使用的鹵化劑，較佳為例如溴化劑或碘化劑，更佳為碘化劑。 The monohalogen of benzopyrene is obtained by the reaction up to the third stage of the scheme 1, and can be used in the schemes 2 and 3 described later. Further, by performing the halogenation reaction to the fourth stage, a dihalogen of benzopyrene can be obtained, which can be used in the schemes 4 and 5 described later. Further, since the X 2 group (for example, chlorine) has a low reactivity as described above, the halogenating agent used in the fourth stage is used as a reason for introducing a group having a higher reactivity than the X 2 group into the X 3 group. Preferably, for example, a brominating agent or an iodinating agent, more preferably an iodinating agent.

流程2是由通式(1)所表示的化合物中，使二苯基胺基側的合計2個相當於苯基的部位1個1個地鍵結後，使咔唑基鍵結的方法。另外，流程3是事先合成二苯基胺基，使其鍵結於苯并茀骨架上後，使咔唑基鍵結的方法。於流程2及流程3中，表示先使二苯基胺基鍵結的方法，但亦可先使咔唑基鍵結，然後使二苯基胺基鍵結。 In the compound represented by the formula (1), a method in which a total of two sites corresponding to a phenyl group on the diphenylamine group side is bonded one by one, and then a carbazole group is bonded. Further, Scheme 3 is a method in which a diphenylamine group is synthesized in advance and bonded to a benzofluorene skeleton to bond the carbazole group. In the schemes 2 and 3, a method of bonding a diphenylamine group first is described, but the carbazolyl group may be bonded first, and then the diphenylamine group may be bonded.

流程4及流程5分別為相對於流程2及流程3(以苯并茀的單鹵素體為起點的合成法)，以二鹵素體為起點的情況下的合成法。於該些情況下，亦表示先使二苯基胺基鍵結的方法，但亦可先使咔唑基鍵結，然後使二苯基胺基鍵結。 Scheme 4 and Scheme 5 are synthesis methods in the case of using a dihalogen as a starting point, respectively, with respect to Scheme 2 and Scheme 3 (synthesis method starting from a monohalogen of benzindene). In these cases, it also means a method of bonding a diphenylamine group first, but it is also possible to bond the carbazole group first, and then bond the diphenylamine group.

各流程中的R、R1、m及n分別與通式(1)或式(1-1)及式(1-2)中所使用的R、R1、m及n相對應。 Each process in the R, the R 1, m and n in the general formula (1) or Formula (1-1) and (1-2) used in the R, R 1, m and n, respectively.

以上的反應中所使用的鈀觸媒的具體例為[1,1-雙(二苯基膦基)二茂鐵]二氯化鈀(II)：Pd(dppf)Cl2、四(三苯基膦)鈀(0)：Pd(PPh3)4、雙(三苯基膦)二氯化鈀(II)：PdCl2(PPh3)2、乙酸鈀(II)：Pd(OAc)2、三(二亞苄基丙酮)二鈀(0)：Pd2(dba)3、三(二亞苄基丙酮)二鈀(0)氯仿錯合物：Pd2(dba)3．CHCl3、雙(二亞苄基丙酮)鈀(0)：Pd(dba)2、PdCl2{P(t-Bu)2-(p-NMe2-Ph)}2、雙(三-鄰甲苯基膦)-二氯化 鈀(II)(PdCl2(o-tolyl3)2)等。 A specific example of the palladium catalyst used in the above reaction is [1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloride: Pd(dppf)Cl 2 , tetrakis (triphenyl) Palladium (0): Pd(PPh 3 ) 4 , bis(triphenylphosphine)palladium(II) chloride: PdCl 2 (PPh 3 ) 2 , palladium(II) acetate: Pd(OAc) 2 , Tris(dibenzylideneacetone)dipalladium (0): Pd 2 (dba) 3 , tris(dibenzylideneacetone) dipalladium (0) chloroform complex: Pd 2 (dba) 3 . CHCl 3 , bis(dibenzylideneacetone)palladium(0): Pd(dba) 2 , PdCl 2 {P(t-Bu) 2 -(p-NMe 2 -Ph)} 2 , bis(tri-o-toluene) Palladium (II) (PdCl 2 (o-tolyl 3 ) 2 ) and the like.

為了促進反應，有時亦可向該些鈀化合物中添加膦化合物。該膦化合物的具體例為三(第三丁基)膦、三環己基膦、1-(N,N-二甲胺基甲基)-2-(二第三丁基膦基)二茂鐵、1-(N,N-二丁胺基甲基)-2-(二第三丁基膦基)二茂鐵、1-(甲氧基甲基)-2-(二第三丁基膦基)二茂鐵、1,1'-雙(二第三丁基膦基)二茂鐵、2,2'-雙(二第三丁基膦基)-1,1'-聯萘、2-甲氧基-2'-(二第三丁基膦基)-1,1'-聯萘、1,1'-雙(二苯基膦基)二茂鐵、雙(二苯基膦基)聯萘、4-二甲胺基苯基二第三丁基膦、苯基二第三丁基膦等。 In order to promote the reaction, a phosphine compound may be added to the palladium compounds. Specific examples of the phosphine compound are tris(t-butyl)phosphine, tricyclohexylphosphine, 1-(N,N-dimethylaminomethyl)-2-(di-t-butylphosphino)ferrocene , 1-(N,N-dibutylaminomethyl)-2-(di-t-butylphosphino)ferrocene, 1-(methoxymethyl)-2-(di-t-butylphosphine) Ferrocenyl, 1,1'-bis(di-t-butylphosphino)ferrocene, 2,2'-bis(di-t-butylphosphino)-1,1'-binaphthyl, 2 -Methoxy-2'-(di-t-butylphosphino)-1,1'-binaphthyl, 1,1'-bis(diphenylphosphino)ferrocene, bis(diphenylphosphino) Binary naphthalene, 4-dimethylaminophenyl ditributylphosphine, phenyl ditributylphosphine, and the like.

該反應中所使用的鹼的具體例為碳酸鈉、碳酸鉀、碳酸銫、碳酸氫鈉、氫氧化鈉、氫氧化鉀、氫氧化鋇、乙醇鈉(sodium ethoxide)、第三丁醇鈉、乙酸鈉、磷酸三鉀、氟化鉀等。 Specific examples of the base used in the reaction are sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium butoxide, acetic acid. Sodium, tripotassium phosphate, potassium fluoride, and the like.

進而，該反應中所使用的溶劑的具體例為苯、1,2,4-三甲基苯、甲苯、二甲苯、N,N-二甲基甲醯胺、四氫呋喃、二***、第三丁基甲醚、1,4-二噁烷、甲醇、乙醇、異丙醇等。該些溶劑可對應於進行反應的芳香族鹵化物、三氟甲磺酸酯(triflate)、芳香族硼酸酯及芳香族硼酸的結構而適宜選擇。溶劑可單獨使用，亦可用作混合溶劑。 Further, specific examples of the solvent used in the reaction are benzene, 1,2,4-trimethylbenzene, toluene, xylene, N,N-dimethylformamide, tetrahydrofuran, diethyl ether, and tert-butyl group. Ether, 1,4-dioxane, methanol, ethanol, isopropanol, and the like. These solvents can be suitably selected in accordance with the structure of the aromatic halide, the triflate, the aromatic boronic acid ester, and the aromatic boronic acid which react. The solvent can be used singly or as a mixed solvent.

另外，Ullmann反應是於鹼的存在下，使用銅觸媒，對芳香族鹵化物與一級芳香族胺或二級芳香族胺進行偶合的方法。Ullmann反應中所使用的銅觸媒的具體例為銅粉、氯化銅、溴化銅或碘化銅等。另外，該反應中所使用 的鹼的具體例可選擇與Buchwald-Hartwig反應相同者。進而，Ullmann反應中所使用的溶劑的具體例為硝基苯、二氯苯、N,N-二甲基甲醯胺等。 Further, the Ullmann reaction is a method of coupling an aromatic halide with a primary aromatic amine or a secondary aromatic amine in the presence of a base using a copper catalyst. Specific examples of the copper catalyst used in the Ullmann reaction are copper powder, copper chloride, copper bromide or copper iodide. In addition, used in the reaction Specific examples of the base can be selected in the same manner as the Buchwald-Hartwig reaction. Further, specific examples of the solvent used in the Ullmann reaction are nitrobenzene, dichlorobenzene, N,N-dimethylformamide, and the like.

另外，由通式(1)所表示的化合物亦可利用以下的反應來製造(流程6、流程7)。作為一例，表示鍵結有咔唑基與二苯基胺基的類型，但當設為包含二苯基胺基的二芳基胺基時，亦可藉由相同的方法來合成。再者，流程6及流程7的第一階段所示的反應為鈴木偶合，即便將進行反應的2種化合物中的X基與Y基相互調換，亦可進行反應。進而，於該第一階段的反應中，亦可使用根岸偶合而非鈴木偶合，於此情況下，作為具有Y基的化合物，使用氯化鋅錯合物來代替硼酸或硼酸酯。另外，於該根岸偶合的情況下，與上述同樣地，即便將X基與Y基相互調換，亦可進行反應。再者，各流程中的R、R1、m及n分別與通式(1)或式(1-1)及式(1-2)中所使用的R、R1、m及n相對應。 Further, the compound represented by the formula (1) can also be produced by the following reaction (Scheme 6, Scheme 7). As an example, a type in which a carbazolyl group and a diphenylamino group are bonded is shown, but when it is a diarylamine group containing a diphenylamino group, it can also synthesize by the same method. Further, the reaction shown in the first stage of the schemes 6 and 7 is Suzuki coupling, and the reaction can be carried out even if the X group and the Y group of the two kinds of compounds to be reacted are exchanged. Further, in the first-stage reaction, root-shore coupling instead of Suzuki coupling may be used. In this case, a zinc chloride complex is used as a compound having a Y group instead of boric acid or a boric acid ester. Further, in the case of coupling the roots, the reaction can be carried out even if the X group and the Y group are exchanged with each other in the same manner as described above. Further, each of the processes R, R in R 1, m and n in the general formula (1) or Formula (1-1) and (1-2) used, R 1, m and n corresponding .

另外，本發明的化合物亦包含至少一部分的氫原子由 重氫取代的化合物，此種化合物可藉由使用所期望的部位經重氫化的原料，而與上述同樣地合成。 In addition, the compounds of the invention also contain at least a portion of the hydrogen atoms A compound substituted with a heavy hydrogen, which can be synthesized in the same manner as described above by using a material which is subjected to hydrogenation at a desired site.

另外，關於由式(1)或式(1-1)及式(1-2)所表示的苯并茀化合物中，2個R鍵結而形成茀環的化合物(例如，由式(1'-1)或式(1'-2)所表示的化合物)，可參考例如日本專利特開2009-184933號公報中所記載的具有螺結構的苯并茀化合物的合成方法來合成。於該公報的段落[0055]中記載有以下所引用的合成方法(流程1c)，可藉由如下方式來合成：先選擇反應性彼此不同的取代基作為取代於2個部位上的反應性取代基X，然後利用上述流程4或流程5。 Further, in the benzofluorene compound represented by the formula (1) or the formula (1-1) and the formula (1-2), two compounds in which R is bonded to form an anthracene ring (for example, by the formula (1') -1) or a compound represented by the formula (1'-2) can be synthesized by, for example, a method for synthesizing a benzofluorene compound having a spiro structure as described in JP-A-2009-184933. The synthesis method (Scheme 1c) cited below is described in paragraph [0055] of the publication, and can be synthesized by first selecting substituents different in reactivity from each other as reactive substitutions at two sites. Base X, then utilize Flow 4 or Flow 5 above.

3.有機電場發光元件 3. Organic electric field light-emitting element

本發明的苯并茀化合物例如可用作有機電場發光元件的材料。 The benzofluorene compound of the present invention can be used, for example, as a material of an organic electric field light-emitting element.

基於圖式對該實施形態的有機電場發光元件進行詳細說明。圖1是表示本實施形態的有機電場發光元件的概略剖面圖。 The organic electroluminescent device of this embodiment will be described in detail based on the drawings. Fig. 1 is a schematic cross-sectional view showing an organic electroluminescence device of the embodiment.

<有機電場發光元件的構造> <Configuration of Organic Electric Field Light-Emitting Element>

圖1所示的有機電場發光元件100包括：基板101、設置於基板101上的陽極102、設置於陽極102上的電洞注入層103、設置於電洞注入層103上的電洞傳輸層104、設置於電洞傳輸層104上的發光層105、設置於發光層105上的電子傳輸層106、設置於電子傳輸層106上的電子注入層107、以及設置於電子注入層107上的陰極108。 The organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, and a hole transport layer 104 disposed on the hole injection layer 103. The light emitting layer 105 disposed on the hole transport layer 104, the electron transport layer 106 disposed on the light emitting layer 105, the electron injection layer 107 disposed on the electron transport layer 106, and the cathode 108 disposed on the electron injection layer 107 .

再者，有機電場發光元件100亦可使製作順序相反而形成例如以下的構成，該構成包括：基板101、設置於基板101上的陰極108、設置於陰極108上的電子注入層107、設置於電子注入層107上的電子傳輸層106、設置於電子傳輸層106上的發光層105、設置於發光層105上的電洞傳輸層104、設置於電洞傳輸層104上的電洞注入層103、以及設置於電洞注入層103上的陽極102。 Further, the organic electroluminescent device 100 may have a configuration in which the order of fabrication is reversed to include, for example, a substrate 101, a cathode 108 provided on the substrate 101, an electron injection layer 107 provided on the cathode 108, and An electron transport layer 106 on the electron injection layer 107, a light emitting layer 105 disposed on the electron transport layer 106, a hole transport layer 104 disposed on the light emitting layer 105, and a hole injection layer 103 disposed on the hole transport layer 104. And an anode 102 disposed on the hole injection layer 103.

上述各層並非全部是不可或缺的層，將最小構成單位設為包含陽極102與發光層105及陰極108的構成，電洞注入層103、電洞傳輸層104、電子傳輸層106及電子注入層107是可任意設置的層。另外，上述各層可分別包含單一層，亦可包含多層。 Not all of the above layers are indispensable layers, and the smallest constituent unit is a structure including the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer. 107 is a layer that can be arbitrarily set. In addition, each of the above layers may include a single layer or a plurality of layers.

作為構成有機電場發光元件的層的形態，除上述「基板/陽極/電洞注入層/電洞傳輸層/發光層/電子傳輸層/電子注入層/陰極」的構成形態以外，亦可為「基板/陽極/電洞傳輸層/發光層/電子傳輸層/電子注入層/陰極」、「基板/陽極/電洞注入層/發光層/電子傳輸層/電子注入層/陰極」、「基板/陽極/電洞注入層/電洞傳輸層/發光層/電子注入層/陰極」、「基板/陽極/電洞注入層/電洞傳輸層/發光層/電子傳輸層/陰極」、「基板/陽極/發光層/電子傳輸層/電子注入層/陰極」、「基板/陽極/電洞傳輸層/發光層/電子注入層/陰極」、「基板/陽極/電洞傳輸層/發光層/電子傳輸層/陰極」、「基板/陽極/電洞注入層/發光層/電子注入層/陰極」、「基板/陽極/電洞注入層/發光層/電子傳輸層/陰極」、「基板/陽極/電洞注入層/電洞傳輸層/發光層/陰極」、「基板/陽極/電洞注入層/發光層/陰極」、「基板/陽極/電洞傳輸層/發光層/陰極」、「基板/陽極/發光層/電子傳輸層/陰極」、「基板/陽極/發光層/電子注入層/陰極」、「基板/陽極/發光層/陰極」的構成形態。 The form of the layer constituting the organic electroluminescent device may be other than the configuration of the substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode. Substrate/anode/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole injection layer/light-emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/ Anode/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode”, “substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode”, “substrate/ Anode/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/electron Transport layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", "substrate/anode" / hole injection layer / hole transmission layer / luminescent layer / cathode", "substrate / anode / hole injection / luminescent layer / cathode", "substrate / anode / hole transport layer / luminescent layer / cathode", "substrate / anode / luminescent layer / electron transport layer / cathode", "substrate / anode / luminescent layer / electron injection layer / The configuration of the cathode, the substrate/anode/light-emitting layer/cathode.

<有機電場發光元件中的基板> <Substrate in Organic Electric Field Light-Emitting Element>

基板101是成為有機電場發光元件100的支撐體者，通常使用石英、玻璃、金屬、塑膠等。基板101根據目的而形成為板狀、膜狀或片狀，例如可使用玻璃板、金屬板、金屬箔、塑膠膜或塑膠片等。其中，較佳為玻璃板及聚酯、聚甲基丙烯酸酯、聚碳酸酯、聚碸等的透明的合成樹脂製的板。若為玻璃基板，則可使用鈉鈣玻璃或無鹼玻璃等，另外，厚度亦只要是足以保持機械強度的厚度即可，因此 例如只要有0.2 mm以上即可。厚度的上限值例如為2 mm以下，較佳為1 mm以下。關於玻璃的材質，因來自玻璃的溶出離子越少越好，故較佳為無鹼玻璃，由於施加了SiO2等的隔離塗層的鈉鈣玻璃亦有市售，因此可使用該鈉鈣玻璃。另外，為了提高阻氣性，亦可於基板101的至少一面設置細密的氧化矽膜等阻氣膜，尤其於將阻氣性低的合成樹脂製的板、膜或片用作基板101的情況下，較佳為設置阻氣膜。 The substrate 101 is a support for the organic electroluminescent device 100, and quartz, glass, metal, plastic, or the like is usually used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like can be used. Among them, a glass plate and a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polyfluorene are preferable. In the case of a glass substrate, soda lime glass, alkali-free glass, or the like may be used, and the thickness may be a thickness sufficient to maintain mechanical strength. Therefore, for example, it may be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The material of the glass is preferably an alkali-free glass because the eluted ions from the glass are as small as possible. Since the soda lime glass to which the barrier coating layer of SiO 2 or the like is applied is also commercially available, the soda lime glass can be used. . In addition, in order to improve gas barrier properties, a gas barrier film such as a fine ruthenium oxide film may be provided on at least one surface of the substrate 101, and in particular, a plate, a film or a sheet made of a synthetic resin having low gas barrier properties may be used as the substrate 101. Preferably, a gas barrier film is provided.

<有機電場發光元件中的陽極> <Anode in Organic Electric Field Light-Emitting Element>

陽極102是發揮向發光層105注入電洞的作用者。再者，當在陽極102與發光層105之間設置有電洞注入層103及/或電洞傳輸層104時，經由該些層向發光層105注入電洞。 The anode 102 is a person who exerts a hole in the light-emitting layer 105. Further, when the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through the layers.

作為形成陽極102的材料，可列舉無機化合物及有機化合物。作為無機化合物，例如可列舉：金屬(鋁、金、銀、鎳、鈀、鉻等)、金屬氧化物(銦的氧化物、錫的氧化物、銦-錫氧化物(Indium Tin Oxide，ITO)等)、鹵化金屬(碘化銅等)、硫化銅、碳黑、ITO玻璃或奈塞玻璃等。作為有機化合物，例如可列舉：聚(3-甲基噻吩)等聚噻吩、聚吡咯、聚苯胺等導電性聚合物等。此外，可自用作有機電場發光元件的陽極的物質中適宜選擇來使用。 Examples of the material for forming the anode 102 include an inorganic compound and an organic compound. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.) and metal oxides (indium oxides, tin oxides, and indium tin oxides (ITO)). Etc.), halogenated metal (copper iodide, etc.), copper sulfide, carbon black, ITO glass or nylon glass. Examples of the organic compound include conductive polymers such as polythiophene such as poly(3-methylthiophene), polypyrrole, and polyaniline. Further, it can be suitably selected and used as a material which can be used as an anode of an organic electroluminescence element.

透明電極的電阻只要可對發光元件的發光供給足夠的電流，則並無特別限定，但就發光元件的消耗電力的觀點而言，理想的是低電阻。例如，若為300 Ω/□以下的ITO 基板，則作為元件電極發揮功能，但現在亦可供給10 Ω/□左右的基板，因此特別理想的是使用例如100 Ω/□~5 Ω/□，較佳為50 Ω/□~5 Ω/□的低電阻品。ITO的厚度可配合電阻值而任意地選擇，但通常於100 nm~300 nm之間使用的情況多。 The electric resistance of the transparent electrode is not particularly limited as long as it can supply a sufficient current to the light emission of the light-emitting element. However, from the viewpoint of power consumption of the light-emitting element, it is preferable to have a low electric resistance. For example, if it is 300 Ω/□ or less ITO The substrate functions as an element electrode. However, it is now possible to supply a substrate of about 10 Ω/□. Therefore, it is particularly preferable to use, for example, 100 Ω/□ to 5 Ω/□, preferably 50 Ω/□ to 5 Ω/ □ low resistance products. The thickness of ITO can be arbitrarily selected in accordance with the resistance value, but it is usually used in the range of 100 nm to 300 nm.

<有機電場發光元件中的電洞注入層、電洞傳輸層> <Pore injection layer and hole transport layer in organic electric field light-emitting element>

電洞注入層103是發揮將自陽極102移動而來的電洞高效地注入至發光層105內或電洞傳輸層104內的作用的層。電洞傳輸層104是發揮將自陽極102所注入的電洞、或自陽極102經由電洞注入層103所注入的電洞高效地傳輸至發光層105的作用的層。電洞注入層103及電洞傳輸層104分別將電洞注入．傳輸材料的一種或兩種以上加以積層、混合而形成，或者由電洞注入．傳輸材料與高分子黏結劑的混合物形成。另外，亦可向電洞注入．傳輸材料中添加如氯化鐵(III)般的無機鹽來形成層。 The hole injection layer 103 is a layer that functions to efficiently inject a hole that has moved from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. The hole transport layer 104 functions as a layer that efficiently transports holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 respectively inject holes. One or two or more of the transport materials are formed by lamination, mixing, or injection by a hole. The transport material is formed from a mixture of polymeric binders. Alternatively, it can be injected into the hole. An inorganic salt such as iron (III) chloride is added to the transport material to form a layer.

作為電洞注入．傳輸性物質，必須於已被供給電場的電極間高效地注入．傳輸來自正極的電洞，理想的是電洞注入效率高、且高效地傳輸所注入的電洞。因此，較佳為游離電位小、且電洞移動率大、進而穩定性優異、製造時及使用時不易產生成為陷阱的雜質的物質。 Injected as a hole. The transporting substance must be efficiently injected between the electrodes to which the electric field has been supplied. The hole from the positive electrode is transmitted, and it is desirable that the hole injection efficiency is high and the injected hole is efficiently transmitted. Therefore, it is preferable that the free potential is small, the hole mobility is large, and the stability is excellent, and it is difficult to generate impurities which are traps during production and use.

作為形成電洞注入層103及電洞傳輸層104的材料，可自先前以來在光導電材料中作為電洞的電荷傳輸材料所慣用的化合物，用於p型半導體、有機電場發光元件的電洞注入層及電洞傳輸層的公知的材料中選擇使用任意的材 料。該些材料的具體例為咔唑衍生物(N-苯基咔唑、聚乙烯咔唑等)、雙(N-芳基咔唑)或雙(N-烷基咔唑)等雙咔唑衍生物、三芳胺衍生物(主鏈或側鏈上具有芳香族三級胺基的聚合物、1,1-雙(4-二-對甲苯基胺基苯基)環己烷、N,N'-二苯基-N,N'-二(3-甲基苯基)-4,4'-二胺基聯苯、N,N'-二苯基-N,N'-二萘基-4,4'-二胺基聯苯(以下，略記為NPD)、N,N'-二苯基-N,N'-二(3-甲基苯基)-4,4'-二苯基-1,1'-二胺、N,N'-二萘基-N,N'-二苯基-4,4'-二苯基-1,1'-二胺、4,4',4"-三(3-甲基苯基(苯基)胺基)三苯基胺等三苯基胺衍生物、星爆狀胺衍生物等)、二苯乙烯衍生物、酞菁衍生物(無金屬、銅酞菁等)、吡唑啉衍生物、腙系化合物、苯并呋喃衍生物或噻吩衍生物、噁二唑衍生物、卟啉衍生物等雜環化合物、聚矽烷等。聚合物系中，較佳為側鏈上具有上述單體的聚碳酸酯或苯乙烯衍生物、聚乙烯咔唑及聚矽烷等，但只要是形成發光元件的製作所需的薄膜，可自陽極注入電洞，進而可傳輸電洞的化合物，則並無特別限定。 As a material for forming the hole injection layer 103 and the hole transport layer 104, a compound which is conventionally used as a charge transport material for a hole in a photoconductive material, and a hole for a p-type semiconductor or an organic electric field light-emitting element. Select any material from the well-known materials of the injection layer and the hole transport layer. material. Specific examples of such materials are biscarbazole derivatives such as carbazole derivatives (N-phenylcarbazole, polyvinyl carbazole, etc.), bis(N-arylcarbazole) or bis(N-alkylcarbazole). , triarylamine derivative (polymer having an aromatic tertiary amino group in the main chain or side chain, 1,1-bis(4-di-p-tolylamidophenyl)cyclohexane, N,N' -diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4 , 4'-diaminobiphenyl (hereinafter, abbreviated as NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl- 1,1'-Diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine, 4,4',4" - a triphenylamine derivative such as tris(3-methylphenyl(phenyl)amino)triphenylamine, a starburst amine derivative, etc., a stilbene derivative, a phthalocyanine derivative (no metal , copper phthalocyanine, etc., pyrazoline derivatives, oxime compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, porphyrin derivatives and other heterocyclic compounds, polydecane, etc. Preferably, the polycarbonate or styrene derivative having the above monomer in the side chain, polyvinyl carbazole, polydecane, etc. Forming a thin film as long as required to produce the light emitting element, holes injected from the anode can, in turn, may transmit a compound of holes, it is not particularly limited.

另外，有機半導體的導電性因其摻雜而受到強烈影響這一點亦為人所知。此種有機半導體基質物質包含電子供應性良好的化合物、或電子接受性良好的化合物。為了摻雜電子供應物質，已知有四氰基醌二甲烷(TCNQ)或2,3,5,6-四氟四氰基-1,4-苯醌二甲烷(F4TCNQ)等強電子接受體(例如，參照文獻「M.Pfeiffer,A.Beyer,T.Fritz,K.Leo,《應用物理學快報》(Appl.Phys.Lett.),73(22),3202-3204(1998)」及文獻「J.Blochwitz,M.Pheiffer,T.Fritz,K.Leo, 《應用物理學快報》(Appl.Phys.Lett.),73(6),729-731(1998)」)。該些藉由電子供應型基礎物質(電洞傳輸物質)中的電子移動過程而生成所謂的電洞。基礎物質的傳導性根據電洞的數量及移動率而產生相當大的變化。作為具有電洞傳輸特性的基質物質，已知有例如聯苯胺衍生物(TPD等)或星爆狀胺衍生物(TDATA等)、或者特定的金屬酞菁(特別是鋅酞菁ZnPc等)(日本專利特開2005-167175號公報)。 Further, it is also known that the conductivity of an organic semiconductor is strongly affected by its doping. Such an organic semiconductor host material contains a compound having good electron supply properties or a compound having good electron acceptability. Strong electron acceptors such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinodimethane (F4TCNQ) are known for doping electron supply materials. (For example, the reference "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, "Appl. Phys. Lett.", 73 (22), 3202-3204 (1998)" and The document "J.Blochwitz, M.Pheiffer, T.Fritz, K.Leo, Applied Physics Letters (Appl. Phys. Lett.), 73 (6), 729-731 (1998)"). These so-called holes are generated by electron movement processes in the electron supply type base material (hole transport material). The conductivity of the base material varies considerably depending on the number of holes and the rate of movement. As a matrix substance having a hole transporting property, for example, a benzidine derivative (TPD or the like) or a starburst amine derivative (TDATA or the like), or a specific metal phthalocyanine (particularly zinc phthalocyanine ZnPc or the like) is known ( Japanese Patent Laid-Open Publication No. 2005-167175).

<有機電場發光元件中的發光層> <Light-emitting layer in organic electric field light-emitting element>

發光層105是藉由在已被供給電場的電極間，使自陽極102所注入的電洞與自陰極108所注入的電子再結合而發光的層。作為形成發光層105的材料，只要是由電洞與電子的再結合激發而發光的化合物(發光性化合物)即可，較佳為可形成穩定的薄膜形狀、且於固體狀態下顯示強的發光(螢光及/或磷光)效率的化合物。 The light-emitting layer 105 is a layer that emits light by recombining a hole injected from the anode 102 with electrons injected from the cathode 108 between electrodes that have been supplied with an electric field. The material for forming the light-emitting layer 105 may be a compound (light-emitting compound) which is excited by recombination of a hole and electrons, and preferably has a stable film shape and exhibits strong light emission in a solid state. (fluorescent and/or phosphorescent) efficiency compounds.

發光層可為單一層，亦可包含多層，且分別由發光材料(主體材料、摻雜劑材料)形成，其可為主體材料與摻雜劑材料的混合物，亦可僅為主體材料。即，於發光層的各層中，可僅主體材料或摻雜劑材料發光，亦可主體材料與摻雜劑材料均發光。主體材料與摻雜劑材料分別可為一種，亦可為多種的組合。摻雜劑材料可包含於整個主體材料內，亦可包含於部分主體材料內。摻雜劑的使用量根據摻雜劑而不同，只要配合該摻雜劑的特性來決定即可。摻雜劑的使用量的基準較佳為整個發光材料的0.001 wt%(重 量百分比)~50 wt%，更佳為0.1 wt%~10 wt%，進而更佳為1 wt%~5 wt%。作為摻雜方法，可藉由與主體材料的共蒸鍍法來形成，亦可事先與主體材料混合後同時蒸鍍。 The luminescent layer may be a single layer or a plurality of layers, and is formed of a luminescent material (host material, dopant material), which may be a mixture of the host material and the dopant material, or may be only the host material. That is, in each layer of the light-emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. The host material and the dopant material may be one type or a combination of a plurality of types. The dopant material may be included throughout the host material or may be included in a portion of the host material. The amount of the dopant used varies depending on the dopant, and may be determined by blending the characteristics of the dopant. The reference amount of the dopant used is preferably 0.001 wt% of the entire luminescent material (weight The percentage of the amount is ~50 wt%, more preferably 0.1 wt% to 10 wt%, and even more preferably 1 wt% to 5 wt%. The doping method may be formed by a co-evaporation method with a host material, or may be simultaneously vapor-deposited after being mixed with a host material.

作為主體材料，並無特別限定，可適宜使用自先前以來作為發光體而為人所知的蒽或芘等縮合環衍生物、以三(8-羥基喹啉)鋁為首的金屬螯合化類咢辛化合物(metal chelated oxinoid compounds)、雙苯乙烯基蒽衍生物或二苯乙烯基苯衍生物等雙苯乙烯基衍生物、四苯基丁二烯衍生物、香豆素衍生物、噁二唑衍生物、吡咯并吡啶衍生物、紫環酮衍生物、環戊二烯衍生物、噻二唑并吡啶衍生物、吡咯并吡咯衍生物，於聚合物系中，可適宜使用聚苯乙炔(polyphenylene vinylene)衍生物、聚對苯衍生物、以及聚噻吩衍生物。 The host material is not particularly limited, and a condensed ring derivative such as ruthenium or osmium which has been known as an illuminant from the prior art, and a metal chelate compound such as tris(8-hydroxyquinoline)aluminum can be suitably used. a bisstyryl derivative such as a metal chelated oxinoid compound, a bisstyrylhydrazine derivative or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a coumarin derivative, or a dioxin An azole derivative, a pyrrolopyridinium derivative, a benzalkonone derivative, a cyclopentadiene derivative, a thiadiazole pyridine derivative, a pyrrolopyrrole derivative, and a polyphenylacetylene can be suitably used in the polymer system ( Polyphenylene vinylene) derivatives, polyparaphenylene derivatives, and polythiophene derivatives.

此外，作為主體材料，可自化學工業2004年6月號第13頁、及其中所列舉的參考文獻等中所記載的化合物等中適宜選擇來使用。 In addition, as the host material, it can be suitably selected and used from the compounds described in the Chemical Industry No. 13 of June 2004, and the references cited therein.

主體材料的使用量較佳為發光材料整體的50 wt%~99.999 wt%、更佳為80 wt%~99.95 wt%、進而更佳為90 wt%~99.9 wt%。 The amount of the host material used is preferably from 50% by weight to 99.999% by weight, more preferably from 80% by weight to 99.95% by weight, even more preferably from 90% by weight to 99.9% by weight.

另外，作為摻雜劑材料，可使用上述通式(1)的苯并茀化合物，尤其，較佳為使用由上述式(1-1)或上述式(1-2)所表示的化合物，更佳為使用由上述式(1-1-1)~式(1-1-120)、上述式(1-1-121)~式(1-1-175)、上述式(1-2-1)~式(1-2-120)及上述式(1-2-121)~式(1-2-180) 所表示的化合物。另外，亦可使用由通式(1'-1)或通式(1'-2)所表示的苯并茀化合物。該些苯并茀化合物作為摻雜劑材料的使用量較佳為發光材料整體的0.001 wt%~50 wt%、更佳為0.05 wt%~20 wt%、進而更佳為0.1 wt%~10 wt%。作為摻雜方法，可藉由與主體材料的共蒸鍍法來形成，亦可事先與主體材料混合後同時蒸鍍。 Further, as the dopant material, a benzofluorene compound of the above formula (1) can be used, and in particular, a compound represented by the above formula (1-1) or the above formula (1-2) is preferably used. Preferably, the above formula (1-1-1) to formula (1-1-120), the above formula (1-1-121) to formula (1-1-175), and the above formula (1-2-1) are used. )~(1-2-120) and above (1-2-121)~(1-2-180) The compound represented. Further, a benzofluorene compound represented by the formula (1'-1) or the formula (1'-2) can also be used. The use amount of the benzofluorene compound as a dopant material is preferably 0.001 wt% to 50 wt%, more preferably 0.05 wt% to 20 wt%, and even more preferably 0.1 wt% to 10 wt% of the entire luminescent material. %. The doping method may be formed by a co-evaporation method with a host material, or may be simultaneously vapor-deposited after being mixed with a host material.

另外，亦可同時使用其他摻雜劑材料。作為其他摻雜劑材料，並無特別限定，可使用已知的化合物，可對應於所期望的發光色而自各種材料中選擇。具體而言，例如可列舉：菲、蒽、芘、稠四苯、稠五苯、苝、萘并芘、二苯并芘(naphthopyrene)及紅螢烯(rubrene)等縮合環衍生物，苯并噁唑衍生物，苯并噻唑衍生物，苯并咪唑衍生物，苯并***衍生物，噁唑衍生物，噁二唑衍生物，噻唑衍生物，咪唑衍生物，噻二唑衍生物，***衍生物，吡唑啉衍生物，二苯乙烯衍生物，噻吩衍生物，四苯基丁二烯衍生物，環戊二烯衍生物，雙苯乙烯基蒽衍生物或二苯乙烯基苯衍生物等雙苯乙烯基衍生物(日本專利特開平1-245087號公報)，雙苯乙烯基伸芳基衍生物(日本專利特開平2-247278號公報)，二氮雜苯并二茚(diazaindacene)衍生物，呋喃衍生物，苯并呋喃衍生物，苯基異苯并呋喃、二(2,4,6-三甲苯基)異苯并呋喃、二(2-甲基苯基)異苯并呋喃、二(2-三氟甲基苯基)異苯并呋喃、苯基異苯并呋喃等異苯并呋喃衍生物、二苯并呋喃衍生物、7-二烷基胺基香豆素衍生物、7-哌啶基香豆素衍生物、7-羥基香豆素衍生 物、7-甲氧基香豆素衍生物、7-乙醯氧基香豆素衍生物、3-苯并噻唑基香豆素衍生物、3-苯并咪唑基香豆素衍生物、3-苯并噁唑基香豆素衍生物等香豆素衍生物，二氰基亞甲基吡喃衍生物，二氰基亞甲基噻喃衍生物，聚次甲基衍生物，花青衍生物，氧代苯并蒽衍生物，二苯并哌喃衍生物，玫瑰紅(rhodamine)衍生物，螢光素(fluorescein)衍生物，吡喃鎓(pyrylium)衍生物，2(1H)-喹啉酮(carbostyril)衍生物，吖啶衍生物，噁嗪衍生物，苯醚衍生物，喹吖啶酮衍生物，喹唑啉衍生物，吡咯并吡啶衍生物，呋喃并吡啶衍生物，1,2,5-噻二唑并芘衍生物，吡咯亞甲基衍生物，紫環酮衍生物，吡咯并吡咯衍生物，方酸內鎓鹽(squarylium)衍生物，紫蒽酮(violanthrone)衍生物，啡嗪衍生物，吖啶酮衍生物及脫氮黃素衍生物等。 In addition, other dopant materials can be used simultaneously. The other dopant material is not particularly limited, and known compounds can be used, and can be selected from various materials in accordance with a desired luminescent color. Specific examples thereof include condensed ring derivatives such as phenanthrene, anthracene, anthracene, fused tetraphenyl, fused pentabenzene, anthracene, naphthoquinone, naphthopyrene, and rubrene. Oxazole derivative, benzothiazole derivative, benzimidazole derivative, benzotriazole derivative, oxazole derivative, oxadiazole derivative, thiazole derivative, imidazole derivative, thiadiazole derivative, three An azole derivative, a pyrazoline derivative, a stilbene derivative, a thiophene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative, a bisstyrylfluorene derivative or a distyrylbenzene derivative A bisstyryl derivative such as a bisstyryl derivative (Japanese Patent Laid-Open No. Hei 1-245087), a bisstyryl aryl derivative (Japanese Patent Laid-Open No. Hei 2-247278), diazaindacene Derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, bis(2,4,6-trimethylphenyl)isobenzofuran, bis(2-methylphenyl)isobenzofuran , isobenzofuran derivatives such as bis(2-trifluoromethylphenyl)isobenzofuran, phenylisobenzofuran, dibenzofuran derivatives He was 7-alkylamino coumarin derivatives, 7-piperidinyl coumarin derivative, 7-hydroxycoumarin derivative , 7-methoxycoumarin derivative, 7-acetoxycoumarin derivative, 3-benzothiazolylcoumarin derivative, 3-benzimidazolyl coumarin derivative, 3 - coumarin derivatives such as benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives , oxobenzopyrene derivative, dibenzopyran derivative, rhodamine derivative, fluorescein derivative, pyrylium derivative, 2(1H)-quinaline Carbostyril derivative, acridine derivative, oxazine derivative, phenyl ether derivative, quinacridone derivative, quinazoline derivative, pyrrolopyridine derivative, furopyridine derivative, 1, 2,5-thiadiazolofluorene derivative, pyrrolethymethylene derivative, benzalkonone derivative, pyrrolopyrrole derivative, squarylium derivative, violanthrone derivative , a phenazine derivative, an acridone derivative, and a denitrification derivative.

若對每種發色光進行例示，則作為藍色~藍綠色摻雜劑材料，可列舉：萘、蒽、菲、芘、聯伸三苯(triphenylene)、苝、茀、茚等芳香族烴化合物或其衍生物，呋喃、吡咯、噻吩、噻咯、9-矽茀、9,9'-螺二矽茀、苯并噻吩、苯并呋喃、吲哚、二苯并噻吩、二苯并呋喃、咪唑并吡啶、啡啉、吡嗪、萘啶、喹噁啉、吡咯并吡啶、噻噸等芳香族雜環化合物或其衍生物，二苯乙烯基苯衍生物，四苯基丁二烯衍生物，二苯乙烯衍生物，醛連氮(aldazine)衍生物，香豆素衍生物，咪唑、噻唑、噻二唑、咔唑、噁唑、噁二唑、***等唑衍生物及其金屬錯合物，及以N,N'-二苯基-N,N'-二(3-甲基苯基)-4,4'-二苯基-1,1'-二胺為代表的芳香族胺衍 生物等。 When exemplifying each color light, examples of the blue to blue-green dopant material include naphthalene, anthracene, phenanthrene, anthracene, triphenylene, anthracene, anthracene, anthracene, and the like. Its derivatives, furan, pyrrole, thiophene, silole, 9-fluorene, 9,9'-spirobifluorene, benzothiophene, benzofuran, anthracene, dibenzothiophene, dibenzofuran, imidazole And an aromatic heterocyclic compound such as pyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene or a derivative thereof, a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a stilbene derivative, an aldazine derivative, a coumarin derivative, an azole derivative such as imidazole, thiazole, thiadiazole, oxazole, oxazole, oxadiazole or triazole, and a metal mismatch thereof And an aromatic amine represented by N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine Yan Creatures, etc.

另外，作為綠色~黃色摻雜劑材料，可列舉香豆素衍生物、鄰苯二甲醯亞胺衍生物、萘二甲醯亞胺衍生物、紫環酮衍生物、吡咯并吡咯衍生物、環戊二烯衍生物、吖啶酮衍生物、喹吖啶酮衍生物及紅螢烯等稠四苯衍生物等，進而，亦可列舉如下的化合物作為合適的例子：向作為上述藍色~藍綠色摻雜劑材料所例示的化合物中導入芳基、雜芳基、芳基乙烯基、胺基、氰基等可長波長化的取代基而成的化合物。 Further, examples of the green to yellow dopant material include a coumarin derivative, a phthalimide derivative, a naphthylquinone imide derivative, a beodoxone derivative, and a pyrrolopyrrole derivative. Examples of the cyclopentadiene derivative, the acridone derivative, the quinacridone derivative, and the thick tetraphenyl derivative such as erythritol, and the following compounds are also exemplified as the above-mentioned blue color. The compound exemplified as the cyan dopant material is a compound obtained by introducing a substituent having a long wavelength such as an aryl group, a heteroaryl group, an arylvinyl group, an amine group or a cyano group.

進而，作為橙色~紅色摻雜劑材料，可列舉雙(二異丙基苯基)苝四羧酸醯亞胺等萘二甲醯亞胺衍生物，紫環酮衍生物，將乙醯丙酮或苯甲醯丙酮與啡啉等作為配位基的Eu錯合物等稀土類錯合物，4-(二氰基亞甲基)-2-甲基-6-(對二甲基胺基苯乙烯基)-4H-吡喃或其類似物，鎂酞菁、鋁氯酞菁等金屬酞菁衍生物，玫瑰紅化合物，脫氮黃素衍生物，香豆素衍生物，喹吖啶酮衍生物，啡噁嗪衍生物、噁嗪衍生物、喹唑啉衍生物、吡咯并吡啶衍生物、方酸內鎓鹽衍生物、紫蒽酮衍生物、啡嗪衍生物、啡噁嗪酮(phenoxazone)衍生物及噻二唑并芘衍生物等，進而，亦可列舉如下的化合物作為合適的例子：向作為上述藍色~藍綠色及綠色~黃色摻雜劑材料所例示的化合物中導入芳基、雜芳基、芳基乙烯基、胺基、氰基等可長波長化的取代基而成的化合物。進而，亦可列舉以三(2-苯基吡啶)銥(III)為代表的將銥或鉑作為中心金屬的磷光性金屬錯合物作為合適的例 子。 Further, examples of the orange-red dopant material include naphthoquinone imine derivatives such as bis(diisopropylphenyl)phosphonium tetracarboxylate, and a perylene derivative, which is acetonitrile or A rare earth complex such as benzamidine acetone and morpholine as a ligand Eu complex, 4-(dicyanomethylidene)-2-methyl-6-(p-dimethylaminobenzene) Vinyl)-4H-pyran or its analogue, metal phthalocyanine derivative such as magnesium phthalocyanine, aluminum chlorophthalocyanine, rose red compound, deazaflavin derivative, coumarin derivative, quinacridone derivative , phenoxazine derivative, oxazine derivative, quinazoline derivative, pyrrolopyridine derivative, squaraine ylide derivative, purpurin derivative, morphazine derivative, phenoxazone a derivative, a thiadiazole hydrazine derivative, etc., and further, as a suitable example, an aryl group is introduced into a compound exemplified as the blue to cyan and green to yellow dopant materials. A compound having a long-wavelength substituent such as a heteroaryl group, an arylvinyl group, an amine group or a cyano group. Further, as a suitable example, a phosphorescent metal complex containing ruthenium or platinum as a central metal represented by tris(2-phenylpyridine)ruthenium (III) may be mentioned. child.

作為適合於本發明的發光層用材料的摻雜劑材料，上述摻雜劑材料之中，最適合的是由上述通式(1)所表示的苯并茀化合物，作為可同時使用的摻雜劑材料，較佳為苝衍生物、硼烷衍生物、含胺的苯乙烯基衍生物、芳香族胺衍生物、香豆素衍生物、吡喃衍生物、銥錯合物或鉑錯合物。 As a dopant material suitable for the material for a light-emitting layer of the present invention, among the above dopant materials, a benzofluorene compound represented by the above formula (1) is most suitable as a doping which can be used at the same time. The agent material is preferably an anthracene derivative, a borane derivative, an amine-containing styryl derivative, an aromatic amine derivative, a coumarin derivative, a pyran derivative, a ruthenium complex or a platinum complex. .

作為苝衍生物，例如可列舉：3,10-雙(2,6-二甲基苯基)苝、3,10-雙(2,4,6-三甲基苯基)苝、3,10-二苯基苝、3,4-二苯基苝、2,5,8,11-四-第三丁基苝、3,4,9,10-四苯基苝、3-(1'-芘基)-8,11-二(第三丁基)苝、3-(9'-蒽基)-8,11-二(第三丁基)苝、3,3'-雙(8,11-二(第三丁基)苝基)等。 Examples of the anthracene derivative include 3,10-bis(2,6-dimethylphenyl)anthracene, 3,10-bis(2,4,6-trimethylphenyl)anthracene, and 3,10. -diphenylanthracene, 3,4-diphenylanthracene, 2,5,8,11-tetra-t-butylindole, 3,4,9,10-tetraphenylanthracene, 3-(1'- Indenyl)-8,11-di(t-butyl)anthracene, 3-(9'-indenyl)-8,11-di(t-butyl)anthracene, 3,3'-double (8,11 - bis(t-butyl) fluorenyl) and the like.

另外，亦可使用日本專利特開平11-97178號公報、日本專利特開2000-133457號公報、日本專利特開2000-26324號公報、日本專利特開2001-267079號公報、日本專利特開2001-267078號公報、日本專利特開2001-267076號公報、日本專利特開2000-34234號公報、日本專利特開2001-267075號公報、及日本專利特開2001-217077號公報等中所記載的苝衍生物。 In addition, Japanese Patent Laid-Open No. Hei 11-97178, Japanese Patent Laid-Open No. 2000-133457, Japanese Patent Laid-Open No. 2000-26324, Japanese Patent Laid-Open No. 2001-267079, and Japanese Patent Laid-Open No. 2001 Japanese Laid-Open Patent Publication No. 2001-267076, Japanese Patent Laid-Open No. Hei. No. 2001-267076, Japanese Patent Application Laid-Open No. Hei No. Hei. Anthraquinone derivatives.

作為硼烷衍生物，例如可列舉：1,8-二苯基-10-(二(2,4,6-三甲苯基)氧硼基)蒽、9-苯基-10-(二(2,4,6-三甲苯基)氧硼基)蒽、4-(9'-蒽基)二(2,4,6-三甲苯基)氧硼基萘、4-(10'-苯基-9'-蒽基)二(2,4,6-三甲苯基)氧硼基萘、9-(二(2,4,6-三甲苯基)氧硼基)蒽、9-(4'-聯苯基)-10-(二(2,4,6-三甲苯基) 氧硼基)蒽、9-(4'-(N-咔唑基)苯基)-10-(二(2,4,6-三甲苯基)氧硼基)蒽等。 Examples of the borane derivative include 1,8-diphenyl-10-(bis(2,4,6-trimethylphenyl)boroluon)fluorene, and 9-phenyl-10-(di(2). ,4,6-trimethylphenyl)oxonium)anthracene, 4-(9'-indenyl)bis(2,4,6-trimethylphenyl)boroluene, 4-(10'-phenyl- 9'-fluorenyl) bis(2,4,6-trimethylphenyl)oxyborylnaphthalene, 9-(bis(2,4,6-trimethylphenyl)oxyboronic) fluorene, 9-(4'- Biphenyl)-10-(bis(2,4,6-trimethylphenyl) Oxyboronic acid), 9-(4'-(N-carbazolyl)phenyl)-10-(bis(2,4,6-trimethylphenyl)boroluonyl)anthracene.

另外，亦可使用國際公開第2000/40586號手冊等中所記載的硼烷衍生物。 Further, a borane derivative described in International Publication No. 2000/40586 and the like can also be used.

作為含胺的苯乙烯基衍生物，例如可列舉：N,N,N',N'-四(4-聯苯基)-4,4'-二胺基二苯乙烯、N,N,N',N'-四(1-萘基)-4,4'-二胺基二苯乙烯、N,N,N',N'-四(2-萘基)-4,4'-二胺基二苯乙烯、N,N'-二(2-萘基)-N,N'-二苯基-4,4'-二胺基二苯乙烯、N,N'-二(9-菲基)-N,N'-二苯基-4,4'-二胺基二苯乙烯、4,4'-雙[4"-雙(二苯基胺基)苯乙烯基]-聯苯、1,4-雙[4'-雙(二苯基胺基)苯乙烯基]-苯、2,7-雙[4'-雙(二苯基胺基)苯乙烯基]-9,9-二甲基茀、4,4'-雙(9-乙基-3-咔唑乙烯基)-聯苯、4,4'-雙(9-苯基-3-咔唑乙烯基)-聯苯等。另外，亦可使用日本專利特開2003-347056號公報、及日本專利特開2001-307884號公報等中所記載的含胺的苯乙烯基衍生物。 As the amine-containing styryl derivative, for example, N,N,N',N'-tetrakis(4-biphenyl)-4,4'-diaminostilbene, N, N, N can be cited. ',N'-tetrakis(1-naphthyl)-4,4'-diaminostilbene, N,N,N',N'-tetrakis(2-naphthyl)-4,4'-diamine Styrene, N,N'-bis(2-naphthyl)-N,N'-diphenyl-4,4'-diaminostilbene, N,N'-bis(9-phenanthryl) )-N,N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis[4"-bis(diphenylamino)styryl]-biphenyl, 1 ,4-bis[4'-bis(diphenylamino)styryl]-benzene, 2,7-bis[4'-bis(diphenylamino)styryl]-9,9-di Methyl hydrazine, 4,4'-bis(9-ethyl-3-carbazolevinyl)-biphenyl, 4,4'-bis(9-phenyl-3-carbazolevinyl)-biphenyl, etc. Further, an amine-containing styryl derivative described in JP-A-2003-347056, and JP-A-2001-307884, etc., may be used.

作為芳香族胺衍生物，例如可列舉：N,N,N,N-四苯基蒽-9,10-二胺、9,10-雙(4-二苯基胺基-苯基)蒽、9,10-雙(4-二(1-萘胺基)苯基)蒽、9,10-雙(4-二(2-萘胺基)苯基)蒽、10-二-對甲苯基胺基-9-(4-二-對甲苯基胺基-1-萘基)蒽、10-二苯基胺基-9-(4-二苯基胺基-1-萘基)蒽、10-二苯基胺基-9-(6-二苯基胺基-2-萘基)蒽、[4-(4-二苯基胺基-苯基)萘-1-基]-二苯基胺、[6-(4-二苯基胺基-苯基)萘-2-基]-二苯基胺、4,4'-雙[4-二苯基胺基萘-1-基]聯苯、4,4'-雙[6-二苯基胺基萘-2-基]聯苯、4,4"-雙[4-二苯基胺基萘-1-基]-對聯三 苯、4,4"-雙[6-二苯基胺基萘-2-基]-對聯三苯等。 Examples of the aromatic amine derivative include N,N,N,N-tetraphenylphosphonium-9,10-diamine and 9,10-bis(4-diphenylamino-phenyl)fluorene. 9,10-bis(4-bis(1-naphthylamino)phenyl)anthracene, 9,10-bis(4-di(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamine 9-(4-di-p-tolylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(4-diphenylamino-1-naphthyl)anthracene, 10- Diphenylamino-9-(6-diphenylamino-2-naphthyl)anthracene, [4-(4-diphenylamino-phenyl)naphthalen-1-yl]-diphenylamine , [6-(4-Diphenylamino-phenyl)naphthalen-2-yl]-diphenylamine, 4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenyl , 4,4'-bis[6-diphenylaminonaphthalen-2-yl]biphenyl, 4,4"-bis[4-diphenylaminonaphthalen-1-yl]-pair three Benzene, 4,4"-bis[6-diphenylaminonaphthalen-2-yl]-para-triphenyl or the like.

另外，亦可使用日本專利特開2006-156888號公報等中所記載的芳香族胺衍生物。 Further, an aromatic amine derivative described in JP-A-2006-156888 or the like can also be used.

作為香豆素衍生物，可列舉香豆素-6、香豆素-334等。 Examples of the coumarin derivative include coumarin-6 and coumarin-334.

另外，亦可使用日本專利特開2004-43646號公報、日本專利特開2001-76876號公報、及日本專利特開平6-298758號公報等中所記載的香豆素衍生物。 Further, the coumarin derivative described in JP-A-2004-43646, JP-A-2001-76876, and JP-A-6-298758, and the like can be used.

作為吡喃衍生物，可列舉下述的DCM、DCJTB等。 Examples of the pyran derivative include DCM, DCJTB, and the like described below.

另外，亦可使用日本專利特開2005-126399號公報、日本專利特開2005-097283號公報、日本專利特開2002-234892號公報、日本專利特開2001-220577號公報、日本專利特開2001-081090號公報、及日本專利特開2001-052869號公報等中所記載的吡喃衍生物。 In addition, Japanese Patent Laid-Open Publication No. 2005-126399, Japanese Patent Laid-Open No. Hei. No. 2005-097283, Japanese Patent Laid-Open No. Hei No. 2002-234892, Japanese Patent Laid-Open No. 2001-220577, and Japanese Patent Laid-Open No. 2001 The pyran derivative described in Japanese Laid-Open Patent Publication No. 2001-052869, and the like.

作為銥錯合物，可列舉下述的Ir(ppy)3等。 Examples of the ruthenium complex include Ir(ppy) 3 and the like described below.

另外，亦可使用日本專利特開2006-089398號公報、日本專利特開2006-080419號公報、日本專利特開2005-298483號公報、日本專利特開2005-097263號公報、及日本專利特開2004-111379號公報等中所記載的銥錯合物。 In addition, Japanese Patent Laid-Open No. 2006-089398, Japanese Patent Laid-Open No. Hei. No. 2006-080419, Japanese Patent Laid-Open No. Hei No. 2005-298483, Japanese Patent Laid-Open No. 2005-097263, and Japanese Patent Laid-Open The ruthenium complex described in JP-A-2004-111379.

作為鉑錯合物，可列舉下述的PtOEP等。 Examples of the platinum complex compound include the following PtOEP and the like.

另外，亦可使用日本專利特開2006-190718號公報、日本專利特開2006-128634號公報、日本專利特開2006-093542號公報、日本專利特開2004-335122號公報、及日本專利特開2004-331508號公報等中所記載的鉑錯合物。 In addition, Japanese Patent Laid-Open No. Hei. No. 2006-190718, Japanese Patent Laid-Open No. Hei. No. 2006-128634, Japanese Patent Laid-Open No. Hei. No. Hei. No. 2006-093542, Japanese Patent Laid-Open No. 2004-335122, and Japanese Patent Laid-Open A platinum complex as described in JP-A-2004-331508.

此外，作為摻雜劑，可自化學工業2004年6月號第 13頁、及其中所列舉的參考文獻等中所記載的化合物等中適宜選擇來使用。 In addition, as a dopant, it can be used in the June 2004 issue of the chemical industry. The compounds described in the thirteenth page, the references cited therein, and the like are suitably selected and used.

<有機電場發光元件中的電子注入層、電子傳輸層> <Electron Injection Layer, Electron Transport Layer in Organic Electric Field Light-Emitting Element>

電子注入層107是發揮將自陰極108移動而來的電子高效地注入至發光層105內或電子傳輸層106內的作用的層。電子傳輸層106是發揮將自陰極108所注入的電子、或自陰極108經由電子注入層107所注入的電子高效地傳輸至發光層105的作用的層。電子傳輸層106及電子注入層107分別將電子傳輸．注入材料的一種或兩種以上加以積層、混合而形成，或者由電子傳輸．注入材料與高分子黏結劑的混合物形成。 The electron injection layer 107 is a layer that functions to efficiently inject electrons moved from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 is a layer that functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light-emitting layer 105. The electron transport layer 106 and the electron injection layer 107 respectively transmit electrons. One or more of the injected materials are formed by lamination, mixing, or by electron transport. The injection material is formed with a mixture of polymer binders.

所謂電子注入．傳輸層，是指掌管自陰極注入電子，進而傳輸電子的層，理想的是電子注入效率高、且高效地傳輸所注入的電子。因此，較佳為電子親和力大、且電子移動率大、進而穩定性優異，製造時及使用時不易產生成為陷阱的雜質的物質。但是，於考慮了電洞與電子的傳輸平衡的情況下，當主要發揮可高效地阻止來自陽極的電洞未再結合而流向陰極側的作用時，即便電子傳輸能力並不那麼高，亦與電子傳輸能力高的材料同等地具有提昇發光效率的效果。因此，本實施形態中的電子注入．傳輸層亦可包含可高效地阻止電洞的移動的層的功能。 The so-called electron injection. The transport layer refers to a layer that injects electrons from the cathode and transports electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. Therefore, it is preferable that the electron affinity is large, the electron mobility is large, and the stability is excellent, and it is difficult to generate impurities which are traps during production and use. However, when the transmission balance between the hole and the electron is considered, when the main function is to effectively prevent the hole from the anode from flowing back to the cathode side, even if the electron transporting ability is not so high, A material having a high electron transporting ability has an effect of improving luminous efficiency equally. Therefore, the electron injection in this embodiment. The transport layer may also include a function of a layer that can effectively block the movement of the hole.

作為電子傳輸層及電子注入層中所使用的材料，可自先前以來於光導電材料中作為電子傳遞化合物所慣用的化合物、用於有機電場發光元件的電子注入層及電子傳輸層 的公知的化合物中任意地選擇來使用。 As a material used in the electron transport layer and the electron injecting layer, a compound conventionally used as an electron transporting compound in a photoconductive material, an electron injecting layer and an electron transporting layer for an organic electroluminescent element. Any of the known compounds is optionally used.

具體而言，可列舉：吡啶衍生物、萘衍生物、蒽衍生物、啡啉衍生物、紫環酮衍生物、香豆素衍生物、萘二甲醯亞胺衍生物、蒽醌衍生物、聯苯醌衍生物、二苯基醌衍生物、苝衍生物、噻吩衍生物、噻二唑衍生物、喹噁啉衍生物、喹噁啉衍生物的聚合物、苯并唑類化合物、吡唑衍生物、全氟化伸苯基衍生物、三嗪衍生物、吡嗪衍生物、咪唑并吡啶衍生物、硼烷衍生物、苯并噁唑衍生物、苯并噻唑衍生物、喹啉衍生物、醛連氮衍生物、咔唑衍生物、吲哚衍生物、氧化磷衍生物、雙苯乙烯基衍生物等。另外，可列舉：噁二唑衍生物(1,3-雙[(4-第三丁基苯基)1,3,4-噁二唑基]伸苯基等)、***衍生物(N-萘基-2,5-二苯基-1,3,4-***等)、苯并喹啉衍生物(2,2'-雙(苯并[h]喹啉-2-基)-9,9'-螺二茀等)、苯并咪唑衍生物(三(N-苯基苯并咪唑-2-基)苯等)、聯吡啶衍生物、三聯吡啶衍生物(1,3-雙(4'-(2,2'：6'2"-三聯吡啶))苯等)、萘啶衍生物(雙(1-萘基)-4-(1,8-萘啶-2-基)苯基氧化膦等)等。該些材料可單獨使用，亦可與不同的材料混合使用。 Specific examples thereof include a pyridine derivative, a naphthalene derivative, an anthracene derivative, a phenanthroline derivative, a purple ring ketone derivative, a coumarin derivative, a naphthoquinone imine derivative, an anthracene derivative, and the like. Biphenyl hydrazine derivative, diphenyl hydrazine derivative, hydrazine derivative, thiophene derivative, thiadiazole derivative, quinolinate derivative, polymer of quinoxaline derivative, benzoxazole compound, pyrazole Derivatives, perfluorinated phenyl derivatives, triazine derivatives, pyrazine derivatives, imidazopyridine derivatives, borane derivatives, benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives An aldehyde nitrogen derivative, a carbazole derivative, an anthracene derivative, a phosphorus oxide derivative, a bisstyryl derivative or the like. Further, examples thereof include an oxadiazole derivative (1,3-bis[(4-tert-butylphenyl) 1,3,4-oxadiazolyl]phenylene), and a triazole derivative (N) -naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), benzoquinoline derivative (2,2'-bis(benzo[h]quinolin-2-yl)- 9,9'-spirobifluorene, etc., benzimidazole derivatives (tris(N-phenylbenzimidazol-2-yl)benzene, etc.), bipyridine derivatives, terpyridine derivatives (1,3-double (4'-(2,2':6'2"-terpyridine)) phenyl, etc.), naphthyridine derivative (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl) Phenylphosphine oxide, etc., etc. These materials may be used singly or in combination with different materials.

另外，亦可使用具有電子接受性氮的金屬錯合物，例如可列舉：羥基喹啉系金屬錯合物或羥苯基噁唑錯合物等羥基唑錯合物、甲亞胺(azomethine)錯合物、環庚三烯酚酮(tropolone)金屬錯合物、黃酮醇(flavonol)金屬錯合物及苯并喹啉金屬錯合物等。該些材料可單獨使用，亦可與不同的材料混合使用。 Further, a metal complex having electron-accepting nitrogen may be used, and examples thereof include a hydroxyquinoline metal complex or a hydroxyzole complex such as a hydroxyphenyl oxazole complex, and azomethine. Complex, tropolone metal complex, flavonol metal complex, benzoquinoline metal complex, and the like. These materials can be used alone or in combination with different materials.

上述材料之中，較佳為羥基喹啉系金屬錯合物、吡啶衍生物、啡啉衍生物、硼烷衍生物或苯并咪唑衍生物。 Among the above materials, a quinolinol metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative or a benzimidazole derivative is preferred.

羥基喹啉系金屬錯合物是由下述通式(E-1)所表示的化合物。 The hydroxyquinoline metal complex is a compound represented by the following formula (E-1).

式中，R1~R6為氫或取代基，M為Li、Al、Ga、Be或Zn，n為1~3的整數。 In the formula, R 1 to R 6 are hydrogen or a substituent, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.

作為羥基喹啉系金屬錯合物的具體例，可列舉：8-羥基喹啉鋰、三(8-羥基喹啉)鋁、三(4-甲基-8-羥基喹啉)鋁、三(5-甲基-8-羥基喹啉)鋁、三(3,4-二甲基-8-羥基喹啉)鋁、三(4,5-二甲基-8-羥基喹啉)鋁、三(4,6-二甲基-8-羥基喹啉)鋁、雙(2-甲基-8-羥基喹啉)(苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2-甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(3-甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(4-甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2-苯基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(3-苯基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(4-苯基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2,3-二甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2,6-二甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(3,4-二甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(3,5-二甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(3,5-二-第三丁基苯酚)鋁、雙(2-甲基-8- 羥基喹啉)(2,6-二苯基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2,4,6-三苯基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2,4,6-三甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(2,4,5,6-四甲基苯酚)鋁、雙(2-甲基-8-羥基喹啉)(1-萘酚)鋁、雙(2-甲基-8-羥基喹啉)(2-萘酚)鋁、雙(2,4-二甲基-8-羥基喹啉)(2-苯基苯酚)鋁、雙(2,4-二甲基-8-羥基喹啉)(3-苯基苯酚)鋁、雙(2,4-二甲基-8-羥基喹啉)(4-苯基苯酚)鋁、雙(2,4-二甲基-8-羥基喹啉)(3,5-二甲基苯酚)鋁、雙(2,4-二甲基-8-羥基喹啉)(3,5-二-第三丁基苯酚)鋁、雙(2-甲基-8-羥基喹啉)鋁-μ-側氧基-雙(2-甲基-8-羥基喹啉)鋁、雙(2,4-二甲基-8-羥基喹啉)鋁-μ-側氧基-雙(2,4-二甲基-8-羥基喹啉)鋁、雙(2-甲基-4-乙基-8-羥基喹啉)鋁-μ-側氧基-雙(2-甲基-4-乙基-8-羥基喹啉)鋁、雙(2-甲基-4-甲氧基-8-羥基喹啉)鋁-μ-側氧基-雙(2-甲基-4-甲氧基-8-羥基喹啉)鋁、雙(2-甲基-5-氰基-8-羥基喹啉)鋁-μ-側氧基-雙(2-甲基-5-氰基-8-羥基喹啉)鋁、雙(2-甲基-5-三氟甲基-8-羥基喹啉)鋁-μ-側氧基-雙(2-甲基-5-三氟甲基-8-羥基喹啉)鋁、雙(10-羥基苯并[h]喹啉)鈹等。 Specific examples of the hydroxyquinoline-based metal complex include lithium 8-hydroxyquinolate, aluminum tris(8-hydroxyquinoline), aluminum tris(4-methyl-8-hydroxyquinoline), and tris(3). 5-methyl-8-hydroxyquinoline aluminum, tris(3,4-dimethyl-8-hydroxyquinoline) aluminum, tris(4,5-dimethyl-8-hydroxyquinoline) aluminum, three (4,6-Dimethyl-8-hydroxyquinoline) aluminum, bis(2-methyl-8-hydroxyquinoline) (phenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2 -methylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline)(3-methylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(4-methylphenol)aluminum , bis(2-methyl-8-hydroxyquinoline)(2-phenylphenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2-methyl (8-hydroxyquinoline) (4-phenylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,3-dimethylphenol) aluminum, bis(2-methyl-8 -hydroxyquinoline) (2,6-dimethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (3,4-dimethylphenol) aluminum, bis(2-methyl-8 -hydroxyquinoline) (3,5-dimethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (3,5-di-t-butylphenol) aluminum, double (2-A Base-8- Hydroxyquinoline) (2,6-diphenylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,4,6-triphenylphenol) aluminum, bis(2-methyl- 8-hydroxyquinoline) (2,4,6-trimethylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2,4,5,6-tetramethylphenol) aluminum, double (2-methyl-8-hydroxyquinoline) (1-naphthol) aluminum, bis(2-methyl-8-hydroxyquinoline) (2-naphthol) aluminum, bis(2,4-dimethyl -8-hydroxyquinoline) (2-phenylphenol) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2,4-dimethyl -8-hydroxyquinoline) (4-phenylphenol) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (3,5-dimethylphenol) aluminum, bis (2,4- Dimethyl-8-hydroxyquinoline) (3,5-di-tert-butylphenol) aluminum, bis(2-methyl-8-hydroxyquinoline)aluminum-μ-sideoxy-double (2- Methyl-8-hydroxyquinoline)aluminum, bis(2,4-dimethyl-8-hydroxyquinoline)aluminum-μ-sideoxy-bis(2,4-dimethyl-8-hydroxyquinoline Aluminum, bis(2-methyl-4-ethyl-8-hydroxyquinoline) aluminum-μ-sideoxy-bis(2-methyl-4-ethyl-8-hydroxyquinoline) aluminum, double (2-methyl-4-methoxy-8-hydroxyquinoline) aluminum-μ-sideoxy-bis(2-methyl-4-methoxy-8-hydroxyquinoline) aluminum, double (2 -methyl-5-cyano-8-hydroxyquinoline -μ-Sideoxy-bis(2-methyl-5-cyano-8-hydroxyquinoline)aluminum, bis(2-methyl-5-trifluoromethyl-8-hydroxyquinoline)aluminum-μ - oxo-bis(2-methyl-5-trifluoromethyl-8-hydroxyquinoline)aluminum, bis(10-hydroxybenzo[h]quinoline)indole, and the like.

吡啶衍生物是由下述通式(E-2)所表示的化合物。 The pyridine derivative is a compound represented by the following formula (E-2).

式中，G表示單一的鍵結鍵或n價的連結基，n為2~8的整數。另外，未用於吡啶-吡啶或吡啶-G的鍵結的碳 原子亦可被取代。 In the formula, G represents a single bond bond or an n-valent linker, and n is an integer of 2-8. In addition, carbon not used for the bonding of pyridine-pyridine or pyridine-G Atoms can also be replaced.

作為通式(E-2)的G，例如可列舉以下結構式的化合物。再者，下述結構式中的R分別獨立為氫、甲基、乙基、異丙基、環己基、苯基、1-萘基、2-萘基、聯苯基或聯三苯基。 Examples of G of the formula (E-2) include compounds of the following structural formulas. Further, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or terphenyl.

作為吡啶衍生物的具體例，可列舉：2,5-雙(2,2'-聯吡啶-6-基)-1,1-二甲基-3,4-二苯基嘧咯、2,5-雙(2,2'-聯吡啶-6-基)-1,1-二甲基-3,4-二(2,4,6-三甲苯基)噻咯、2,5-雙(2,2'-聯吡啶-5-基)-1,1-二甲基-3,4-二苯基噻咯、2,5-雙(2,2'-聯吡啶-5-基)-1,1-二甲基-3,4-二(2,4,6-三甲苯基)噻咯、9,10-二(2,2'-聯吡啶-6-基)蒽、9,10-二(2,2'-聯吡啶-5-基)蒽、9,10-二(2,3'-聯吡啶-6-基)蒽、9,10-二(2,3'-聯吡啶-5-基)蒽、9,10-二(2,3'-聯吡啶-6-基)-2-苯基蒽、9,10-二(2,3'-聯吡啶-5-基)-2-苯基蒽、9,10-二(2,2'-聯吡啶-6-基)-2-苯基蒽、9,10-二(2,2'-聯吡啶-5-基)-2-苯基蒽、9,10-二(2,4'-聯吡啶-6-基)-2-苯基蒽、9,10-二(2,4'-聯吡啶-5-基)-2-苯基蒽、9,10-二(3,4'-聯吡啶-6-基)-2-苯基蒽、9,10-二(3,4'-聯吡啶-5-基)-2-苯基蒽、3,4-二苯基-2,5-二(2,2'-聯吡啶-6-基)噻吩、3,4-二苯基-2,5-二(2,3'-聯吡啶-5-基)噻吩、6',6"-二(2-吡啶基)2,2'：4',4"：2",2'''-四聯吡啶等。 Specific examples of the pyridine derivative include 2,5-bis(2,2'-bipyridin-6-yl)-1,1-dimethyl-3,4-diphenylpyrrole, 2, 5-bis(2,2'-bipyridin-6-yl)-1,1-dimethyl-3,4-di(2,4,6-trimethylphenyl)thiol, 2,5-bis ( 2,2'-bipyridyl-5-yl)-1,1-dimethyl-3,4-diphenylthiazole, 2,5-bis(2,2'-bipyridin-5-yl)- 1,1-dimethyl-3,4-bis(2,4,6-trimethylphenyl)thiazole, 9,10-bis(2,2'-bipyridin-6-yl)anthracene, 9,10 -bis(2,2'-bipyridin-5-yl)anthracene, 9,10-bis(2,3'-bipyridin-6-yl)anthracene, 9,10-di(2,3'-bipyridine -5-yl)fluorene, 9,10-bis(2,3'-bipyridin-6-yl)-2-phenylindole, 9,10-di(2,3'-bipyridin-5-yl) -2-phenylindole, 9,10-bis(2,2'-bipyridin-6-yl)-2-phenylindole, 9,10-di(2,2'-bipyridin-5-yl) -2-phenylindole, 9,10-bis(2,4'-bipyridin-6-yl)-2-phenylindole, 9,10-di(2,4'-bipyridin-5-yl) -2-phenylindole, 9,10-bis(3,4'-bipyridin-6-yl)-2-phenylindole, 9,10-di(3,4'-bipyridin-5-yl) -2-phenylindole, 3,4-diphenyl-2,5-di(2,2'-bipyridin-6-yl)thiophene, 3,4-diphenyl-2,5-di(2) , 3'-bipyridyl-5-yl)thiophene, 6',6"-bis(2-pyridyl)2,2':4',4":2",2'''-quadruple Pyridine and so on.

啡啉衍生物是由下述通式(E-3-1)或通式(E-3-2)所表示的化合物。 The phenanthroline derivative is a compound represented by the following formula (E-3-1) or formula (E-3-2).

式中，R1~R8為氫或取代基，鄰接的基可相互鍵結而 形成縮合環，G表示單一的鍵結鍵或n價的連結基，n為2~8的整數。另外，作為通式(E-3-2)的G，例如可列舉與聯吡啶衍生物一欄中所說明的G相同者。 In the formula, R 1 to R 8 are hydrogen or a substituent, and adjacent groups may be bonded to each other to form a condensed ring, G represents a single bond bond or an n-valent linker, and n is an integer of 2-8. Further, as G of the formula (E-3-2), for example, the same as G described in the column of the bipyridine derivative can be mentioned.

作為啡啉衍生物的具體例，可列舉：4,7-二苯基-1,10-啡啉、2,9-二甲基-4,7-二苯基-1,10-啡啉、9,10-二(1,10-啡啉-2-基)蒽、2,6-二(1,10-啡啉-5-基)吡啶、1,3,5-三(1,10-啡啉-5-基)苯、9,9'-二氟-雙(1,10-啡啉-5-基)、2,9-二甲基-4,7-聯苯-1,10-啡啉(bathocuproine)或1,3-雙(2-苯基-1,10-啡啉-9-基)苯等。 Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-morpholine and 2,9-dimethyl-4,7-diphenyl-1,10-morpholine. 9,10-bis(1,10-morpholin-2-yl)anthracene, 2,6-di(1,10-morpholin-5-yl)pyridine, 1,3,5-tris (1,10- Morpholine-5-yl)benzene, 9,9'-difluoro-bis(1,10-morpholin-5-yl), 2,9-dimethyl-4,7-biphenyl-1,10- Bathocuproine or 1,3-bis(2-phenyl-1,10-morpholin-9-yl)benzene.

尤其，對將啡啉衍生物用於電子傳輸層、電子注入層的情況進行說明。為了獲得長時間穩定的發光，期望一種熱穩定性或薄膜形成性優異的材料，較佳為啡啉衍生物之中，取代基本身具有三維立體結構、或者藉由與啡啉骨架的立體排斥或與鄰接取代基的立體排斥而具有三維立體結構者，或者連結有多個啡啉骨架者。進而，當連結多個啡啉骨架時，更佳為連結單元中含有共軛鍵、經取代或未經取代的芳香族烴、經取代或未經取代的芳香雜環的化合物。 In particular, a case where a phenanthroline derivative is used for an electron transport layer or an electron injection layer will be described. In order to obtain long-term stable luminescence, a material excellent in thermal stability or film formability is preferable, and among the phenanthroline derivatives, the substitution has a three-dimensional structure or a steric repulsion with a phenanthroline skeleton or Those having a three-dimensional structure with steric repulsion of adjacent substituents or having a plurality of morpholine skeletons. Further, when a plurality of morpholine skeletons are bonded, a compound having a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring in the linking unit is more preferable.

硼烷衍生物是由下述通式(E-4)所表示的化合物，詳細情況於日本專利特開2007-27587號公報中有所揭示。 The borane derivative is a compound represented by the following formula (E-4), which is disclosed in detail in Japanese Patent Laid-Open Publication No. 2007-27587.

式中，R11及R12分別獨立為氫、烷基、可被取代的芳基、取代矽烷基、可被取代的含氮的雜環、或氰基的至少一者，R13~R16分別獨立為可被取代的烷基、或可被取代的芳基，X為可被取代的伸芳基，Y為可被取代的碳數為16以下的芳基、取代氧硼基、或可被取代的咔唑，而且，n分別獨立為0~3的整數。 Wherein R 11 and R 12 are each independently at least one of hydrogen, an alkyl group, an aryl group which may be substituted, a substituted fluorenyl group, a nitrogen-containing hetero ring which may be substituted, or a cyano group, R 13 to R 16 Each independently is an alkyl group which may be substituted, or an aryl group which may be substituted, X is a aryl group which may be substituted, and Y is an aryl group having a carbon number of 16 or less which may be substituted, a substituted oxyboron group, or The substituted carbazole, and n is independently an integer of 0 to 3.

由上述通式(E-4)所表示的化合物之中，較佳為由下述通式(E-4-1)所表示的化合物，更佳為由下述通式(E-4-1-1)~通式(E-4-1-4)所表示的化合物。作為具體例，可列舉：9-[4-(4-二(2,4,6-三甲苯基)氧硼基萘-1-基)苯基]咔唑、9-[4-(4-二(2,4,6-三甲苯基)氧硼基萘-1-基)萘-1-基]咔唑等。 Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-1) is preferred, and it is more preferred to have the following formula (E-4-1). -1)~ A compound represented by the formula (E-4-1-4). Specific examples thereof include 9-[4-(4-bis(2,4,6-trimethylphenyl)oxyborylnaphthalen-1-yl)phenyl]carbazole, 9-[4-(4- Bis(2,4,6-trimethylphenyl)oxaborylnaphthalen-1-yl)naphthalen-1-yl]carbazole and the like.

式中，R11及R12分別獨立為氫、烷基、可被取代的芳基、取代矽烷基、可被取代的含氮的雜環、或氰基的至少一者，R13~R16分別獨立為可被取代的烷基、或可被取代的芳基，R21及R22分別獨立為氫、烷基、可被取代的芳基、取代矽烷基、可被取代的含氮的雜環、或氰基的至少一者，X1為可被取代的碳數為20以下的伸芳基，n分別獨立為0 ~3的整數，而且，m分別獨立為0~4的整數。 Wherein R 11 and R 12 are each independently at least one of hydrogen, an alkyl group, an aryl group which may be substituted, a substituted fluorenyl group, a nitrogen-containing hetero ring which may be substituted, or a cyano group, R 13 to R 16 Each independently is an alkyl group which may be substituted, or an aryl group which may be substituted, and R 21 and R 22 are each independently hydrogen, an alkyl group, an aryl group which may be substituted, a substituted fluorenyl group, and a nitrogen-containing impurity which may be substituted. At least one of a ring or a cyano group, X 1 is an extendable aryl group having a carbon number of 20 or less, and n is independently an integer of 0 to 3, and m is independently an integer of 0 to 4.

各式中，R31~R34分別獨立為甲基、異丙基或苯基的任一者，而且，R35及R36分別獨立為氫、甲基、異丙基或苯基的任一者。 In each formula, R 31 to R 34 are each independently a methyl group, an isopropyl group or a phenyl group, and R 35 and R 36 are each independently hydrogen, methyl, isopropyl or phenyl. By.

由上述通式(E-4)所表示的化合物之中，較佳為由下述通式(E-4-2)所表示的化合物，更佳為由下述通式(E-4-2-1)所表示的化合物。 Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-2) is preferred, and more preferably a formula (E-4-2) -1) The compound represented.

式中，R11及R12分別獨立為氫、烷基、可被取代的芳基、取代矽烷基、可被取代的含氮的雜環、或氰基的至少 一者，R13~R16分別獨立為可被取代的烷基、或可被取代的芳基，X1為可被取代的碳數為20以下的伸芳基，而且，n分別獨立為0~3的整數。 Wherein R 11 and R 12 are each independently at least one of hydrogen, an alkyl group, an aryl group which may be substituted, a substituted fluorenyl group, a nitrogen-containing hetero ring which may be substituted, or a cyano group, R 13 to R 16 Each of them is independently an alkyl group which may be substituted or an aryl group which may be substituted, and X 1 is an exoaryl group having a carbon number of 20 or less which may be substituted, and n is independently an integer of 0 to 3.

式中，R31~R34分別獨立為甲基、異丙基或苯基的任一者，而且，R35及R36分別獨立為氫、甲基、異丙基或苯基的任一者。 In the formula, R 31 to R 34 are each independently a methyl group, an isopropyl group or a phenyl group, and R 35 and R 36 are each independently hydrogen, methyl, isopropyl or phenyl. .

由上述通式(E-4)所表示的化合物之中，較佳為由下述通式(E-4-3)所表示的化合物，更佳為由下述通式(E-4-3-1)或通式(E-4-3-2)所表示的化合物。 Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-3) is preferred, and a compound of the formula (E-4-3) is more preferred. -1) or a compound represented by the formula (E-4-3-2).

式中，R11及R12分別獨立為氫、烷基、可被取代的芳基、取代矽烷基、可被取代的含氮的雜環、或氰基的至少一者，R13~R16分別獨立為可被取代的烷基、或可被取代的芳基，X1為可被取代的碳數為10以下的伸芳基，Y1為 可被取代的碳數為14以下的芳基，而且，n分別獨立為0~3的整數。 Wherein R 11 and R 12 are each independently at least one of hydrogen, an alkyl group, an aryl group which may be substituted, a substituted fluorenyl group, a nitrogen-containing hetero ring which may be substituted, or a cyano group, R 13 to R 16 Each of which is independently an alkyl group which may be substituted or an aryl group which may be substituted, X 1 is a aryl group having a carbon number of 10 or less which may be substituted, and Y 1 is an aryl group having a carbon number of 14 or less which may be substituted And, n is independently an integer of 0~3.

各式中，R31~R34分別獨立為甲基、異丙基或苯基的任一者，而且，R35及R36分別獨立為氫、甲基、異丙基或苯基的任一者。 In each formula, R 31 to R 34 are each independently a methyl group, an isopropyl group or a phenyl group, and R 35 and R 36 are each independently hydrogen, methyl, isopropyl or phenyl. By.

苯并咪唑衍生物是由下述通式(E-5)所表示的化合物。 The benzimidazole derivative is a compound represented by the following formula (E-5).

式中，Ar1~Ar3分別獨立為氫或可被取代的碳數為6~20的芳基。尤其，較佳為Ar1為可被取代的蒽基的苯并咪唑衍生物。 In the formula, Ar 1 to Ar 3 are each independently hydrogen or an optionally substituted aryl group having 6 to 20 carbon atoms. In particular, it is preferred that Ar 1 is a benzimidazole derivative of a mercapto group which may be substituted.

碳數為6~30的芳基的具體例為苯基、1-萘基、2-萘基、苊-1-基、苊-3-基、苊-4-基、苊-5-基、茀-1-基、茀-2-基、茀-3-基、茀-4-基、茀-9-基、萉-1-基、萉-2-基、1-菲 基、2-菲基、3-菲基、4-菲基、9-菲基、1-蒽基、2-蒽基、9-蒽基、熒蒽-1-基、熒蒽-2-基、熒蒽-3-基、熒蒽-7-基、熒蒽-8-基、聯伸三苯-1-基、聯伸三苯-2-基、芘-1-基、芘-2-基、芘-4-基、屈-1-基(chrysene-1-yl)、屈-2-基、屈-3-基、屈-4-基、屈-5-基、屈-6-基、稠四苯-1-基、稠四苯-2-基、稠四苯-5-基、苝-1-基、苝-2-基、苝-3-基、稠五苯-1-基、稠五苯-2-基、稠五苯-5-基、稠五苯-6-基。 Specific examples of the aryl group having 6 to 30 carbon atoms are phenyl, 1-naphthyl, 2-naphthyl, indol-1-yl, indol-3-yl, indol-4-yl, indol-5-yl, Ind-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-9-yl, indol-1-yl, indol-2-yl, 1-phenanthrene , 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-indenyl, 2-indolyl, 9-fluorenyl, fluoranthene-1-yl, fluoranthen-2-yl , fluoranthene-3-yl, fluoranthene-7-yl, fluoranthene-8-yl, tert-triphenyl-1-yl, tert-triphenyl-2-yl, indol-1-yl, indol-2-yl,芘-4-yl, chrysene-1-yl, quin-2-yl, quin-3-yl, quin-4-yl, quin-5-yl, quin-6-yl, thick Tetraphenyl-1-yl, fused tetraphenyl-2-yl, fused tetraphenyl-5-yl, indol-1-yl, indol-2-yl, indol-3-yl, fused pentaphenyl-1-yl, thick Penta-2-yl, fused pentaphenyl-5-yl, fused pentaphenyl-6-yl.

苯并咪唑衍生物的具體例為1-苯基-2-(4-(10-苯基蒽-9-基)苯基)-1H-苯并[d]咪唑、2-(4-(10-(萘-2-基)蒽-9-基)苯基)-1-苯基-1H-苯并[d]咪唑、2-(3-(10-(萘-2-基)蒽-9-基)苯基)-1-苯基-1H-苯并[d]咪唑、5-(10-(萘-2-基)蒽-9-基)-1,2-二苯基-1H-苯并[d]咪唑、1-(4-(10-(萘-2-基)蒽-9-基)苯基)-2-苯基-1H-苯并[d]咪唑、2-(4-(9,10-二(萘-2-基)蒽-2-基)苯基)-1-苯基-1H-苯并[d]咪唑、1-(4-(9,10-二(萘-2-基)蒽-2-基)苯基)-2-苯基-1H-苯并[d]咪唑、5-(9,10-二(萘-2-基)蒽-2-基)-1,2-二苯基-1H-苯并[d]咪唑。 A specific example of a benzimidazole derivative is 1-phenyl-2-(4-(10-phenylfluoren-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10) -(naphthalen-2-yl)fluoren-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)fluorene-9 -yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)fluoren-9-yl)-1,2-diphenyl-1H- Benzo[d]imidazole, 1-(4-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4) -(9,10-bis(naphthalen-2-yl)indol-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-di() Naphthalen-2-yl)indol-2-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)indol-2-yl )-1,2-diphenyl-1H-benzo[d]imidazole.

於電子傳輸層或電子注入層中，進而可包含可將形成電子傳輸層或電子注入層的材料還原的物質。該還原性物質只要是具有一定的還原性的物質，則可使用各種物質，例如可適宜地使用選自由鹼金屬、鹼土金屬、稀土金屬、鹼金屬的氧化物、鹼金屬的鹵化物、鹼土金屬的氧化物、鹼土金屬的鹵化物、稀土金屬的氧化物、稀土金屬的鹵化物、鹼金屬的有機錯合物、鹼土金屬的有機錯合物及稀土金屬的有機錯合物所組成的組群中的至少一者。 The electron transport layer or the electron injection layer may further comprise a substance capable of reducing a material forming the electron transport layer or the electron injection layer. As the reducing substance, any substance having a certain reducing property can be used. For example, an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, or an alkaline earth metal can be suitably used. Groups of oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes At least one of them.

作為較佳的還原性物質，可列舉Na(功函數為2.36 eV)、K(功函數為2.28 eV)、Rb(功函數為2.16 eV)或Cs(功函數為1.95 eV)等鹼金屬，或者Ca(功函數為2.9 eV)、Sr(功函數為2.0 eV~2.5 eV)或Ba(功函數為2.52 eV)等鹼土金屬，特佳為功函數為2.9 eV以下的還原性物質。該些還原性物質之中，更佳的還原性物質是K、Rb或Cs的鹼金屬，進而更佳為Rb或Cs，最佳為Cs。該些鹼金屬的還原能力特別高，藉由向形成電子傳輸層或電子注入層的材料中比較少量地添加該些鹼金屬，可謀求有機EL(Eleetroluminescence，電場發光)元件的發光亮度的提昇或長壽命化。另外，作為功函數為2.9 eV以下的還原性物質，2種以上的上述鹼金屬的組合亦較佳，特佳為包含Cs的組合，例如Cs與Na、Cs與K、Cs與Rb、或Cs與Na及K的組合。藉由包含Cs，可有效率地發揮還原能力，藉由添加至形成電子傳輸層或電子注入層的材料中，可謀求有機EL元件的發光亮度的提昇或長壽命化。 Preferred examples of the reducing substance include alkali metals such as Na (work function is 2.36 eV), K (work function is 2.28 eV), Rb (work function is 2.16 eV), or Cs (work function is 1.95 eV), or An alkaline earth metal such as Ca (work function is 2.9 eV), Sr (work function is 2.0 eV to 2.5 eV) or Ba (work function is 2.52 eV), and a reducing substance having a work function of 2.9 eV or less is particularly preferable. Among these reducing substances, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. The reduction ability of the alkali metal is particularly high, and by adding the alkali metal to a material which forms the electron transport layer or the electron injection layer in a relatively small amount, the luminance of the organic EL (e.g., electric field emission) element can be improved or Long life. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more kinds of the above alkali metals is also preferable, and particularly preferably a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or Cs. Combination with Na and K. By including Cs, the reducing ability can be efficiently exhibited, and by adding to the material forming the electron transport layer or the electron injecting layer, the luminance of the organic EL element can be improved or the life can be extended.

<有機電場發光元件中的陰極> <Cathode in Organic Electric Field Light-Emitting Element>

陰極108是發揮經由電子注入層107及電子傳輸層106而將電子注入至發光層105的作用者。 The cathode 108 is a function of injecting electrons into the light-emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

作為形成陰極108的材料，若為可將電子高效地注入至有機層的物質，則並無特別限定，可使用與形成陽極102的材料相同的材料。其中，較佳為錫、銦、鈣、鋁、銀、銅、鎳、鉻、金、鉑、鐵、鋅、鋰、鈉、鉀、銫及鎂等金屬或該些的合金(鎂-銀合金、鎂-銦合金、氟化鋰/鋁等的 鋁-鋰合金等)等。為了提高電子注入效率來提昇元件特性，有效的是鋰、鈉、鉀、銫、鈣、鎂或包含該些低功函數金屬的合金。但是，該些低功函數金屬一般於大氣中不穩定的情況多。為了改善該點，已知有例如向有機層中摻雜微量的鋰、銫或鎂，並使用穩定性高的電極的方法。作為其他摻雜劑，亦可使用如氟化鋰、氟化銫、氧化鋰及氧化銫般的無機鹽。但是，並不限定於該些。 The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as that of the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, rubidium, and magnesium or alloys thereof (magnesium-silver alloys) are preferred. , magnesium-indium alloy, lithium fluoride/aluminum, etc. Aluminum-lithium alloy, etc.). In order to improve the electron injection efficiency to enhance the characteristics of the element, lithium, sodium, potassium, barium, calcium, magnesium or an alloy containing the low work function metals is effective. However, these low work function metals are generally unstable in the atmosphere. In order to improve this point, for example, a method of doping a small amount of lithium, ruthenium or magnesium into an organic layer and using an electrode having high stability is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cerium oxide can also be used. However, it is not limited to these.

進而，可列舉如下的較佳例：為了保護電極而將鉑、金、銀、銅、鐵、錫、鋁及銦等金屬，或使用該些金屬的合金，及二氧化矽、二氧化鈦及氮化矽等無機物，聚乙烯醇，氯乙烯，烴系高分子化合物等進行積層。該些電極的製作方法只要為電阻加熱、電子線、濺鍍、離子鍍及塗佈等可取得導通的方法，則亦無特別限制。 Further, preferred examples include metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys using the metals, and ceria, titania, and nitridation for protecting the electrodes. An inorganic substance such as hydrazine, polyvinyl alcohol, vinyl chloride, or a hydrocarbon-based polymer compound is laminated. The methods for manufacturing the electrodes are as long as resistance heating and electron lines There is no particular limitation on the method of conducting the sputtering, the ion plating, the coating, and the like.

<可用於各層的黏結劑> <Binders that can be used for each layer>

用於以上的電洞注入層、電洞傳輸層、發光層、電子傳輸層及電子注入層的材料可單獨地形成各層，亦可分散於作為高分子黏結劑的聚氯乙烯、聚碳酸酯、聚苯乙烯、聚(N-乙烯咔唑)、聚甲基丙烯酸甲酯、聚甲基丙烯酸丁酯、聚酯、聚碸、聚苯醚、聚丁二烯、烴樹脂、酮樹脂、苯氧基樹脂、聚醯胺、乙基纖維素、乙酸乙烯酯樹脂、丙烯腈-丁二烯-苯乙烯(Acrylonitrile Butadiene Styrene，ABS)樹脂、聚胺基甲酸酯樹脂等溶劑可溶性樹脂，或者酚樹脂、二甲苯樹脂、石油樹脂、脲樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、醇酸樹脂、環氧樹脂、矽酮樹脂等硬化性樹脂 等中來使用。 The materials for the above hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and electron injection layer may be separately formed into layers, or may be dispersed in polyvinyl chloride, polycarbonate, or the like as a polymer binder. Polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polyfluorene, polyphenylene ether, polybutadiene, hydrocarbon resin, ketone resin, phenoxy Solvent-soluble resin such as base resin, polyamine, ethyl cellulose, vinyl acetate resin, acrylonitrile-butadiene-styrene (ABS) resin, polyurethane resin, or phenol resin , xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, fluorenone resin, etc. Use it in time.

<有機電場發光元件的製作方法> <Method for Producing Organic Electric Field Light-Emitting Element>

構成有機電場發光元件的各層可藉由利用蒸鍍法、電阻加熱蒸鍍、電子束蒸鍍、濺鍍、分子積層法、印刷法、旋塗法或澆鑄法、塗佈法等方法將應構成各層的材料製成薄膜來形成。以上述方式形成的各層的膜厚並無特別限定，可對應於材料的性質而適宜設定，但通常為2 nm~5000 nm的範圍。膜厚通常可利用石英振盪式膜厚測定裝置等來測定。當利用蒸鍍法進行薄膜化時，其蒸鍍條件根據材料的種類、作為膜的目標的結晶結構及締合結構等而不同。蒸鍍條件通常較佳為於舟皿加熱溫度+50℃~+400℃、真空度10-6 Pa~10-3 Pa、蒸鍍速度0.01 nm/秒~50 nm/秒、基板溫度-150℃~+300℃、膜厚2 nm~5 μm的範圍內適宜設定。 Each layer constituting the organic electroluminescent device can be formed by a vapor deposition method, resistance heating vapor deposition, electron beam evaporation, sputtering, molecular lamination method, printing method, spin coating method, casting method, coating method, or the like. The material of each layer is formed into a film. The film thickness of each layer formed as described above is not particularly limited and may be appropriately set depending on the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can be usually measured by a quartz oscillation type film thickness measuring device or the like. When the film formation is carried out by a vapor deposition method, the vapor deposition conditions differ depending on the type of the material, the crystal structure and the association structure which are the targets of the film. The evaporation condition is usually preferably at a heating temperature of the boat of +50 ° C to +400 ° C, a vacuum of 10 -6 Pa to 10 -3 Pa, an evaporation rate of 0.01 nm / sec to 50 nm / sec, and a substrate temperature of -150 ° C. It is suitable to set in the range of ~+300 °C and film thickness of 2 nm~5 μm.

其次，作為製作有機電場發光元件的方法的一例，對有機電場發光元件的製作法進行說明，該有機電場發光元件包括陽極/電洞注入層/電洞傳輸層/包含主體材料與摻雜劑材料的發光層/電子傳輸層/電子注入層/陰極。於適當的基板上，利用蒸鍍法等形成陽極材料的薄膜來製作陽極後，於該陽極上形成電洞注入層及電洞傳輸層的薄膜。於其上對主體材料與摻雜劑材料進行共蒸鍍而形成薄膜來作為發光層，於該發光層上形成電子傳輸層、電子注入層，進而利用蒸鍍法等形成包含陰極用物質的薄膜來作為陰極，藉此獲得作為目標的有機電場發光元件。再者，於上 述有機電場發光元件的製作中，亦可使製作順序相反，而以陰極、電子注入層、電子傳輸層、發光層、電洞傳輸層、電洞注入層、陽極的順序製作。 Next, a method of fabricating an organic electroluminescent device including an anode/hole injection layer/hole transport layer/including a host material and a dopant material will be described as an example of a method of fabricating an organic electric field light-emitting device. Light-emitting layer/electron transport layer/electron injection layer/cathode. A thin film of an anode material is formed on a suitable substrate by a vapor deposition method or the like to form an anode, and then a film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited to form a thin film as a light-emitting layer, an electron transport layer and an electron injection layer are formed on the light-emitting layer, and a film containing a cathode material is formed by a vapor deposition method or the like. As a cathode, an organic electric field light-emitting element as a target is obtained thereby. Again, on In the production of the organic electroluminescent device, the order of fabrication may be reversed, and the cathode, the electron injecting layer, the electron transporting layer, the light emitting layer, the hole transporting layer, the hole injecting layer, and the anode may be sequentially formed.

當對以上述方式獲得的有機電場發光元件施加直流電壓時，只要將陽極作為+的極性來施加，將陰極作為-的極性來施加即可，若施加2 V~40 V左右的電壓，則可自透明或半透明的電極側(陽極或陰極、及雙方)觀測發光。另外，該有機電場發光元件於施加有脈衝電流或交流電流的情況下亦發光。再者，施加的交流的波形可任意。 When a DC voltage is applied to the organic electroluminescent device obtained as described above, the anode may be applied as a polarity of +, and the cathode may be applied as a polarity of -, and when a voltage of about 2 V to 40 V is applied, Luminescence was observed from the transparent or translucent electrode side (anode or cathode, and both). Further, the organic electroluminescent element emits light even when a pulse current or an alternating current is applied. Furthermore, the waveform of the applied alternating current can be arbitrary.

<有機電場發光元件的應用例> <Application Example of Organic Electric Field Light-Emitting Element>

另外，本發明亦可應用於具備有機電場發光元件的顯示裝置或具備有機電場發光元件的照明裝置等。 Further, the present invention is also applicable to a display device including an organic electroluminescence device or an illumination device including an organic electroluminescence device.

具備有機電場發光元件的顯示裝置或照明裝置可藉由將本實施形態的有機電場發光元件與公知的驅動裝置連接等公知的方法來製造，且可適宜使用直流驅動、脈衝驅動、交流驅動等公知的驅動方法來進行驅動。 A display device or an illumination device including an organic electroluminescence device can be manufactured by a known method such as connecting an organic electroluminescence device of the present embodiment to a known driving device, and a DC drive, a pulse drive, an AC drive, or the like can be suitably used. The driving method is to drive.

作為顯示裝置，例如可列舉：彩色平板顯示器等面板顯示器、撓性彩色有機電場發光(EL)顯示器等撓性顯示器等(例如，參照日本專利特開平10-335066號公報、日本專利特開2003-321546號公報、日本專利特開2004-281086號公報等)。另外，作為顯示器的顯示方式，例如可列舉矩陣及/或分段方式等。再者，矩陣顯示與分段顯示可於相同的面板中共存。 For example, a flexible display such as a panel display such as a color flat panel display or a flexible color organic electroluminescence (EL) display can be used (for example, see Japanese Patent Laid-Open No. Hei 10-335066, Japanese Patent Laid-Open No. 2003-- Japanese Patent Publication No. 321546, Japanese Patent Laid-Open No. 2004-281086, and the like. Further, examples of the display method of the display include a matrix and/or a segmentation method. Furthermore, the matrix display and the segment display can coexist in the same panel.

所謂矩陣，是指將用於顯示的畫素二維地配置成格子 狀或馬賽克狀等而成者，其藉由畫素的集合來顯示文字或圖像。畫素的形狀或尺寸是根據用途來決定。例如於個人電腦、監視器、電視機的圖像及文字顯示中，通常使用一邊為300 μm以下的四邊形的畫素，另外，於如顯示面板般的大型顯示器的情況下，使用一邊為mm級的畫素。於單色顯示的情況下，只要排列相同顏色的畫素即可，於彩色顯示的情況下，使紅、綠、藍的畫素並列來進行顯示。於此情況下，典型的有三角型與條紋型。而且，作為該矩陣的驅動方法，可為線順序驅動方法或主動矩陣的任一者。線順序驅動有結構簡單這一優點，但於考慮了動作特性的情況下，有時主動矩陣更優異，因此驅動方法亦必須根據用途而區分使用。 The so-called matrix means that the pixels used for display are two-dimensionally arranged into a lattice. A shape, a mosaic, or the like, which displays a character or an image by a collection of pixels. The shape or size of the pixels is determined according to the purpose. For example, in the image and character display of a personal computer, a monitor, a television, a quadrilateral pixel having a side of 300 μm or less is usually used, and in the case of a large display such as a display panel, the use side is mm-level. The pixels. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, pixels of red, green, and blue are displayed in parallel. In this case, there are typically triangular and striped patterns. Further, as the driving method of the matrix, either the line sequential driving method or the active matrix may be used. The line sequential driving has the advantage of being simple in structure, but in the case where the operating characteristics are considered, the active matrix is sometimes more excellent, and therefore the driving method must also be used depending on the use.

於分段方式(類型)中，以顯示事先所決定的資訊的方式形成圖案，並使所決定的區域發光。例如可列舉：數位時鐘或溫度計中的時刻或溫度顯示、聲頻機器或電磁爐等的動作狀態顯示及汽車的面板顯示等。 In the segmentation method (type), a pattern is formed in such a manner as to display information determined in advance, and the determined region is illuminated. For example, a time or temperature display in a digital clock or a thermometer, an operation state display such as an audio device or an induction cooker, and a panel display of a car can be cited.

作為照明裝置，例如可列舉：室內照明等的照明裝置、液晶顯示裝置的背光源等(例如，參照日本專利特開2003-257621號公報、日本專利特開2003-277741號公報、日本專利特開2004-119211號公報等)。背光源主要為了提昇不進行自發光的顯示裝置的視認性而使用，其用於液晶顯示裝置、時鐘、聲頻裝置、汽車面板、顯示板及標識等。尤其，作為液晶顯示裝置之中，薄型化正成為課題的個人電腦用途的背光源，若考慮到先前方式的背光源因包含螢 光燈或導光板而難以薄型化，則使用本實施形態的發光元件的背光源具有薄型、輕量的特徵。 For example, an illumination device such as an indoor illumination, a backlight of a liquid crystal display device, and the like can be used, for example, Japanese Patent Laid-Open No. 2003-257621, Japanese Patent Laid-Open No. 2003-277741, and Japanese Patent Laid-Open Gazette 2004-119211, etc.). The backlight is mainly used for improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a logo, and the like. In particular, as a backlight for personal computer applications where thinning is becoming a problem among liquid crystal display devices, it is considered that the backlight of the prior art includes firefly. When the light or the light guide plate is difficult to be thinned, the backlight using the light-emitting element of the present embodiment has a thin and lightweight feature.

[實例] [Example] <苯并茀化合物的合成例> <Synthesis Example of Benzoindole Compound>

以下，對由式(1-1-24)、式(1-1-54)、式(1-1-84)、式(1-2-84)、式(1-1-70)、式(1-2-121)、式(1-2-85)、式(1-2-24)、式(1-2-174)、式(1-1-140)、式(1-1-101)、式(1-1-113)、式(1-1-1)、式(1-1-10)、式(1-1-123)、式(1-1-61)、式(1-1-76)、式(1-1-103)及式(1-1-154)所表示的化合物的合成例進行說明。 Hereinafter, the formula (1-1-24), the formula (1-1-54), the formula (1-1-84), the formula (1-2-84), the formula (1-1-70), and the formula (1-2-121), formula (1-2-85), formula (1-2-24), formula (1-2-174), formula (1-1-140), formula (1-1- 101), formula (1-1-113), formula (1-1-1), formula (1-1-10), formula (1-1-123), formula (1-1-61), formula ( 1-1-76), a synthesis example of the compound represented by the formula (1-1-103) and the formula (1-1-154) will be described.

[合成例1]化合物(1-1-24)的合成 [Synthesis Example 1] Synthesis of Compound (1-1-24)

<4-(第三丁基)-N-(4-(第三丁基)苯基)-N-苯基苯胺的合成> Synthesis of <4-(t-butyl)-N-(4-(t-butyl)phenyl)-N-phenylaniline>

於氮氣環境下，將加入有苯胺(20.0 g)、1-溴-4-(第三丁基)苯(100.0 g)、乙酸鈀(1.1 g)、三-第三丁基膦(2.8 g)、第三丁醇鈉(52.0 g)及甲苯(300ml)的燒瓶在回流溫度下攪拌14小時。將反應液冷卻至室溫為止後，利用鋪滿矽藻土的桐山漏斗進行濾除，然後向濾液中添加水及乙酸乙 酯來進行分液。將溶劑減壓餾去後，利用矽膠短柱(展開液：甲苯)進行精製。將溶劑減壓餾去後，於0.01 kPa、100℃的條件下餾去低沸點成分，而獲得4-(第三丁基)-N-(4-(第三丁基)苯基)-N-苯基苯胺(78.0 g)。 Under nitrogen, aniline (20.0 g), 1-bromo-4-(t-butyl)benzene (100.0 g), palladium acetate (1.1 g), tri-tert-butylphosphine (2.8 g) will be added. A flask of sodium butoxide (52.0 g) and toluene (300 ml) was stirred at reflux temperature for 14 hours. After cooling the reaction solution to room temperature, it was filtered off with a Kiriyama funnel covered with diatomaceous earth, and then water and acetic acid B were added to the filtrate. The ester is used for liquid separation. The solvent was distilled off under reduced pressure, and then purified by a silica gel short column (developing liquid: toluene). After distilling off the solvent under reduced pressure, the low-boiling component was distilled off at 0.01 kPa and 100 ° C to obtain 4-(t-butyl)-N-(4-(t-butyl)phenyl)-N. -Phenylaniline (78.0 g).

<4-溴-N,N-雙(4-(第三丁基)苯基)苯胺的合成> Synthesis of <4-bromo-N,N-bis(4-(t-butyl)phenyl)aniline>

於氮氣環境下，利用冰浴對溶解有4-(第三丁基)-N-(4-(第三丁基)苯基)-N-苯基苯胺(78.0 g)的四氫呋喃(Tetrahydrofuran，THF)(300 ml)溶液進行冷卻，然後一點點地添加N-溴丁二醯亞胺(38.0 g)。添加結束後，於室溫下攪拌1小時後，添加亞硫酸氫鈉水溶液，並使反應停止。將THF減壓餾去後，添加水進行抽吸過濾。利用矽膠短柱(展開液：甲苯)進行精製後，自庚烷中進行再結晶，而獲得4-溴-N,N-雙(4-(第三丁基)苯基)苯胺(79.4 g)。 Tetrahydrofuran (THF) in which 4-(t-butyl)-N-(4-(t-butyl)phenyl)-N-phenylaniline (78.0 g) was dissolved in an ice bath under a nitrogen atmosphere. (300 ml) The solution was cooled, and then N-bromosuccinimide (38.0 g) was added little by little. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and then an aqueous sodium hydrogensulfite solution was added to stop the reaction. After THF was distilled off under reduced pressure, water was added and suction filtered. After refining by a silica gel short column (developing solution: toluene), recrystallization was carried out from heptane to obtain 4-bromo-N,N-bis(4-(t-butyl)phenyl)aniline (79.4 g). .

<4-(第三丁基)-N-(4-(第三丁基)苯基)-N-(4-(4,4,5,5-四甲基-1,3,2-二氧雜硼烷-2-基)苯基)苯胺的合成> <4-(t-butyl)-N-(4-(t-butyl)phenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-di Synthesis of oxaborolan-2-yl)phenyl)aniline >

於氮氣環境下，將加入有4-溴-N,N-雙(4-(第三丁基)苯基)苯胺(79.4 g)、雙頻哪醇合二硼(bis(pinacolato)diboron)(55.0 g)、Pd(dppf)Cl2(4.4 g)、乙酸鉀(53.0 g)及環戊基甲醚(500 ml)的燒瓶在回流溫度下攪拌6小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠短柱(展開液：甲苯)進行精製。將溶劑減壓餾去後，利用庚烷進行清洗，而獲得4-(第三丁基)-N-(4-(第三丁基)苯 基)-N-(4-(4,4,5,5-四甲基-1,3,2-二氧雜硼烷-2-基)苯基)苯胺(74.3 g)。 Under nitrogen, 4-bromo-N,N-bis(4-(t-butyl)phenyl)aniline (79.4 g) and bis(pinacolato) diboron (bis(pinacolato) diboron) will be added. A flask of 55.0 g), Pd(dppf)Cl 2 (4.4 g), potassium acetate (53.0 g) and cyclopentyl methyl ether (500 ml) was stirred at reflux temperature for 6 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by a silica gel short column (developing liquid: toluene). The solvent was distilled off under reduced pressure and washed with heptane to give 4-(t-butyl)-N-(4-(t-butyl)phenyl)-N-(4-(4,4, 5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phenylamine (74.3 g).

<1-(4-(雙(4-(第三丁基)苯基)胺基)苯基)-2-萘甲酸甲酯的合成> Synthesis of <1-(4-(bis(4-(t-butyl)phenyl)amino)phenyl)-2-naphthoic acid methyl ester>

於氮氣環境下，將加入有利用公知的方法所合成的1-(((三氟甲基)磺醯基)氧基)-2-萘甲酸甲酯(61.0 g)、4-(第三丁基)-N-(4-(第三丁基)苯基)-N-(4-(4,4,5,5-四甲基-1,3,2-二氧雜硼烷-2-基)苯基)苯胺(74.3 g)、Pd(PPh3)4(1.8 g)、磷酸鉀(65.0 g)、甲苯(500 ml)、乙醇(150 ml)及水(50 ml)的燒瓶在回流溫度下攪拌2小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠進行精製，繼而利用活性氧化鋁短柱(展開液：甲苯/庚烷=1/1(容量比))進行精製，藉此獲得1-(4-(雙(4-(第三丁基)苯基)胺基)苯基)-2-萘甲酸甲酯(77.0 g)。 Methyl 1-(((trifluoromethyl)sulfonyl)oxy)-2-naphthoate (61.0 g), 4-(Third), synthesized by a known method, under a nitrogen atmosphere -N-(4-(t-butyl)phenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2- Flasks of phenyl)phenylamine (74.3 g), Pd(PPh 3 ) 4 (1.8 g), potassium phosphate (65.0 g), toluene (500 ml), ethanol (150 ml) and water (50 ml) were refluxed Stir at temperature for 2 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel, followed by purification using an activated alumina short column (developing solution: toluene/heptane = 1/1 (capacity ratio)), whereby 1-(4-(double) was obtained. Methyl 4-(t-butyl)phenyl)amino)phenyl)-2-naphthoate (77.0 g).

<2-(1-(4-(雙(4-(第三丁基)苯基)胺基)苯基)萘-2-基)丙烷-2-醇的合成> Synthesis of <2-(1-(4-(bis(4-(t-butyl)phenyl))amino)phenyl)naphthalen-2-yl)propan-2-ol >

於室溫．氮氣環境下，向加入有1-(4-(雙(4-(第三丁基)苯基)胺基)苯基)-2-萘甲酸甲酯(77.0 g)及THF(200 ml)的燒瓶中滴加甲基溴化鎂THF溶液(1.1 M，300 ml)。滴加結束後，於室溫下攪拌15小時，添加水並使反應停止。向反應液中添加乙酸乙酯及氯化銨水溶液來進行分液，進而利用水對乙酸乙酯層進行清洗。將溶劑減壓餾去後，利用活性氧化鋁管柱層析法(展開液：甲苯/乙酸乙酯混合溶 劑)進行精製。此時，參考「有機化學實驗入門(1)-物質處理法與分離精製法-」化學同人股份有限公司出版、第94頁中所記載的方法，緩慢地增加展開液中的乙酸乙酯的比率來使目標物溶出。將溶出液減壓餾去，而獲得2-(1-(4-(雙(4-(第三丁基)苯基)胺基)苯基)萘-2-基)丙烷-2-醇(44.0 g)。 At room temperature. To a solution of methyl 1-(4-(bis(4-(t-butyl)phenyl)amino)phenyl)-2-naphthoate (77.0 g) and THF (200 ml) A methyl magnesium bromide THF solution (1.1 M, 300 ml) was added dropwise to the flask. After completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours, and water was added to stop the reaction. Ethyl acetate and an aqueous ammonium chloride solution were added to the reaction liquid to carry out liquid separation, and the ethyl acetate layer was further washed with water. After distilling off the solvent under reduced pressure, it was subjected to activated alumina column chromatography (developing solution: toluene/ethyl acetate) Refining). At this time, the ratio of ethyl acetate in the developing solution is slowly increased by referring to the method described in "Introduction to Organic Chemistry (1) - Substance Treatment and Separation and Refining - "Chemical Co., Ltd., published on page 94). To dissolve the target. The eluate was distilled off under reduced pressure to give 2-(1-(4-(bis(4-(t-butyl)phenyl)amino)phenyl)phthalen-2-yl)propan-2-ol ( 44.0 g).

<N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺的合成> Synthesis of <N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-7H-benzo[c]indole-9-amine>

於室溫．氮氣環境下，向加入有2-(1-(4-(雙(4-(第三丁基)苯基)胺基)苯基)萘-2-基)丙烷-2-醇(44.0 g)及氯仿(400 ml)的燒瓶中滴加三氟化硼二***錯合物(16 g)。滴加結束後，添加水並使反應停止，然後利用碳酸氫鈉進行中和。進行分液後，將溶劑減壓餾去，然後利用活性氧化鋁管柱層析法(展開液：甲苯/庚烷=1/9(容量比))進行精製。進而，利用甲醇進行清洗，藉此獲得N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(38.0 g)。 At room temperature. 2-(1-(4-(bis(4-(t-butyl)phenyl))amino)phenyl)naphthalen-2-yl)propan-2-ol (44.0 g) was added under a nitrogen atmosphere. A boron trifluoride diethyl ether complex (16 g) was added dropwise to a flask of chloroform (400 ml). After the completion of the dropwise addition, water was added and the reaction was stopped, followed by neutralization with sodium hydrogencarbonate. After liquid separation, the solvent was distilled off under reduced pressure, and then purified by an activated alumina column chromatography (developing liquid: toluene / heptane = 1 / 9 (capacity ratio)). Further, washing with methanol was carried out, thereby obtaining N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-7H-benzo[c]indole-9-amine (38.0 g).

<5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺的合成> Synthesis of <5-bromo-N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-7H-benzo[c]indole-9-amine>

於氮氣環境下，一面利用冰浴對加入有N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(38.0 g)及THF(300 ml)的燒瓶進行冷卻，一面一點點添加N-溴丁二醯亞胺(13.6 g)。添加結束後，於室溫下攪拌15小時，然後添加亞硫酸氫鈉水溶液，並使反應停止。藉由抽吸過濾而取得所析出的固體，利用水對該固體進行清洗，繼而 利用甲醇對該固體進行清洗。進而，使該固體溶解於甲苯中並添加庚烷，而使其再沈澱，藉此獲得5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(33.3 g)。 N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-7H-benzo[c]fluoren-9-amine was added to the ice bath under nitrogen atmosphere. The flask (38.0 g) and THF (300 ml) were cooled, and N-bromosuccinimide (13.6 g) was added little by little. After completion of the addition, the mixture was stirred at room temperature for 15 hours, then an aqueous solution of sodium hydrogensulfite was added, and the reaction was stopped. The precipitated solid is obtained by suction filtration, and the solid is washed with water, and then The solid was washed with methanol. Further, the solid is dissolved in toluene and heptane is added to reprecipitate it, thereby obtaining 5-bromo-N,N-bis(4-(t-butyl)phenyl)-7,7-di Methyl-7H-benzo[c]indole-9-amine (33.3 g).

<化合物(1-1-24)的合成> <Synthesis of Compound (1-1-24)>

於氮氣環境下，將加入有咔唑(0.67 g)、5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(2.00 g)、Pd(dba)2(0.17 g)、三-第三丁基膦的1M甲苯溶液(0.9 ml)、第三丁醇鈉(0.50 g)及二甲苯(15 ml)的燒瓶在回流溫度下攪拌20小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用活性氧化鋁管柱層析法(展開液：甲苯/庚烷混合溶液)進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。繼而，利用矽膠管柱層析法(展開液：氯苯/庚烷=1/5(容量比))進行精製後，自甲苯中進行再結晶，而獲得由式(1-1-24)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-5-(9H-咔唑-9-基)-7,7-二甲基-7H-苯并[c]茀-9-胺(0.78 g)。 Under nitrogen, carbazole (0.67 g), 5-bromo-N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-7H-benzo[ c] fluorene 9-amine (2.00 g), Pd (dba ) 2 (0.17 g), three - 1M toluene solution of tert-butyl phosphine (0.9 ml), sodium tertiary butoxide (0.50 g) and xylene The (15 ml) flask was stirred at reflux temperature for 20 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by an activated alumina column chromatography (developing liquid: toluene/heptane mixed solution). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Then, it is purified by a silica gel column chromatography (developing liquid: chlorobenzene/heptane = 1/5 (capacity ratio)), and then recrystallized from toluene to obtain a formula (1-1-24). a compound represented by N,N-bis(4-(t-butyl)phenyl)-5-(9H-carbazol-9-yl)-7,7-dimethyl-7H-benzo[c ]茀-9-amine (0.78 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.79(d,1H),8.22(d,3H),7.71(s,1H),7.62(m,1H),7.26-7.40(m,12H),7.13(m,4H),7.05(d,2H),1.53(s,6H),1.35(s,18H)。 1 H-NMR (CDCl 3 ): δ=8.79 (d, 1H), 8.22 (d, 3H), 7.71 (s, 1H), 7.62 (m, 1H), 7.26-7.40 (m, 12H), 7.13 ( m, 4H), 7.05 (d, 2H), 1.53 (s, 6H), 1.35 (s, 18H).

[合成例2]化合物(1-1-54)的合成 [Synthesis Example 2] Synthesis of Compound (1-1-54)

<化合物(1-1-54)的合成> <Synthesis of Compound (1-1-54)>

於氮氣環境下，將加入有3,6-二-第三丁基-9H-咔唑(1.10 g)、5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(2.00 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.50 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌10小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/乙酸乙酯混合溶液)進行精製。此時，不改變展開液中的乙酸乙酯的量，而緩慢地增加甲苯/庚烷中的甲苯的比率來使目標物溶出。將溶劑減壓餾去後，溶解於乙酸乙酯中，然後添加甲醇，藉此進行再沈澱，進而利用活性碳管柱層析法(展開液：甲苯/庚烷=1/4(容量比))進行精製，而獲得由式(1-1-54)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-5-(3,6-二-第三丁基-9H-咔唑-9-基)-7,7-二甲基-7H-苯并[c]茀-9-胺(0.99 g)。 Under nitrogen, 3,6-di-t-butyl-9H-carbazole (1.10 g), 5-bromo-N,N-bis(4-(t-butyl)phenyl)- 1,7-Dimethyl-7H-benzo[c]indole-9-amine (2.00 g), Pd(dba) 2 (0.06 g), tris-tert-butylphosphine in 1 M toluene (0.3 ml The flask of sodium butoxide (0.50 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 10 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (eluent: toluene / heptane / ethyl acetate mixture). At this time, the amount of ethyl acetate in the developing solution was not changed, and the ratio of toluene in toluene/heptane was gradually increased to elute the target. The solvent was distilled off under reduced pressure, and then dissolved in ethyl acetate, and then methanol was added thereto to carry out reprecipitation, and further by activated carbon column chromatography (developing solution: toluene / heptane = 1/4 (capacity ratio) Purification is carried out to obtain a compound represented by the formula (1-1-54), that is, N,N-bis(4-(t-butyl)phenyl)-5-(3,6-di-third Butyl-9H-carbazol-9-yl)-7,7-dimethyl-7H-benzo[c]indole-9-amine (0.99 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.79(d,1H),8.21(m,3H), 7.60-7.70(m,2H),7.46(m,1H),7.40(dd,2H),7.05-7.20(m,11H),6.97(d,2H),1.48(s,24H),1.35(s,18H)。 1 H-NMR (CDCl 3 ): δ = 8.79 (d, 1H), 8.21 (m, 3H), 7.60-7.70 (m, 2H), 7.46 (m, 1H), 7.40 (dd, 2H), 7.05- 7.20 (m, 11H), 6.97 (d, 2H), 1.48 (s, 24H), 1.35 (s, 18H).

[合成例3]化合物(1-1-84)的合成 [Synthesis Example 3] Synthesis of Compound (1-1-84)

<化合物(1-1-84)的合成> <Synthesis of Compound (1-1-84)>

於氮氣環境下，將加入有3,6-二苯基-9H-咔唑(1.30 g)、5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(2.00 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.50 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌8小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/乙酸乙酯=5/95/1(容量比))進行精製。將溶劑減壓餾去後，利用活性碳管柱層析法(展開液：甲苯/庚烷=7/3(容量比))進行精製。將溶劑減壓餾去後，自庚烷中進行再結晶，而獲得由式(1-1-84)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-5-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基 -7H-苯并[c]茀-9-胺(1.13 g)。 Under nitrogen, 3,6-diphenyl-9H-carbazole (1.30 g), 5-bromo-N,N-bis(4-(t-butyl)phenyl)-7,7 will be added. - 1 M toluene solution (0.3 ml) of dimethyl-7H-benzo[c]indole-9-amine (2.00 g), Pd(dba) 2 (0.06 g), tri-tert-butylphosphine, A flask of sodium tributolate (0.50 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 8 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene / heptane / ethyl acetate = 5 / 95 / 1 (capacity ratio)). The solvent was distilled off under reduced pressure, and then purified by an activated carbon column chromatography (developing liquid: toluene / heptane = 7 / 3 (capacity ratio)). After the solvent is distilled off under reduced pressure, it is recrystallized from heptane to obtain a compound represented by formula (1-1-84), that is, N,N-bis(4-(t-butyl)phenyl) 5-(3,6-Diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-7H-benzo[c]indole-9-amine (1.13 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.83(d,1H),8.48(m,2H),8.23(d,1H),7.75(m,5H),7.64(d,1H),7.62(dd,2H),7.45-7.51(m,5H),7.30-7.39(m,8H),7.14(m,7H),1.53(s,6H),1.35(s,18H)。 1 H-NMR (CDCl 3 ): δ=8.83 (d, 1H), 8.48 (m, 2H), 8.23 (d, 1H), 7.75 (m, 5H), 7.64 (d, 1H), 7.62 (dd, 2H), 7.45-7.51 (m, 5H), 7.30-7.39 (m, 8H), 7.14 (m, 7H), 1.53 (s, 6H), 1.35 (s, 18H).

[合成例4]化合物(1-2-84)的合成 [Synthesis Example 4] Synthesis of Compound (1-2-84)

<5-氯-2-(萘-1-基)苯甲酸甲酯的合成> Synthesis of <5-Chloro-2-(naphthalen-1-yl)benzoic acid methyl ester>

於氮氣環境下，將加入有1-萘硼酸(38.0 g)、2-溴-5-氯苯甲酸甲酯(50.0 g)、Pd(PPh3)4(2.3 g)、磷酸鉀(85.0 g)、甲苯(500 ml)、2-丙醇(150 ml)及水(50 ml)的燒瓶在回流溫度下攪拌2小時。將反應液冷卻至室溫為止後，添加水來進行分液，然後將溶劑減壓餾去。利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)對所獲得的油狀物質進行精製，而獲得5-氯-2-(萘-1-基)苯甲酸甲酯(58.3 g)。此時，緩慢地增加展開液中的甲苯的比率來使目標物 溶出。 Under a nitrogen atmosphere, 1-naphthalene boronic acid (38.0 g), methyl 2-bromo-5-chlorobenzoate (50.0 g), Pd(PPh 3 ) 4 (2.3 g), potassium phosphate (85.0 g) will be added. A flask of toluene (500 ml), 2-propanol (150 ml) and water (50 ml) was stirred at reflux temperature for 2 hours. After cooling the reaction liquid to room temperature, water was added to carry out liquid separation, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by a silica gel column chromatography (developing liquid: toluene/heptane mixed solvent) to obtain methyl 5-chloro-2-(naphthalen-1-yl)benzoate (58.3 g). ). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target.

<2-(5-氯-2-(萘-1-基)苯基)丙烷-2-醇的合成> Synthesis of <2-(5-chloro-2-(naphthalen-1-yl)phenyl)propan-2-ol >

於氮氣環境下，利用水浴對溶解有5-氯-2-(萘-1-基)苯甲酸甲酯(58.0 g)的THF(250 ml)溶液進行冷卻，然後向該溶液中滴加甲基溴化鎂THF溶液(1.1 M，300 ml)。滴加結束後，卸除水浴，並於30℃下攪拌3小時。其後，利用冰浴進行冷卻，並添加氯化銨水溶液，使反應停止，將約一半的THF減壓餾去。向該溶液中添加乙酸乙酯，進行分液後，將溶劑減壓餾去。利用活性氧化鋁管柱層析法(展開液：甲苯/庚烷混合溶劑)對所獲得的固體進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。繼而，將溶出液減壓餾去後，利用庚烷對所獲得的固體進行清洗，而獲得2-(5-氯-2-(萘-1-基)苯基)丙烷-2-醇(43.0 g)。 The solution of methyl 5-chloro-2-(naphthalen-1-yl)benzoate (58.0 g) in THF (250 ml) was cooled with a water bath under a nitrogen atmosphere, and then a methyl group was added dropwise to the solution. Magnesium bromide THF solution (1.1 M, 300 ml). After the completion of the dropwise addition, the water bath was removed and stirred at 30 ° C for 3 hours. Thereafter, the mixture was cooled in an ice bath, and an aqueous ammonium chloride solution was added to stop the reaction, and about half of the THF was distilled off under reduced pressure. Ethyl acetate was added to the solution, and after liquid separation, the solvent was distilled off under reduced pressure. The obtained solid was purified by activated alumina column chromatography (developing solution: toluene/heptane mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Then, after the eluate was distilled off under reduced pressure, the obtained solid was washed with heptane to obtain 2-(5-chloro-2-(naphthalen-1-yl)phenyl)propan-2-ol (43.0). g).

<9-氯-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <9-chloro-7,7-dimethyl-7H-benzo[c]indole>

於氮氣環境下，利用冰浴對加入有三氟化硼二***錯合物(29.0 g)及氯仿(400 ml)的燒瓶進行冷卻，然後向其中滴加2-(5-氯-2-(萘-1-基)苯基)丙烷-2-醇(43.0 g)的氯仿溶液。滴加結束後，卸除冰浴，於室溫下攪拌1小時後，添加水並使反應停止。繼而，添加碳酸氫鈉進行中和，並進行分液，然後將溶劑減壓餾去，藉此獲得9-氯-7,7-二甲基-7H-苯并[c]茀(41.3 g)。 The flask to which boron trifluoride diethyl ether complex (29.0 g) and chloroform (400 ml) were added was cooled in an ice bath, and then 2-(5-chloro-2-(naphthalene) was added dropwise thereto. A solution of -1-yl)phenyl)propan-2-ol (43.0 g) in chloroform. After completion of the dropwise addition, the ice bath was removed, and after stirring at room temperature for 1 hour, water was added and the reaction was stopped. Then, sodium hydrogencarbonate was added for neutralization, and liquid separation was carried out, and then the solvent was distilled off under reduced pressure, thereby obtaining 9-chloro-7,7-dimethyl-7H-benzo[c]indole (41.3 g). .

<9-氯-5-碘-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <9-chloro-5-iodo-7,7-dimethyl-7H-benzo[c]indole>

於氮氣環境下，將加入有9-氯-7,7-二甲基-7H-苯并[c] 茀(41.3 g)、碘(3.9 g)、正過碘酸(2.6 g)、乙酸(200 ml)及硫酸(4 ml)的燒瓶在100℃下攪拌4小時。將反應液冷卻至室溫為止後，添加亞硫酸氫鈉水溶液，使反應停止，進而添加乙酸乙酯來進行分液。將溶劑減壓餾去，利用矽膠短柱(展開液：甲苯)對所獲得的油狀物質進行精製。進而，利用矽膠管柱層析法(展開液：庚烷)進行精製，而獲得9-氯-5-碘-7,7-二甲基-7H-苯并[c]茀(8.1 g)。 Under a nitrogen atmosphere, 9-chloro-7,7-dimethyl-7H-benzo[c] will be added. A flask of hydrazine (41.3 g), iodine (3.9 g), n-periodic acid (2.6 g), acetic acid (200 ml) and sulfuric acid (4 ml) was stirred at 100 ° C for 4 hours. After cooling the reaction liquid to room temperature, an aqueous solution of sodium hydrogensulfite was added to stop the reaction, and ethyl acetate was further added to carry out liquid separation. The solvent was distilled off under reduced pressure, and the obtained oily substance was purified using a silica gel short column (developing liquid: toluene). Further, it was purified by silica gel column chromatography (developing solution: heptane) to give 9-chloro-5-iodo-7,7-dimethyl-7H-benzo[c]indole (8.1 g).

<N,N-雙(4-(第三丁基)苯基)-9-氯-7,7-二甲基-7H-苯并[c]茀-5-胺的合成> Synthesis of <N,N-bis(4-(t-butyl)phenyl)-9-chloro-7,7-dimethyl-7H-benzo[c]indole-5-amine>

於氮氣環境下，將加入有9-氯-5-碘-7,7-二甲基-7H-苯并[c]茀(4.0 g)、雙(4-(第三丁基)苯基)胺(2.8 g)、雙(三-鄰甲苯基膦)-二氯化鈀(II)(PdCl2(o-tolyl3)2)(0.4 g)、第三丁醇鈉(1.4 g)及1,2,4-三甲基苯(30 ml)的燒瓶在130℃下攪拌3小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/乙酸乙酯=5/95/1(容量比))進行精製，繼而利用活性氧化鋁管柱層析法(展開液：甲苯/庚烷/乙酸乙酯=5/95/1(容量比))進行精製。將溶劑減壓餾去後，使其溶解於甲醇中，然後添加水，藉此進行再沈澱，而獲得N,N-雙(4-(第三丁基)苯基)-9-氯-7,7-二甲基-7H-苯并[c]茀-5-胺(4.0 g)。 Under a nitrogen atmosphere, 9-chloro-5-iodo-7,7-dimethyl-7H-benzo[c]indole (4.0 g), bis(4-(t-butyl)phenyl) will be added. Amine (2.8 g), bis(tri-o-tolylphosphine)-palladium(II) chloride (PdCl 2 (o-tolyl 3 ) 2 ) (0.4 g), sodium butoxide (1.4 g) and 1 The 2,4-trimethylbenzene (30 ml) flask was stirred at 130 ° C for 3 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing liquid: toluene / heptane / ethyl acetate = 5 / 95 / 1 (capacity ratio)), followed by activated alumina column chromatography The method (developing solution: toluene/heptane/ethyl acetate = 5/95/1 (capacity ratio)) was purified. After distilling off the solvent under reduced pressure, it was dissolved in methanol, and then water was added thereto to carry out reprecipitation to obtain N,N-bis(4-(t-butyl)phenyl)-9-chloro-7. , 7-Dimethyl-7H-benzo[c]indole-5-amine (4.0 g).

<化合物(1-2-84)的合成> <Synthesis of Compound (1-2-84)>

於氮氣環境下，將加入有N,N-雙(4-(第三丁基)苯基)-9-氯-7,7-二甲基-7H-苯并[c]茀-5-胺(2.0 g)、3,6-二苯 基-9H-咔唑(1.4 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.5 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌8小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。使將溶劑減壓餾去而獲得的固體溶解於氯苯中，然後添加庚烷，藉此使其再沈澱，而獲得由式(1-2-84)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-9-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-7H-苯并[c]茀-5-胺(2.3 g)。 Under nitrogen, N,N-bis(4-(t-butyl)phenyl)-9-chloro-7,7-dimethyl-7H-benzo[c]indole-5-amine will be added. (2.0 g), 3,6-diphenyl-9H-carbazole (1.4 g), Pd(dba) 2 (0.06 g), tris-tert-butylphosphine in 1 M toluene (0.3 ml), A flask of sodium tributoxide (0.5 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 8 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solid obtained by distilling off the solvent under reduced pressure is dissolved in chlorobenzene, and then heptane is added thereto to reprecipitate it, thereby obtaining a compound represented by the formula (1-2-84), that is, N,N- Bis(4-(t-butyl)phenyl)-9-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-7H-benzo[c]茀-5-amine (2.3 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.82(d,1H),8.55(d,1H),8.44(m,2H),8.16(d,1H),7.68-7.76(m,8H),7.66(t,1H),7.60(d,2H),7.55(s,1H),7.50(t,4H)7.43(m,1H),7.36(t,2H),7.22(d,4H),7.01(d,4H),1.58(s,6H),1.30(s,18H)。 1 H-NMR (CDCl 3 ): δ=8.82 (d, 1H), 8.55 (d, 1H), 8.44 (m, 2H), 8.16 (d, 1H), 7.68-7.76 (m, 8H), 7.66 ( t,1H), 7.60 (d, 2H), 7.55 (s, 1H), 7.50 (t, 4H) 7.43 (m, 1H), 7.36 (t, 2H), 7.22 (d, 4H), 7.01 (d, 4H), 1.58 (s, 6H), 1.30 (s, 18H).

[合成例5]化合物(1-1-70)的合成 [Synthesis Example 5] Synthesis of Compound (1-1-70)

<5-溴-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <5-bromo-7,7-dimethyl-7H-benzo[c]indole>

於氮氣環境下，將加入有7,7-二甲基-7H-苯并[c]茀(10.0 g)、N-溴丁二醯亞胺(7.3 g)及乙酸(200 ml)的 燒瓶在70℃下攪拌1小時。將反應液冷卻至室溫為止後，添加亞硫酸氫鈉水溶液，繼而添加乙酸乙酯來進行分液。將有機層的溶劑減壓餾去，利用甲醇對所獲得的固體進行清洗後，自庚烷中進行再結晶，繼而自乙酸乙酯/乙醇混合溶劑中進行再結晶，藉此獲得5-溴-7,7-二甲基-7H-苯并[c]茀(11.0 g)。 Under nitrogen, 7,7-dimethyl-7H-benzo[c]indole (10.0 g), N-bromosuccinimide (7.3 g) and acetic acid (200 ml) were added. The flask was stirred at 70 ° C for 1 hour. After cooling the reaction liquid to room temperature, an aqueous solution of sodium hydrogensulfite was added, followed by addition of ethyl acetate to carry out liquid separation. The solvent of the organic layer was distilled off under reduced pressure, and the obtained solid was washed with methanol, and then recrystallized from heptane, followed by recrystallization from a mixed solvent of ethyl acetate/ethanol to obtain 5-bromo- 7,7-Dimethyl-7H-benzo[c]indole (11.0 g).

<5-溴-9-碘-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c]indole>

於氮氣環境下，將加入有5-溴-7,7-二甲基-7H-苯并[c]茀(11.0 g)、碘(3.4 g)、碘酸(3.0 g)、乙酸(200 ml)及硫酸(4 ml)的燒瓶在120℃下攪拌2小時。將反應液冷卻至室溫為止後，添加亞硫酸氫鈉水溶液，使反應停止，繼而添加可中和所使用的硫酸的量的碳酸鈉。進而，添加甲苯及水來進行分液，將有機層的溶劑減壓餾去後，利用矽膠管柱層析法(展開液：庚烷)進行精製。將溶劑減壓餾去，向所獲得的油狀物質中添加庚烷，藉此進行再沈澱，而獲得5-溴-9-碘-7,7-二甲基-7H-苯并[c]茀(10.0 g)。 Under nitrogen, 5-bromo-7,7-dimethyl-7H-benzo[c]indole (11.0 g), iodine (3.4 g), iodic acid (3.0 g), acetic acid (200 ml) will be added. The flask with sulfuric acid (4 ml) was stirred at 120 ° C for 2 hours. After cooling the reaction liquid to room temperature, an aqueous sodium hydrogen sulfite solution was added to stop the reaction, followed by the addition of sodium carbonate in an amount capable of neutralizing the sulfuric acid used. Further, toluene and water were added to carry out liquid separation, and the solvent of the organic layer was distilled off under reduced pressure, and then purified by a silica gel column chromatography (developing liquid: heptane). The solvent was distilled off under reduced pressure, and heptane was added to the obtained oily substance to thereby reprecipitate to obtain 5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c].茀 (10.0 g).

<5-溴-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺的合成> Synthesis of <5-bromo-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]fluoren-9-amine>

於氮氣環境下，將加入有5-溴-9-碘-7,7-二甲基-7H-苯并[c]茀(5.0 g)、N-苯基萘-1-胺(2.4 g)、(PdCl2(o-tolyl3)2)(0.3 g)、第三丁醇鈉(1.6 g)及1,2,4-三甲基苯(50 ml)的燒瓶在90℃下攪拌12小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將有機層的溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/乙酸 乙酯=5/95/1(容量比))進行精製。向將溶劑減壓餾去而獲得的油狀物質中添加庚烷，藉此進行再沈澱，進而使所獲得的固體溶解於氯苯中後添加庚烷，藉此再次進行再沈澱，而獲得5-溴-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(3.6 g)。 Under a nitrogen atmosphere, 5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c]indole (5.0 g), N-phenylnaphthalen-1-amine (2.4 g) will be added. , (PdCl 2 (o-tolyl 3 ) 2 ) (0.3 g), sodium butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) were stirred at 90 ° C for 12 hours. . After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent of the organic layer was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing liquid: toluene / heptane / ethyl acetate = 5 / 95 / 1 (capacity ratio)). By adding heptane to the oily substance obtained by distilling off the solvent under reduced pressure, reprecipitation is carried out, and the obtained solid is dissolved in chlorobenzene, and then heptane is added to reprecipitate again to obtain 5 -Bromo-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]indole-9-amine (3.6 g).

<化合物(1-1-70)的合成> <Synthesis of Compound (1-1-70)>

於氮氣環境下，將加入有5-溴-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(2.0 g)、3,6-二苯基-9H-咔唑(1.3 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.50 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌8小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/乙酸乙酯=10/90/1(容量比))進行精製。進而利用活性碳管柱層析法(展開液：甲苯)進行精製後，溶解於乙酸乙酯中，然後添加庚烷，藉此進行再沈澱，而獲得由式(1-1-70)所表示的化合物，即5-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(1.1 g)。 Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]fluorene-9-amine (2.0 g) will be added. , 3,6-diphenyl-9H-carbazole (1.3 g), Pd(dba) 2 (0.06 g), tris-tert-butylphosphine in 1 M toluene (0.3 ml), third butanol A flask of sodium (0.50 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 8 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene / heptane / ethyl acetate = 10 / 90/1 (capacity ratio)). Further, it is purified by activated carbon column chromatography (developing solution: toluene), dissolved in ethyl acetate, and then added with heptane to carry out reprecipitation, thereby obtaining a formula (1-1-70). a compound, 5-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H- Benzo[c]indole-9-amine (1.1 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.79(d,1H),8.47(m,2H),8.20(d,1H),8.00(d,1H),7.93(d,1H),7.82(d,1H),7.74(m,5H),7.62(m,3H),7.33-7.55(m,12H),7.24-7.30(m,3H),7.17(m,2H),7.12(d,2H),7.06(dd,1H),7.01(t,1H),1.47(s,6H)。 1 H-NMR (CDCl 3 ): δ = 8.79 (d, 1H), 8.47 (m, 2H), 8.20 (d, 1H), 8.00 (d, 1H), 7.93 (d, 1H), 7.82 (d, 1H), 7.74 (m, 5H), 7.62 (m, 3H), 7.33-7.55 (m, 12H), 7.24-7.30 (m, 3H), 7.17 (m, 2H), 7.12 (d, 2H), 7.06 (dd, 1H), 7.01 (t, 1H), 1.47 (s, 6H).

[合成例6]化合物(1-2-121)的合成 [Synthesis Example 6] Synthesis of Compound (1-2-121)

<2-溴-5-氟苯甲酸甲酯的合成> <Synthesis of methyl 2-bromo-5-fluorobenzoate>

於氮氣環境下，將加入有2-溴-5-氟苯甲酸(50.0 g)、硫酸(7 ml)及甲醇(500 ml)的燒瓶在回流溫度下攪拌8小時。將反應液冷卻至室溫為止後，將甲醇減壓餾去，然後添加乙酸乙酯及碳酸氫鈉水溶液來進行分液。將有機層的溶劑減壓餾去，而獲得2-溴-5-氟苯甲酸甲酯(50.0 g)。 The flask to which 2-bromo-5-fluorobenzoic acid (50.0 g), sulfuric acid (7 ml) and methanol (500 ml) were added was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After cooling the reaction liquid to room temperature, methanol was distilled off under reduced pressure, and then ethyl acetate and an aqueous sodium hydrogencarbonate solution were added to carry out liquid separation. The solvent of the organic layer was evaporated under reduced pressure to give ethyl 2-bromo-5-fluorobenzoate (50.0 g).

<5-氟-2-(萘-1-基)苯甲酸甲酯的合成> Synthesis of <5-fluoro-2-(naphthalen-1-yl)benzoic acid methyl ester>

於氮氣環境下，將加入有1-萘硼酸(38.7 g)、2-溴-5-氯苯甲酸甲酯(50.0 g)、Pd(PPh3)4(2.5 g)、磷酸鉀(91.0 g)、二甲苯(500 ml)、2-丙醇(150 ml)及水(50 ml)的燒瓶在回流溫度下攪拌2個半小時。將反應液冷卻至室溫為止後，添加水來進行分液，然後將溶劑減壓餾去。利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)對所獲得的油狀物質進行精製，而獲得5-氟-2-(萘-1-基)苯甲酸甲酯(58.0 g)。此時，緩慢地增加展開液中的甲苯的比率來使 目標物溶出。 Under a nitrogen atmosphere, 1-naphthalene boronic acid (38.7 g), methyl 2-bromo-5-chlorobenzoate (50.0 g), Pd(PPh 3 ) 4 (2.5 g), potassium phosphate (91.0 g) will be added. A flask of xylene (500 ml), 2-propanol (150 ml) and water (50 ml) was stirred at reflux temperature for two and a half hours. After cooling the reaction liquid to room temperature, water was added to carry out liquid separation, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by a silica gel column chromatography (developing liquid: toluene/heptane mixed solvent) to obtain methyl 5-fluoro-2-(naphthalen-1-yl)benzoate (58.0 g). ). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target.

<2-(5-氟-2-(萘-1-基)苯基)丙烷-2-醇的合成> Synthesis of <2-(5-fluoro-2-(naphthalen-1-yl)phenyl)propan-2-ol >

於氮氣環境下，利用水浴對溶解有5-氟-2-(萘-1-基)苯甲酸甲酯(58.0 g)的THF(250 ml)溶液進行冷卻，然後向該溶液中滴加甲基溴化鎂THF溶液(1.0 M，540 ml)。滴加結束後，卸除水浴，並於30℃下攪拌3小時。其後，利用冰浴進行冷卻，然後添加氯化銨水溶液，使反應停止，並將約一半的THF減壓餾去。向該溶液中添加乙酸乙酯，進行分液後，將溶劑減壓餾去。利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)對所獲得的固體進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。繼而，自乙酸乙酯/庚烷混合溶劑中進行再結晶，藉此獲得2-(5-氟-2-(萘-1-基)苯基)丙烷-2-醇(46.0 g)。 A solution of methyl 5-fluoro-2-(naphthalen-1-yl)benzoate (58.0 g) in THF (250 ml) was cooled with a water bath under a nitrogen atmosphere, and then a methyl group was added dropwise to the solution. Magnesium bromide THF solution (1.0 M, 540 ml). After the completion of the dropwise addition, the water bath was removed and stirred at 30 ° C for 3 hours. Thereafter, the mixture was cooled with an ice bath, and then an aqueous ammonium chloride solution was added to stop the reaction, and about half of the THF was distilled off under reduced pressure. Ethyl acetate was added to the solution, and after liquid separation, the solvent was distilled off under reduced pressure. The obtained solid was purified by a silica gel column chromatography (developing solution: toluene/heptane mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Then, recrystallization was carried out from a mixed solvent of ethyl acetate / heptane, whereby 2-(5-fluoro-2-(naphthalen-1-yl)phenyl)propan-2-ol (46.0 g) was obtained.

<9-氟-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <9-fluoro-7,7-dimethyl-7H-benzo[c]indole>

於氮氣環境下，利用冰浴對加入有三氟化硼二***錯合物(33.0 g)及氯仿(100 ml)的燒瓶進行冷卻，然後向其中滴加2-(5-氟-2-(萘-1-基)苯基)丙烷-2-醇(46.0 g)的氯仿溶液。滴加結束後，卸除冰浴，於室溫下攪拌10分鐘後，添加水並使反應停止。繼而，添加碳酸氫鈉進行中和，進行分液後，將有機層的溶劑減壓餾去。利用矽膠管柱層析法(展開液：庚烷)對所獲得的油狀物質進行精製，藉此獲得9-氟-7,7-二甲基-7H-苯并[c]茀(40.0 g)。 The flask to which boron trifluoride diethyl ether complex (33.0 g) and chloroform (100 ml) were added was cooled in an ice bath under a nitrogen atmosphere, and then 2-(5-fluoro-2-(naphthalene) was added dropwise thereto. A solution of -1-yl)phenyl)propan-2-ol (46.0 g) in chloroform. After completion of the dropwise addition, the ice bath was removed, and after stirring at room temperature for 10 minutes, water was added and the reaction was stopped. Then, sodium hydrogencarbonate was added for neutralization, and after liquid separation, the solvent of the organic layer was distilled off under reduced pressure. The obtained oily substance was purified by a silica gel column chromatography (developing liquid: heptane), whereby 9-fluoro-7,7-dimethyl-7H-benzo[c]indole (40.0 g) was obtained. ).

<5-溴-9-氟-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <5-bromo-9-fluoro-7,7-dimethyl-7H-benzo[c]indole >

於氮氣環境下，將加入有9-氟-7,7-二甲基-7H-苯并[c] 茀(40.0 g)、N-溴丁二醯亞胺(28.5 g)及乙酸(400 ml)的燒瓶在70℃下攪拌2小時。將反應液冷卻至室溫為止後，添加亞硫酸氫鈉水溶液，繼而添加甲苯來進行分液。將有機層的溶劑減壓餾去，利用矽膠管柱層析法(展開液：庚烷)對所獲得的油狀物質進行精製，藉此獲得5-溴-9-氟-7,7-二甲基-7H-苯并[c]茀(50.0 g)。 Under a nitrogen atmosphere, 9-fluoro-7,7-dimethyl-7H-benzo[c] will be added. A flask of hydrazine (40.0 g), N-bromosuccinimide (28.5 g) and acetic acid (400 ml) was stirred at 70 ° C for 2 hours. After cooling the reaction liquid to room temperature, an aqueous solution of sodium hydrogen sulfite was added, followed by the addition of toluene to carry out liquid separation. The solvent of the organic layer was distilled off under reduced pressure, and the obtained oily substance was purified by silica gel column chromatography (developing liquid: heptane), whereby 5-bromo-9-fluoro-7,7-di was obtained. Methyl-7H-benzo[c]indole (50.0 g).

<9-(5-溴-7,7-二甲基-7H-苯并[c]茀-9-基)-3,6-二苯基-9H-咔唑的合成> Synthesis of <9-(5-bromo-7,7-dimethyl-7H-benzo[c]fluoren-9-yl)-3,6-diphenyl-9H-carbazole >

於氮氣環境下，將加入有5-溴-9-氟-7,7-二甲基-7H-苯并[c]茀(2.0 g)、3,6-二苯基-9H-咔唑(2.2 g)、碳酸銫(2.9 g)及N-甲基吡咯啶酮(15 ml)的燒瓶在180℃下攪拌8小時。將反應液冷卻至室溫為止後，添加水及甲苯來進行分液，然後將溶劑減壓餾去。向所獲得的油狀物質中添加乙醇來進行再沈澱後，利用矽膠管柱層析法(展開液：庚烷/甲苯=9/1(容積比))進行精製。將溶劑減壓餾去，利用庚烷對所獲得的固體進行清洗，而獲得9-(5-溴-7,7-二甲基-7H-苯并[c]茀-9-基)-3,6-二苯基-9H-咔唑(3.3 g)。 Under a nitrogen atmosphere, 5-bromo-9-fluoro-7,7-dimethyl-7H-benzo[c]indole (2.0 g) and 3,6-diphenyl-9H-carbazole ( A flask of 2.2 g), cesium carbonate (2.9 g) and N-methylpyrrolidone (15 ml) was stirred at 180 ° C for 8 hours. After cooling the reaction liquid to room temperature, water and toluene were added to carry out liquid separation, and the solvent was distilled off under reduced pressure. After ethanol was added to the obtained oily substance to carry out reprecipitation, it was purified by a silica gel column chromatography (developing liquid: heptane / toluene = 9 / 1 (volume ratio)). The solvent was distilled off under reduced pressure, and the obtained solid was washed with heptane to obtain 9-(5-bromo-7,7-dimethyl-7H-benzo[c]fluoren-9-yl)-3. , 6-diphenyl-9H-carbazole (3.3 g).

<化合物(1-2-121)的合成> <Synthesis of Compound (1-2-121)>

於氮氣環境下，將加入有9-(5-溴-7,7-二甲基-7H-苯并[c]茀-9-基)-3,6-二苯基-9H-咔唑(1.6 g)、N-苯基-4-(三甲基矽烷基)苯胺(0.6 g)、Pd(dba)2(0.02 g)、4-二甲胺基苯基二第三丁基膦(0.02 g)、第三丁醇鈉(0.60 g)及二甲苯(15 ml)的燒瓶在90℃下攪拌3小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減 壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/三乙胺=10/90/1(容量比))進行精製。將溶劑減壓餾去，使所獲得的固體溶解於甲苯中，然後添加庚烷，藉此進行再沈澱，而獲得由式(1-2-121)所表示的化合物，即9-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N-苯基-N-(4-(三甲基矽烷基)苯基)-7H-苯并[c]茀-5-胺(1.8 g)。 Under the nitrogen atmosphere, 9-(5-bromo-7,7-dimethyl-7H-benzo[c]fluoren-9-yl)-3,6-diphenyl-9H-carbazole ( 1.6 g), N-phenyl-4-(trimethyldecyl)aniline (0.6 g), Pd(dba) 2 (0.02 g), 4-dimethylaminophenyldibutylphosphine (0.02) The flasks of g), sodium butoxide (0.60 g) and xylene (15 ml) were stirred at 90 ° C for 3 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene / heptane / triethylamine = 10 / 90/1 (capacity ratio)). The solvent is distilled off under reduced pressure, and the obtained solid is dissolved in toluene, and then heptane is added, whereby reprecipitation is carried out to obtain a compound represented by the formula (1-2-121), that is, 9-(3, 6-Diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-N-phenyl-N-(4-(trimethyldecyl)phenyl)-7H-benzo[ c] indole-5-amine (1.8 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.83(d,1H),8.56(d,1H),8.44(m,2H),8.13(d,1H),7.70-7.78(m,8H),7.67(t,1H),7.60(d,2H),7.55(s,1H),7.50(t,4H),7.44(t,1H),7.37(m,4H),7.24(d,2H),7.15(m,2H),7.05(d,2H),6.99(t,1H),1.58(s,6H),0.25(s,9H)。 1 H-NMR (CDCl 3 ): δ=8.83 (d, 1H), 8.56 (d, 1H), 8.44 (m, 2H), 8.13 (d, 1H), 7.70-7.78 (m, 8H), 7.67 ( t,1H), 7.60 (d, 2H), 7.55 (s, 1H), 7.50 (t, 4H), 7.44 (t, 1H), 7.37 (m, 4H), 7.24 (d, 2H), 7.15 (m) , 2H), 7.05 (d, 2H), 6.99 (t, 1H), 1.58 (s, 6H), 0.25 (s, 9H).

[合成例7]化合物(1-2-85)的合成 [Synthesis Example 7] Synthesis of Compound (1-2-85)

<化合物(1-2-85)的合成> <Synthesis of Compound (1-2-85)>

於氮氣環境下，將加入有9-(5-溴-7,7-二甲基-7H-苯并[c]茀-9-基)-3,6-二苯基-9H-咔唑(1.6 g)、4-(第三丁 基)-N-(4-(三甲基矽烷基)苯基)苯胺(0.7 g)、Pd(dba)2(0.02 g)、4-二甲胺基苯基二第三丁基膦(0.02 g)、第三丁醇鈉(0.6 g)及二甲苯(15 ml)的燒瓶在90℃下攪拌2小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，溶解於氯苯中，然後添加乙酸乙酯，藉此進行再沈澱，而獲得由式(1-2-85)所表示的化合物，即N-(4-(第三丁基)苯基)-9-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N-(4-(三甲基矽烷基)苯基)-7H-苯并[c]茀-5-胺(1.8 g)。 Under the nitrogen atmosphere, 9-(5-bromo-7,7-dimethyl-7H-benzo[c]fluoren-9-yl)-3,6-diphenyl-9H-carbazole ( 1.6 g), 4-(t-butyl)-N-(4-(trimethyldecyl)phenyl)phenylamine (0.7 g), Pd(dba) 2 (0.02 g), 4-dimethylamino group A flask of phenylditributylphosphine (0.02 g), sodium butoxide (0.6 g) and xylene (15 ml) was stirred at 90 ° C for 2 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent is distilled off under reduced pressure, dissolved in chlorobenzene, and then ethyl acetate is added thereto to carry out reprecipitation, thereby obtaining a compound represented by the formula (1-2-85), that is, N-(4-( Tributyl)phenyl)-9-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-N-(4-(trimethyldecyl)benzene Base)-7H-benzo[c]indole-5-amine (1.8 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.83(d,1H),8.56(d,1H),8.44(m,2H),8.15(d,1H),7.70-7.78(m,8H),7.66(t,1H),7.61(d,2H),7.58(s,1H),7.50(t,4H),7.45(t,1H),7.32-7.38(m,4H),7.25(d,2H),7.11(d,2H),7.01(d,2H),1.59(s,6H),1.31(s,9H),0.24(s,9H)。 1 H-NMR (CDCl 3 ): δ=8.83 (d, 1H), 8.56 (d, 1H), 8.44 (m, 2H), 8.15 (d, 1H), 7.70-7.78 (m, 8H), 7.66 ( t,1H), 7.61 (d, 2H), 7.58 (s, 1H), 7.50 (t, 4H), 7.45 (t, 1H), 7.32-7.38 (m, 4H), 7.25 (d, 2H), 7.11 (d, 2H), 7.01 (d, 2H), 1.59 (s, 6H), 1.31 (s, 9H), 0.24 (s, 9H).

[合成例8]化合物(1-2-24)的合成 [Synthesis Example 8] Synthesis of Compound (1-2-24)

<化合物(1-2-24)的合成> <Synthesis of Compound (1-2-24)>

於氮氣環境下，將加入有N,N-雙(4-(第三丁基)苯 基)-9-氯-7,7-二甲基-7H-苯并[c]茀-5-胺(1.0 g)、9H-咔唑(0.4 g)、Pd(dba)2(0.03 g)、三-第三丁基膦的1 M甲苯溶液(0.2 ml)、第三丁醇鈉(0.3 g)及1,2,4-三甲基苯(10 ml)的燒瓶在150℃下攪拌2小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)對將溶劑減壓餾去而獲得的固體進行精製，而獲得由式(1-2-24)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-9-(9H-咔唑-9-基)-7,7-二甲基-7H-苯并[c]茀-5-胺(0.8 g)。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。 Under nitrogen, N,N-bis(4-(t-butyl)phenyl)-9-chloro-7,7-dimethyl-7H-benzo[c]indole-5-amine will be added. (1.0 g), 9H-carbazole (0.4 g), Pd(dba) 2 (0.03 g), tris-tert-butylphosphine in 1 M toluene (0.2 ml), sodium butoxide (0.3 g) The flask of 1,2,4-trimethylbenzene (10 ml) was stirred at 150 ° C for 2 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solid obtained by distilling off the solvent under reduced pressure is purified by a silica gel column chromatography (developing liquid: toluene/heptane mixed solvent) to obtain a compound represented by formula (1-2-24), that is, N. , N-bis(4-(t-butyl)phenyl)-9-(9H-carbazol-9-yl)-7,7-dimethyl-7H-benzo[c]indole-5-amine (0.8 g). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target.

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.80(d,1H),8.52(d,1H),8.18(d,2H),8.16(d,1H),7.71(m,1H),7.64(m,2H),7.52(m,3H),7.40-7.47(m,3H),7.31(t,2H),7.21(d,4H),7.01(d,4H),1.55(s,6H),1.30(s,18H)。 1 H-NMR (CDCl 3 ): δ = 8.80 (d, 1H), 8.52 (d, 1H), 8.18 (d, 2H), 8.16 (d, 1H), 7.71 (m, 1H), 7.64 (m, 2H), 7.52 (m, 3H), 7.40-7.47 (m, 3H), 7.31 (t, 2H), 7.21 (d, 4H), 7.01 (d, 4H), 1.55 (s, 6H), 1.30 (s) , 18H).

[合成例9]化合物(1-2-174)的合成 [Synthesis Example 9] Synthesis of Compound (1-2-174)

<5-甲基-2-硝基-1,1'：3',1"-聯三苯的合成> Synthesis of <5-Methyl-2-nitro-1,1':3',1"-bitriphenyl>

於氮氣環境下，將加入有2-氯-4-甲基-1-硝基苯(7.3 g)、1,1'-聯苯-3-基硼酸(8.8 g)、Pd(PPh3)4(0.5 g)、碳酸鈉(11.8 g)、二甲苯(80 ml)、乙醇(20 ml)及水(20 ml)的燒瓶在回流溫度下攪拌4小時。將反應液冷卻至室溫為止後，添加水來進行分液，然後利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)對有機層進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。將溶出液減壓餾去，而獲得5-甲基-2-硝基-1,1'：3',1"-聯三苯(12.1 g)。 Under a nitrogen atmosphere, 2-chloro-4-methyl-1-nitrobenzene (7.3 g), 1,1'-biphenyl-3-ylboronic acid (8.8 g), Pd(PPh 3 ) 4 will be added. (0.5 g), a flask of sodium carbonate (11.8 g), xylene (80 ml), ethanol (20 ml) and water (20 ml) was stirred at reflux temperature for 4 hours. After cooling the reaction liquid to room temperature, water was added to carry out liquid separation, and the organic layer was purified by a silica gel column chromatography (developing liquid: toluene/heptane mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. The eluate was distilled off under reduced pressure to give 5-methyl-2-nitro-1,1':3',1"-biphenyl (12.1 g).

<6-甲基-1-苯基-9H-咔唑及3-甲基-6-苯基-9H-咔唑的合成> Synthesis of <6-Methyl-1-phenyl-9H-carbazole and 3-methyl-6-phenyl-9H-carbazole>

於氮氣環境下，將加入有5-甲基-2-硝基-1,1'：3',1"-聯三苯(12.1 g)、三苯基膦(27.0 g)及N-甲基吡咯啶酮(90 ml)的燒瓶在160℃下攪拌16小時。將反應液冷卻至室溫為止後，利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)進行精製，而獲得6-甲基-1-苯基-9H-咔唑(6.3 g)及3-甲基-6-苯基-9H-咔唑(3.0 g)。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。 Under the nitrogen atmosphere, 5-methyl-2-nitro-1,1':3',1"-biphenyl (12.1 g), triphenylphosphine (27.0 g) and N-methyl group were added. The pyrrolidone (90 ml) flask was stirred at 160 ° C for 16 hours, and the reaction liquid was cooled to room temperature, and then purified by a silica gel column chromatography (developing solution: toluene / heptane mixed solvent). 6-Methyl-1-phenyl-9H-carbazole (6.3 g) and 3-methyl-6-phenyl-9H-carbazole (3.0 g). At this time, slowly increase the toluene in the developing solution. The ratio is to dissolve the target.

<化合物(1-2-174)的合成> <Synthesis of Compound (1-2-174)>

於氮氣環境下，將加入有N,N-雙(4-(第三丁基)苯基)-9-氯-7,7-二甲基-7H-苯并[c]茀-5-胺(1.0 g)、6-甲基-1-苯基-9H-咔唑(0.6 g)、Pd(dba)2(0.03 g)、三-第三丁基膦的1 M甲苯溶液(0.2 ml)、第三丁醇鈉(0.3 g)及1,2,4-三甲基苯(10 ml)的燒瓶在160℃下攪拌2小時。將反應 液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)對將溶劑減壓餾去而獲得的固體進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。進而，利用活性碳管柱層析法(展開液：甲苯/庚烷=1/1(容量比))進行精製後，利用庚烷進行清洗，藉此獲得由式(1-2-174)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-9-(6-甲基-1-苯基-9H-咔唑-9-基)-7H-苯并[c]茀-5-胺(1.1 g)。 Under nitrogen, N,N-bis(4-(t-butyl)phenyl)-9-chloro-7,7-dimethyl-7H-benzo[c]indole-5-amine will be added. (1.0 g), 6-methyl-1-phenyl-9H-carbazole (0.6 g), Pd(dba) 2 (0.03 g), tris-tert-butylphosphine in 1 M toluene (0.2 ml) A flask of sodium butoxide (0.3 g) and 1,2,4-trimethylbenzene (10 ml) was stirred at 160 ° C for 2 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solid obtained by distilling off the solvent under reduced pressure was purified by a silica gel column chromatography (developing liquid: toluene/heptane mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Further, it is purified by activated carbon column chromatography (developing solution: toluene/heptane = 1/1 (capacity ratio)), and then washed with heptane to obtain a formula (1-2-174). The compound represented, ie, N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-9-(6-methyl-1-phenyl-9H-carbazole-9 -yl)-7H-benzo[c]indole-5-amine (1.1 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.68(d,1H),8.18(m,1H),8.12(d,1H),8.10(d,1H),8.00(s,1H),7.60(t,1H),7.44(s,1H),7.38(m,3H),7.17-7.27(m,9H),6.85-7.05(m,8H),2.57(s,3H),1.53(s,6H),1.29(s,18H)。 1 H-NMR (CDCl 3 ): δ=8.68 (d, 1H), 8.18 (m, 1H), 8.12 (d, 1H), 8.10 (d, 1H), 8.00 (s, 1H), 7.60 (t, 1H), 7.44 (s, 1H), 7.38 (m, 3H), 7.17-7.27 (m, 9H), 6.85-7.05 (m, 8H), 2.57 (s, 3H), 1.53 (s, 6H), 1.29 (s, 18H).

[合成例10]化合物(1-1-140)的合成 [Synthesis Example 10] Synthesis of Compound (1-1-140)

<化合物(1-1-140)的合成> <Synthesis of Compound (1-1-140)>

於氮氣環境下，將加入有5-溴-7,7-二甲基-N-(萘-1- 基)-N-苯基-7H-苯并[c]茀-9-胺(1.9 g)、3-甲基-6-苯基-9H-咔唑(1.0 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.5 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌8小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷=3/7(容量比))進行精製。進而，利用活性碳管柱層析法(展開液：甲苯/庚烷=1/1(容量比))進行精製，而獲得由式(1-1-140)所表示的化合物，即7,7-二甲基-5-(3-甲基-6-苯基-9H-咔唑-9-基)-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(1.3 g)。 Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]fluoren-9-amine (1.9 g) will be added. , 3-methyl-6-phenyl-9H-carbazole (1.0 g), Pd(dba) 2 (0.06 g), tri-t-butylphosphine in 1 M toluene (0.3 ml), third A flask of sodium butoxide (0.5 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 8 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing liquid: toluene / heptane = 3 / 7 (capacity ratio)). Further, it is purified by activated carbon column chromatography (developing solution: toluene/heptane = 1/1 (capacity ratio)) to obtain a compound represented by formula (1-1-140), that is, 7,7 -Dimethyl-5-(3-methyl-6-phenyl-9H-carbazol-9-yl)-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]茀-9-amine (1.3 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.77(d,1H),8.39(m,1H),8.18(d,1H),8.06(s,1H),8.00(d,1H),7.92(d,1H),7.82(d,1H),7.72(m,3H),7.62(t,1H),7.58(dd,1H),7.52(t,1H),7.48(m,3H),7.42(m,2H),7.38(d,1H),7.34(m,2H),7.26(m,3H),7.18(m,3H),7.07(m,2H),7.00(t,1H),6.98(d,1H),2.58(s,3H),1.45(m,6H)。 1 H-NMR (CDCl 3 ): δ=8.77 (d, 1H), 8.39 (m, 1H), 8.18 (d, 1H), 8.06 (s, 1H), 8.00 (d, 1H), 7.92 (d, 1H), 7.82 (d, 1H), 7.72 (m, 3H), 7.62 (t, 1H), 7.58 (dd, 1H), 7.52 (t, 1H), 7.48 (m, 3H), 7.42 (m, 2H) ), 7.38 (d, 1H), 7.34 (m, 2H), 7.26 (m, 3H), 7.18 (m, 3H), 7.07 (m, 2H), 7.00 (t, 1H), 6.98 (d, 1H) , 2.58 (s, 3H), 1.45 (m, 6H).

[合成例11]化合物(1-1-101)的合成 [Synthesis Example 11] Synthesis of Compound (1-1-101)

<化合物(1-1-101)的合成> <Synthesis of Compound (1-1-101)>

於氮氣環境下，將加入有5-溴-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(1.8 g)、3,5-二甲基-9H-咔唑(0.7 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.5 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌4小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷=2/8(容量比))進行精製。進而，利用活性碳管柱層析法(展開液：甲苯/庚烷=1/1(容量比))進行精製，而獲得由式(1-1-101)所表示的化合物，即5-(3,6-二甲基-9H-咔唑-9-基)-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(1.4 g)。 Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]fluorene-9-amine (1.8 g) will be added. , 3,5-Dimethyl-9H-carbazole (0.7 g), Pd(dba) 2 (0.06 g), tris-tert-butylphosphine in 1 M toluene (0.3 ml), third butanol A flask of sodium (0.5 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 4 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing liquid: toluene / heptane = 2 / 8 (capacity ratio)). Further, it is purified by activated carbon column chromatography (developing solution: toluene/heptane = 1/1 (capacity ratio)) to obtain a compound represented by formula (1-1-101), that is, 5-( 3,6-Dimethyl-9H-carbazol-9-yl)-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]indole- 9-amine (1.4 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.74(d,1H),8.17(d,1H),7.99(m,3H),7.92(d,1H),7.81(d,1H),7.65(s,1H),7.60(t,1H),7.52(t,1H),7.48(t,1H),7.35-7.44(m,3H),7.23-7.32(m,4H),7.15(m,4H),7.05(dd,1H),7.00(t,1H),6.91(d,2H),2.55(s,6H),1.43(s,6H)。 1 H-NMR (CDCl 3 ): δ = 8.74 (d, 1H), 8.17 (d, 1H), 7.99 (m, 3H), 7.92 (d, 1H), 7.81 (d, 1H), 7.65 (s, 1H), 7.60 (t, 1H), 7.52 (t, 1H), 7.48 (t, 1H), 7.35-7.44 (m, 3H), 7.23-7.32 (m, 4H), 7.15 (m, 4H), 7.05 (dd, 1H), 7.00 (t, 1H), 6.91 (d, 2H), 2.55 (s, 6H), 1.43 (s, 6H).

[合成例12]化合物(1-1-113)的合成 [Synthesis Example 12] Synthesis of Compound (1-1-113)

<化合物(1-1-113)的合成> <Synthesis of Compound (1-1-113)>

於氮氣環境下，將加入有3,6-二甲基-9H-咔唑(0.78 g)、5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(2.00 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.50 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌6小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去並利用甲醇對所獲得的固體進行清洗後，利用矽膠管柱層析法(展開液：甲苯/庚烷)進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。將溶劑減壓餾去並使所獲得的固體於甲苯/庚烷混合溶劑中再沈澱，而獲得由式(1-1-113)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-5-(3,6-二甲基-9H-咔唑-9-基)-7,7-二甲基-7H-苯并[c]茀-9-胺(1.7 g)。 Under nitrogen, 3,6-dimethyl-9H-carbazole (0.78 g), 5-bromo-N,N-bis(4-(t-butyl)phenyl)-7,7 will be added. - 1 M toluene solution (0.3 ml) of dimethyl-7H-benzo[c]indole-9-amine (2.00 g), Pd(dba) 2 (0.06 g), tri-tert-butylphosphine, A flask of sodium tributoxide (0.50 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 6 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was washed with methanol, and then purified by silica gel column chromatography (developing liquid: toluene / heptane). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. The solvent is distilled off under reduced pressure, and the obtained solid is reprecipitated in a toluene/heptane mixed solvent to obtain a compound represented by the formula (1-1-113), that is, N,N-bis (4-( Tributyl)phenyl)-5-(3,6-dimethyl-9H-carbazol-9-yl)-7,7-dimethyl-7H-benzo[c]indole-9-amine ( 1.7 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.78(d,1H),8.21(d,1H),7.98(s,2H),7.67(s,1H),7.61(t,1H),7.40(d,1H),7.31(m,6H),7.09-7.17(m,7H),6.93(d,2H),2.56(s,6H),1.48(s,6H), 1.34(s,18H)。 1 H-NMR (CDCl 3 ): δ = 8.78 (d, 1H), 8.21 (d, 1H), 7.78 (s, 2H), 7.67 (s, 1H), 7.61 (t, 1H), 7.40 (d, 1H), 7.31 (m, 6H), 7.09-7.17 (m, 7H), 6.93 (d, 2H), 2.56 (s, 6H), 1.48 (s, 6H), 1.34 (s, 18H).

[合成例13]化合物(1-1-1)的合成 [Synthesis Example 13] Synthesis of Compound (1-1-1)

<5-氯-2-(4-氟萘-1-基)苯甲酸甲酯的合成> Synthesis of <5-chloro-2-(4-fluoronaphthalen-1-yl)benzoic acid methyl ester>

於氮氣環境下，將加入有4-氟萘-1-硼酸(92.0 g)、2-溴-5-氯苯甲酸甲酯(120.0 g)、Pd(PPh3)4(15.0 g)、磷酸鉀(204.0 g)、甲苯(800 ml)、乙醇(200 ml)及水(200 ml)的燒瓶在回流溫度下攪拌4小時。將反應液冷卻至室溫為止，添加水來進行分液後，利用矽膠管柱層析法(展開液：甲苯)進行精製，而獲得5-氯-2-(4-氟萘-1-基)苯甲酸甲酯(150.0 g)。 Under a nitrogen atmosphere, 4-fluoronaphthalene-1-boronic acid (92.0 g), methyl 2-bromo-5-chlorobenzoate (120.0 g), Pd(PPh 3 ) 4 (15.0 g), potassium phosphate were added. A flask of (204.0 g), toluene (800 ml), ethanol (200 ml) and water (200 ml) was stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, and water was added to carry out liquid separation, followed by purification by a silica gel column chromatography (developing solution: toluene) to obtain 5-chloro-2-(4-fluoronaphthalen-1-yl group). Methyl benzoate (150.0 g).

<2-(5-氯-2-(4-氟萘-1-基)苯基)丙烷-2-醇的合成> Synthesis of <2-(5-chloro-2-(4-fluoronaphthalen-1-yl)phenyl)propan-2-ol >

於氮氣環境下，利用冰浴對溶解有5-氯-2-(4-氟萘-1-基)苯甲酸甲酯(150.0 g)的環戊基甲醚(800 ml)溶液進行冷卻，然後向該溶液中滴加甲基氯化鎂THF溶液(3.0M，320 ml)。滴加結束後，卸除水浴，於室溫下攪拌2個半小時後，於60℃下進而攪拌1小時。其後，利用冰浴進行冷卻，並添加氯化銨水溶液，使反應停止，將約一半的THF減壓餾去。向該溶液中添加乙酸乙酯，進行分液 後，利用矽膠管柱層析法(展開液：甲苯)進行精製，而獲得2-(5-氯-2-(4-氟萘-1-基)苯基)丙烷-2-醇(100.0 g)。 Cooling a solution of methyl 5-chloro-2-(4-fluoronaphthalen-1-yl)benzoate (150.0 g) in cyclopentyl methyl ether (800 ml) with an ice bath under a nitrogen atmosphere, then Methylmagnesium chloride THF solution (3.0 M, 320 ml) was added dropwise to the solution. After completion of the dropwise addition, the water bath was removed, and the mixture was stirred at room temperature for 2 and a half hours, and further stirred at 60 ° C for 1 hour. Thereafter, the mixture was cooled in an ice bath, and an aqueous ammonium chloride solution was added to stop the reaction, and about half of the THF was distilled off under reduced pressure. Adding ethyl acetate to the solution for liquid separation Thereafter, it was purified by a silica gel column chromatography (developing solution: toluene) to obtain 2-(5-chloro-2-(4-fluoronaphthalen-1-yl)phenyl)propan-2-ol (100.0 g). ).

<9-氯-5-氟-7,7-二甲基-7H-苯并[c]茀的合成> Synthesis of <9-chloro-5-fluoro-7,7-dimethyl-7H-benzo[c]indole>

於氮氣環境下，利用冰浴對加入有2-(5-氯-2-(4-氟萘-1-基)苯基)丙烷-2-醇(100.0 g)及氯仿(2000 ml)的燒瓶進行冷卻，然後向其中滴加三氟化硼二***錯合物(54.0 g)。滴加結束後，卸除冰浴，於室溫下攪拌1.5小時後，添加甲醇並使反應停止。繼而，添加碳酸氫鈉進行中和，進行分液後，利用矽膠管柱層析法(展開液：庚烷)進行精製，藉此獲得9-氯-5-氟-7,7-二甲基-7H-苯并[c]茀(64.0 g)。 A flask containing 2-(5-chloro-2-(4-fluoronaphthalen-1-yl)phenyl)propan-2-ol (100.0 g) and chloroform (2000 ml) was added to an ice bath under a nitrogen atmosphere. After cooling, boron trifluoride diethyl ether complex (54.0 g) was added dropwise thereto. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1.5 hours, then methanol was added and the reaction was stopped. Then, sodium hydrogencarbonate was added for neutralization, and after liquid separation, it was purified by a silica gel column chromatography (developing liquid: heptane), thereby obtaining 9-chloro-5-fluoro-7,7-dimethyl group. -7H-benzo[c]indole (64.0 g).

<9-(9-氯-7,7-二甲基-7H-苯并[c]茀-5-基)-9H-咔唑的合成> Synthesis of <9-(9-chloro-7,7-dimethyl-7H-benzo[c]indole-5-yl)-9H-carbazole>

於氮氣環境下，將加入有9-氯-5-氟-7,7-二甲基-7H-苯并[c]茀(40.0 g)、咔唑(27.0 g)、碳酸銫(65.9 g)及二甲基亞碸(DMSO(Dimethyl sulfoxide)、650 ml)的燒瓶在120℃下攪拌5小時。確認反應結束後，將DMSO減壓餾去。繼而，添加甲苯及水來進行分液後，利用矽膠管柱層析法(展開液：庚烷/甲苯=1(容積比))進行精製，而獲得9-(9-氯-7,7-二甲基-7H-苯并[c]茀-5-基)-9H-咔唑(55.1 g)。 Under nitrogen, 9-chloro-5-fluoro-7,7-dimethyl-7H-benzo[c]indole (40.0 g), carbazole (27.0 g), cesium carbonate (65.9 g) will be added. A flask of dimethyl sulfoxide (DMSO (650 ml)) was stirred at 120 ° C for 5 hours. After confirming the completion of the reaction, DMSO was distilled off under reduced pressure. Then, toluene and water were added for liquid separation, and then purified by a silica gel column chromatography (developing solution: heptane / toluene = 1 (volume ratio)) to obtain 9-(9-chloro-7,7- Dimethyl-7H-benzo[c]indole-5-yl)-9H-indazole (55.1 g).

<化合物(1-1-1)的合成> <Synthesis of Compound (1-1-1)>

於氮氣環境下，將加入有9-(9-氯-7,7-二甲基-7H-苯并[c]茀-5-基)-9H-咔唑(18.0 g)、二苯基胺(7.6 g)、Pd(dba)2 (0.2 g)、4-二甲胺基苯基二第三丁基膦(0.2 g)、第三丁醇鈉(4.7 g)及二甲苯(160 ml)的燒瓶在回流溫度下攪拌1小時。將反應液冷卻至室溫為止後，添加水及甲苯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷=1/3(容量比))進行精製。繼而，利用活性碳管柱層析法(展開液：甲苯)進行精製後，自甲苯中進行再結晶，而獲得由式(1-1-1)所表示的化合物，即5-(9H-咔唑-9-基)-7,7-二甲基-N,N-二苯基-7H-苯并[c]茀-9-胺(17.0 g)。 9-(9-chloro-7,7-dimethyl-7H-benzo[c]indol-5-yl)-9H-indazole (18.0 g), diphenylamine was added under a nitrogen atmosphere. (7.6 g), Pd(dba) 2 (0.2 g), 4-dimethylaminophenyl ditributylphosphine (0.2 g), sodium butoxide (4.7 g) and xylene (160 ml) The flask was stirred at reflux temperature for 1 hour. After cooling the reaction liquid to room temperature, water and toluene were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing liquid: toluene / heptane = 1/3 (capacity ratio)). Then, it is purified by activated carbon column chromatography (developing solution: toluene), and then recrystallized from toluene to obtain a compound represented by formula (1-1-1), that is, 5-(9H-oxime). Azul-9-yl)-7,7-dimethyl-N,N-diphenyl-7H-benzo[c]indole-9-amine (17.0 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.80(d,1H),8.23(m,3H),7.71(s,1H),7.64(t,1H),7.26-7.39(m,11H),7.20(m,4H),7.16(dd,1H),7.07(m,4H),1.49(s,6H)。 1 H-NMR (CDCl 3 ): δ = 8.80 (d, 1H), 8.23 (m, 3H), 7.71 (s, 1H), 7.64 (t, 1H), 7.26-7.39 (m, 11H), 7.20 ( m, 4H), 7.16 (dd, 1H), 7.07 (m, 4H), 1.49 (s, 6H).

[合成例14]化合物(1-1-10)的合成 [Synthesis Example 14] Synthesis of Compound (1-1-10)

<化合物(1-1-10)的合成> <Synthesis of Compound (1-1-10)>

於氮氣環境下，將加入有9-(9-氯-7,7-二甲基-7H-苯并[c]茀-5-基)-9H-咔唑(18.0 g)、N-苯基萘-1-胺(9.8 g)、Pd(dba)2(0.2 g)、4-二甲胺基苯基二第三丁基膦(0.2 g)、 第三丁醇鈉(4.7 g)及二甲苯(160 ml)的燒瓶在回流溫度下攪拌2小時。將反應液冷卻至室溫為止後，添加水及甲苯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷=1/2(容量比))進行精製。繼而，利用活性碳管柱層析法(展開液：甲苯)進行精製後，自甲苯中進行再結晶，而獲得由式(1-1-10)所表示的化合物，即5-(9H-咔唑-9-基)-7,7-二甲基-N-(萘-1-基)-N-苯基-7H-苯并[c]茀-9-胺(15.6 g)。 9-(9-chloro-7,7-dimethyl-7H-benzo[c]indole-5-yl)-9H-carbazole (18.0 g), N-phenyl group was added under a nitrogen atmosphere. Naphthalen-1-amine (9.8 g), Pd(dba) 2 (0.2 g), 4-dimethylaminophenyldibutylphosphine (0.2 g), sodium butoxide (4.7 g) and A flask of toluene (160 ml) was stirred at reflux temperature for 2 hours. After cooling the reaction liquid to room temperature, water and toluene were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing liquid: toluene / heptane = 1/2 (capacity ratio)). Then, it is purified by activated carbon column chromatography (developing solution: toluene), and then recrystallized from toluene to obtain a compound represented by formula (1-1-10), that is, 5-(9H-oxime). Azul-9-yl)-7,7-dimethyl-N-(naphthalen-1-yl)-N-phenyl-7H-benzo[c]indole-9-amine (15.6 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.76(d,1H),8.21(d,2H),8.18(d,1H),7.99(d,1H),7.92(d,1H),7.81(d,1H),7.69(s,1H),7.60(t,1H),7.52(t,1H),7.48(t,1H),7.42(d,1H),7.24-7.40(m,10H),7.16(m,2H),7.04(m,3H),7.00(t,1H),1.44(s,6H)。 1 H-NMR (CDCl 3 ): δ = 8.76 (d, 1H), 8.21 (d, 2H), 8.18 (d, 1H), 7.99 (d, 1H), 7.92 (d, 1H), 7.81 (d, 1H), 7.69 (s, 1H), 7.60 (t, 1H), 7.52 (t, 1H), 7.48 (t, 1H), 7.42 (d, 1H), 7.24-7.40 (m, 10H), 7.16 (m) , 2H), 7.04 (m, 3H), 7.00 (t, 1H), 1.44 (s, 6H).

[合成例15]化合物(1-1-123)的合成 [Synthesis Example 15] Synthesis of Compound (1-1-123)

<5-溴-7,7-二甲基-N-苯基-N-(4-(三甲基矽烷基)苯 基)-7H-苯并[c]茀-9-胺的合成> <5-Bromo-7,7-dimethyl-N-phenyl-N-(4-(trimethyldecyl)benzene Synthesis of -7H-benzo[c]fluoren-9-amine>

於氮氣環境下，將加入有5-溴-9-碘-7,7-二甲基-7H-苯并[c]茀(5.0 g)、N-苯基-4-(三甲基矽烷基)苯胺(2.7 g)、(PdCl2(o-tolyl3)2)(0.3 g)、第三丁醇鈉(1.6 g)及1,2,4-三甲基苯(50 ml)的燒瓶在120℃下攪拌2小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將有機層的溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/三乙胺=5/95/1(容量比))進行精製後，進而利用活性碳管柱層析法(展開液：甲苯/庚烷/三乙胺=50/50/1)進行精製，而獲得5-溴-7,7-二甲基-N-苯基-N-(4-(三甲基矽烷基)苯基)-7H-苯并[c]茀-9-胺(2.8 g)。 Under a nitrogen atmosphere, 5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c]indole (5.0 g), N-phenyl-4-(trimethyldecyl) will be added. a flask of aniline (2.7 g), (PdCl 2 (o-tolyl 3 ) 2 ) (0.3 g), sodium butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) Stir at 120 ° C for 2 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent of the organic layer was distilled off under reduced pressure, and then purified by a silica gel column chromatography (developing solution: toluene/heptane/triethylamine = 5/95/1 (capacity ratio)), and then activated carbon tube was used. Column chromatography (developing solution: toluene / heptane / triethylamine = 50/50/1) was purified to give 5-bromo-7,7-dimethyl-N-phenyl-N-(4- (Trimethyldecyl)phenyl)-7H-benzo[c]indole-9-amine (2.8 g).

<化合物(1-1-123)的合成> <Synthesis of Compound (1-1-123)>

於氮氣環境下，將加入有5-溴-7,7-二甲基-N-苯基-N-(4-(三甲基矽烷基)苯基)-7H-苯并[c]茀-9-胺(1.0 g)、3,6-二苯基-9H-咔唑(0.7 g)、Pd(dba)2(0.03 g)、三-第三丁基膦的1 M甲苯溶液(0.2 ml)、第三丁醇鈉(0.26 g)及1,2,4-三甲基苯(10 ml)的燒瓶在回流溫度下攪拌10小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷/三乙胺混合溶劑)進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。進而，利用活性碳管柱層析法(展開液：甲苯/庚烷/三乙胺=50/50/1(容量比))進行精製後，將溶劑減壓餾去並添加甲醇，藉此進行再沈澱，而獲得由式(1-1-123)所表示的化合物，即 5-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N-苯基-N-(4-(三甲基矽烷基)苯基)-7H-苯并[c]茀-9-胺(0.7 g)。 Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N-phenyl-N-(4-(trimethyldecyl)phenyl)-7H-benzo[c]fluorene- 9-Amine (1.0 g), 3,6-diphenyl-9H-carbazole (0.7 g), Pd(dba) 2 (0.03 g), tris-tert-butylphosphine in 1 M toluene (0.2 ml The flask of sodium butoxide (0.26 g) and 1,2,4-trimethylbenzene (10 ml) was stirred at reflux temperature for 10 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene / heptane / triethylamine mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Furthermore, after purifying by activated carbon column chromatography (developing liquid: toluene / heptane / triethylamine = 50/50/1 (capacity ratio)), the solvent is distilled off under reduced pressure, and methanol is added thereto. Reprecipitation to obtain a compound represented by the formula (1-1-123), that is, 5-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-N -Phenyl-N-(4-(trimethyldecyl)phenyl)-7H-benzo[c]indole-9-amine (0.7 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.83(d,1H),8.48(m,2H),8.27(d,1H),7.75(m,5H),7.67(t,1H),7.63(dd,2H),7.47(m,5H),7.43(d,2H),7.29-7.41(m,6H),7.23(d,2H),7.07-7.21(m,6H),1.52(s,6H),0.28(s,9H)。 1 H-NMR (CDCl 3 ): δ=8.83 (d, 1H), 8.48 (m, 2H), 8.27 (d, 1H), 7.75 (m, 5H), 7.67 (t, 1H), 7.63 (dd, 2H), 7.47 (m, 5H), 7.43 (d, 2H), 7.29-7.41 (m, 6H), 7.23 (d, 2H), 7.07-7.21 (m, 6H), 1.52 (s, 6H), 0.28 (s, 9H).

[合成例16]化合物(1-1-61)的合成 [Synthesis Example 16] Synthesis of Compound (1-1-61)

<化合物(1-1-61)的合成> <Synthesis of Compound (1-1-61)>

於氮氣環境下，向由式(1-1-123)所表示的化合物，即5-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N-苯基-N-(4-(三甲基矽烷基)苯基)-7H-苯并[c]茀-9-胺(0.4 g)的甲苯(5 ml)溶液中添加一滴對甲苯磺酸，然後於60℃下攪拌1分鐘。將反應液冷卻至室溫為止後，利用三乙胺進行中和，然後添加水來進行分液。將有機層的溶劑減壓餾去後，添加庚烷來進行再沈澱，而獲得由式(1-1-61)所 表示的化合物，即5-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N,N-二苯基-7H-苯并[c]茀-9-胺(0.3 g)。 Under the nitrogen atmosphere, the compound represented by the formula (1-1-123), that is, 5-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl- Add a drop of p-toluene to a solution of N-phenyl-N-(4-(trimethyldecyl)phenyl)-7H-benzo[c]fluoren-9-amine (0.4 g) in toluene (5 ml) The acid was then stirred at 60 ° C for 1 minute. After the reaction liquid was cooled to room temperature, it was neutralized with triethylamine, and then water was added to carry out liquid separation. After the solvent of the organic layer is distilled off under reduced pressure, heptane is added to carry out reprecipitation, and the formula (1-1-61) is obtained. The compound represented, 5-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-N,N-diphenyl-7H-benzo[c]indole -9-amine (0.3 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.83(d,1H),8.48(m,2H),8.26(d,1H),7.75(m,5H),7.67(t,1H),7.63(dd,2H),7.46(m,5H),7.28-7.40(m,8H),7.21(m,4H),7.18(dd,1H),7.13(d,2H),7.08(t,2H),1.51(s,6H)。 1 H-NMR (CDCl 3 ): δ=8.83 (d, 1H), 8.48 (m, 2H), 8.26 (d, 1H), 7.75 (m, 5H), 7.67 (t, 1H), 7.63 (dd, 2H), 7.46 (m, 5H), 7.28-7.40 (m, 8H), 7.21 (m, 4H), 7.18 (dd, 1H), 7.13 (d, 2H), 7.08 (t, 2H), 1.51 (s) , 6H).

[合成例17]化合物(1-1-76)的合成 [Synthesis Example 17] Synthesis of Compound (1-1-76)

<5-溴-7,7-二甲基-N,N-二-對甲苯基-7H-苯并[c]茀-9-胺的合成> Synthesis of <5-bromo-7,7-dimethyl-N,N-di-p-tolyl-7H-benzo[c]indole-9-amine>

於氮氣環境下，將加入有5-溴-9-碘-7,7-二甲基-7H-苯并[c]茀(5.0 g)、二-對甲苯基胺(2.2 g)、(PdCl2(o-tolyl3)2)(0.3 g)、第三丁醇鈉(1.6 g)及1,2,4-三甲基苯(50 ml)的燒瓶在100℃下攪拌2小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將有機層的溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷=1/9(容 量比))進行精製後，進而利用活性碳管柱層析法(展開液：甲苯/庚烷=1/1)進行精製。將溶劑減壓餾去後，利用庚烷進行清洗，藉此獲得5-溴-7,7-二甲基-N,N-二-對甲苯基-7H-苯并[c]茀-9-胺(2.7 g)。 Under a nitrogen atmosphere, 5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c]indole (5.0 g), di-p-tolylamine (2.2 g), (PdCl) will be added. A flask of 2 (o-tolyl 3 ) 2 ) (0.3 g), sodium butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) was stirred at 100 ° C for 2 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent of the organic layer is distilled off under reduced pressure, and then purified by a silica gel column chromatography (developing liquid: toluene/heptane = 1/9 (capacity ratio)), and further activated carbon column chromatography (expanded) The liquid was purified by toluene/heptane = 1/1. The solvent was distilled off under reduced pressure, and then washed with heptane to obtain 5-bromo-7,7-dimethyl-N,N-di-p-tolyl-7H-benzo[c]indole-9- Amine (2.7 g).

<化合物(1-1-76)的合成> <Synthesis of Compound (1-1-76)>

於氮氣環境下，將加入有5-溴-7,7-二甲基-N,N-二-對甲苯基-7H-苯并[c]茀-9-胺(1.0 g)、3,6-二苯基-9H-咔唑(0.7 g)、Pd(dba)2(0.03 g)、三-第三丁基膦的1 M甲苯溶液(0.2 ml)、第三丁醇鈉(0.28 g)及1,2,4-三甲基苯(10 ml)的燒瓶在回流溫度下攪拌8小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。進而，利用活性碳管柱層析法(展開液：甲苯/庚烷=1/1(容量比))進行精製後，溶解於乙酸乙酯中，然後添加乙醇，藉此進行再沈澱，而獲得由式(1-1-76)所表示的化合物，即5-(3,6-二苯基-9H-咔唑-9-基)-7,7-二甲基-N,N-二甲苯基-7H-苯并[c]茀-9-胺(0.8 g)。 Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N,N-di-p-tolyl-7H-benzo[c]fluoren-9-amine (1.0 g), 3,6 will be added. -1 Phenyl-9H-carbazole (0.7 g), Pd(dba) 2 (0.03 g), tris-tert-butylphosphine in 1 M toluene (0.2 ml), sodium butoxide (0.28 g) The flask of 1,2,4-trimethylbenzene (10 ml) was stirred at reflux temperature for 8 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene/heptane mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Further, it is purified by activated carbon column chromatography (developing solution: toluene/heptane = 1/1 (capacity ratio)), dissolved in ethyl acetate, and then reprecipitated by adding ethanol. a compound represented by the formula (1-1-76), that is, 5-(3,6-diphenyl-9H-carbazol-9-yl)-7,7-dimethyl-N,N-xylene Base-7H-benzo[c]indole-9-amine (0.8 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.81(d,1H),8.48(m,2H),8.21(d,1H),7.75(m,5H),7.66(t,1H),7.62(dd,2H),7.48(m,5H),7.36(m,3H),7.26(m,1H),7.12(m,11H),2.36(s,6H),1.50(s,6H)。 1 H-NMR (CDCl 3 ): δ = 8.81 (d, 1H), 8.48 (m, 2H), 8.21 (d, 1H), 7.75 (m, 5H), 7.66 (t, 1H), 7.62 (dd, 2H), 7.48 (m, 5H), 7.36 (m, 3H), 7.26 (m, 1H), 7.12 (m, 11H), 2.36 (s, 6H), 1.50 (s, 6H).

[合成例18]化合物(1-1-103)的合成 [Synthesis Example 18] Synthesis of Compound (1-1-103)

<化合物(1-1-103)的合成> <Synthesis of Compound (1-1-103)>

於氮氣環境下，將加入有5-溴-7,7-二甲基-N,N-二-對甲苯基-7H-苯并[c]茀-9-胺(1.0 g)、3,6-二甲基-9H-咔唑(0.5 g)、Pd(dba)2(0.03 g)、三-第三丁基膦的1 M甲苯溶液(0.2 ml)、第三丁醇鈉(0.28 g)及1,2,4-三甲基苯(10 ml)的燒瓶在回流溫度下攪拌4小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷混合溶劑)進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。繼而，利用乙醇進行清洗後，於甲苯/庚烷混合溶劑中進行再沈澱，而獲得由式(1-1-103)所表示的化合物，即5-(3,6-二甲基-9H-咔唑-9-基)-7,7-二甲基-N,N-二甲苯基-7H-苯并[c]茀-9-胺(0.9 g)。 Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N,N-di-p-tolyl-7H-benzo[c]fluoren-9-amine (1.0 g), 3,6 will be added. - dimethyl-9H-carbazole (0.5 g), Pd(dba) 2 (0.03 g), tris-tert-butylphosphine in 1 M toluene (0.2 ml), sodium butoxide (0.28 g) The flask of 1,2,4-trimethylbenzene (10 ml) was stirred at reflux temperature for 4 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene/heptane mixed solvent). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. Then, after washing with ethanol, reprecipitation is carried out in a mixed solvent of toluene/heptane to obtain a compound represented by the formula (1-1-103), that is, 5-(3,6-dimethyl-9H- Carbazole-9-yl)-7,7-dimethyl-N,N-dimethylphenyl-7H-benzo[c]indole-9-amine (0.9 g).

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.77(d,1H),8.18(d,1H),7.97(m,2H),7.66(s,1H),7.61(t,1H),7.39(d,1H),7.31(t,1H),7.25(m,1H),7.13(d,2H),7.10(m,9H),6.92(d,2H),2.55(s,6H),2.35(s,6H),1.46(s,6H)。 1 H-NMR (CDCl 3 ): δ=8.77 (d, 1H), 8.18 (d, 1H), 7.97 (m, 2H), 7.66 (s, 1H), 7.61 (t, 1H), 7.39 (d, 1H), 7.31 (t, 1H), 7.25 (m, 1H), 7.13 (d, 2H), 7.10 (m, 9H), 6.92 (d, 2H), 2.55 (s, 6H), 2.35 (s, 6H) ), 1.46 (s, 6H).

[合成例19]化合物(1-1-154)的合成 [Synthesis Example 19] Synthesis of Compound (1-1-154)

<化合物(1-1-154)的合成> <Synthesis of Compound (1-1-154)>

於氮氣環境下，將加入有5-溴-N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-7H-苯并[c]茀-9-胺(2.0 g)、3-甲基-6-苯基-9H-咔唑(1.0 g)、Pd(dba)2(0.06 g)、三-第三丁基膦的1 M甲苯溶液(0.3 ml)、第三丁醇鈉(0.5 g)及1,2,4-三甲基苯(15 ml)的燒瓶在回流溫度下攪拌4小時。將反應液冷卻至室溫為止後，添加水及乙酸乙酯來進行分液。將溶劑減壓餾去後，利用矽膠管柱層析法(展開液：甲苯/庚烷)進行精製。此時，緩慢地增加展開液中的甲苯的比率來使目標物溶出。將溶劑減壓餾去並利用庚烷對所獲得的固體進行清洗，而獲得由式(1-1-154)所表示的化合物，即N,N-雙(4-(第三丁基)苯基)-7,7-二甲基-5-(3-甲基-6-苯基-9H-咔唑-9-基)-7H-苯并[c]茀-9-胺(1.6 g)。 Under the nitrogen atmosphere, 5-bromo-N,N-bis(4-(t-butyl)phenyl)-7,7-dimethyl-7H-benzo[c]fluoren-9-amine will be added. (2.0 g), 3-methyl-6-phenyl-9H-carbazole (1.0 g), Pd(dba) 2 (0.06 g), tris-tert-butylphosphine in 1 M toluene (0.3 ml) A flask of sodium butoxide (0.5 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at reflux temperature for 4 hours. After cooling the reaction liquid to room temperature, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (developing solvent: toluene / heptane). At this time, the ratio of toluene in the developing solution is gradually increased to dissolve the target. The solvent is distilled off under reduced pressure and the obtained solid is washed with heptane to obtain a compound represented by formula (1-1-154), that is, N,N-bis(4-(t-butyl)benzene. -7,7-Dimethyl-5-(3-methyl-6-phenyl-9H-indazol-9-yl)-7H-benzo[c]indole-9-amine (1.6 g) .

藉由NMR測定來確認所獲得的苯并茀化合物的結構。 The structure of the obtained benzofluorene compound was confirmed by NMR measurement.

1H-NMR(CDCl3)：δ=8.80(d,1H),8.40(m,1H),8.22(d,1H),8.06(s,1H),7.72(m,3H),7.62(t,1H),7.59(dd,1H), 7.48(t,2H),7.43(d,1H),7.25-7.38(m,7H),7.20(d,1H),7.12(m,6H),6.97(d,1H),2.58(s,3H),1.50(s,6H),1.35(s,18H)。 1 H-NMR (CDCl 3 ): δ=8.80 (d, 1H), 8.40 (m, 1H), 8.22 (d, 1H), 8.06 (s, 1H), 7.72 (m, 3H), 7.62 (t, 1H), 7.59 (dd, 1H), 7.48 (t, 2H), 7.43 (d, 1H), 7.25-7.38 (m, 7H), 7.20 (d, 1H), 7.12 (m, 6H), 6.97 (d) , 1H), 2.58 (s, 3H), 1.50 (s, 6H), 1.35 (s, 18H).

藉由適宜選擇原料的化合物，並利用基於上述合成例的方法，可合成其他苯并茀化合物。 Other benzofluorene compounds can be synthesized by appropriately selecting a compound of the starting material and using the method based on the above synthesis example.

<用於電場發光元件時的特性> <Characteristics when used in an electric field light-emitting element>

以下，為了更詳細地說明本發明，而表示使用本發明的化合物的有機EL元件的實例，但本發明並不限定於該些實例。 Hereinafter, in order to explain the present invention in more detail, an example of an organic EL device using the compound of the present invention is shown, but the present invention is not limited to the examples.

製作實例1~實例4及比較例1~比較例2的電場發光元件，分別確認發光及其色度，繼而測定以30 mA/cm2的恆定電流進行驅動時亮度衰減至初始值的90%為止的時間(hr)。以下，對實例及比較例進行詳細說明。 The electroluminescent light-emitting elements of Example 1 to Example 4 and Comparative Example 1 to Comparative Example 2 were produced, and the luminescence and the chromaticity thereof were confirmed, and then the luminance was attenuated to 90% of the initial value when driven at a constant current of 30 mA/cm 2 . Time (hr). Hereinafter, examples and comparative examples will be described in detail.

將所製作的實例1~實例4及比較例1~比較例2的元件中的各層的材料構成示於下述表1。再者，於所有例中，利用8-羥基喹啉鋰(Liq)/鎂與銀的共蒸鍍物來構成陰極。 The material compositions of the respective layers of the produced Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1 below. Further, in all of the examples, a cathode was formed using a co-evaporated material of lithium quinolate (Liq)/magnesium and silver.

表1中，「HI」為N4,N4'-二苯基-N4,N4'-雙(9-苯基-9H-咔唑-3-基)-[1,1'-聯苯]-4,4'-二胺，「NPD」為N4,N4'-二(萘-1-基)-N4,N4'-二苯基-[1,1'-聯苯]-4,4'-二胺，化合物(A)為9,10-二(萘-1-基)蒽，化合物(B)為4,4'-((7,7-二甲基-7H-苯并[c]茀-5,9-二基)雙((苯基)胺基))二苄腈，化合物(C)為7,7-二甲基-N5,N5,N9,N9-四苯基-7H-苯并[c]茀-5,9-二胺，化合物(D)為5,5'-(2-苯基蒽-9,10-二基)二-2,2'-聯吡啶。以下表示化學結構，且一併表示用於陰極的「Liq」。 In Table 1, "HI" is N 4 , N 4 '-diphenyl-N 4 , N 4 '-bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-linked Benzene]-4,4'-diamine, "NPD" is N 4 ,N 4 '-bis(naphthalen-1-yl)-N 4 ,N 4 '-diphenyl-[1,1'-biphenyl ]-4,4'-diamine, compound (A) is 9,10-di(naphthalen-1-yl)anthracene, and compound (B) is 4,4'-((7,7-dimethyl-7H) -Benzo[c]indole-5,9-diyl)bis((phenyl)amino))dibenzonitrile, the compound (C) is 7,7-dimethyl-N 5 , N 5 , N 9 , N 9 -tetraphenyl-7H-benzo[c]indole-5,9-diamine, the compound (D) is 5,5'-(2-phenylfluorene-9,10-diyl)di- 2,2'-bipyridyl. The chemical structure is shown below, and "Liq" for the cathode is also shown together.

<實例1> <Example 1> <將化合物(1-1-24)用於發光層的元件> <Component for using compound (1-1-24) for light-emitting layer>

以將藉由濺鍍來製成180 nm的厚度的ITO膜研磨至150 nm為止的26 mm×28 mm×0.7 mm的玻璃基板(Opto Science(股份)製造)作為透明支撐基板。將該透明支撐基板固定於市售的蒸鍍裝置(昭和真空(股份)製造)的基板保持器上，然後安裝添加有HI的鉬製蒸鍍用舟皿、添加有NPD的鉬製蒸鍍用舟皿、添加有化合物(A)的鉬製蒸鍍用舟皿、添加有化合物(1-1-24)的鉬製蒸鍍用舟皿、添加有化合物(D)的鉬製蒸鍍用舟皿、添加有Liq的鉬製蒸鍍用舟皿、添加有鎂的鉬製蒸鍍用舟皿、及添加 有銀的鎢製蒸鍍用舟皿。 A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science Co., Ltd.) in which an ITO film having a thickness of 180 nm was formed by sputtering to a thickness of 150 nm was used as a transparent supporting substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and then a molybdenum vapor deposition boat to which HI is added and a molybdenum vapor deposition plate to which NPD is added are attached. Boat, vapor-deposited boat for molybdenum to which compound (A) is added, boat for vapor deposition of molybdenum to which compound (1-1-24) is added, and boat for vapor deposition of molybdenum to which compound (D) is added a dish, a molybdenum vapor deposition boat to which Liq is added, a molybdenum vapor deposition boat to which magnesium is added, and an addition A boat made of tungsten for vapor deposition.

於透明支撐基板的ITO膜上依次形成下述各層。將真空槽減壓至5×10-4 Pa為止，首先，對添加有HI的蒸鍍用舟皿進行加熱、且以使膜厚成為40 nm的方式進行蒸鍍來形成電洞注入層，繼而，對添加有NPD的蒸鍍用舟皿進行加熱、且以使膜厚成為25 nm的方式進行蒸鍍來形成電洞傳輸層。繼而，對添加有化合物(A)的蒸鍍用舟皿與添加有化合物(1-1-24)的蒸鍍用舟皿同時進行加熱、且以使膜厚成為25 nm的方式進行蒸鍍來形成發光層。以使化合物(A)與化合物(1-1-24)的重量比大致成為95對5的方式調節蒸鍍速度。繼而，對添加有化合物(D)的蒸鍍用舟皿進行加熱、且以使膜厚成為20 nm的方式進行蒸鍍來形成電子傳輸層。以上的蒸鍍速度為0.01 nm/秒~1 nm/秒。 The following layers were sequentially formed on the ITO film of the transparent supporting substrate. When the vacuum chamber is depressurized to 5 × 10 -4 Pa, first, the boat for vapor deposition to which HI is added is heated, and vapor deposition is performed so that the film thickness becomes 40 nm to form a hole injection layer, and then the hole injection layer is formed. The vapor deposition boat to which the NPD was added was heated and vapor-deposited so as to have a film thickness of 25 nm to form a hole transport layer. Then, the vapor deposition boat to which the compound (A) was added and the vapor deposition boat to which the compound (1-1-24) was added were simultaneously heated and vapor-deposited so that the film thickness became 25 nm. A light emitting layer is formed. The vapor deposition rate was adjusted such that the weight ratio of the compound (A) to the compound (1-1-24) was approximately 95 to 5. Then, the vapor deposition boat to which the compound (D) was added was heated and vapor-deposited so as to have a film thickness of 20 nm to form an electron transport layer. The above vapor deposition rate is from 0.01 nm/sec to 1 nm/sec.

其後，對添加有Liq的蒸鍍用舟皿進行加熱、且以使膜厚成為1 nm的方式以0.01 nm/秒~0.1 nm/秒的蒸鍍速度進行蒸鍍。繼而，對添加有鎂的舟皿與添加有銀的舟皿同時進行加熱、且以使膜厚成為100 nm的方式進行蒸鍍來形成陰極。此時，以使鎂與銀的原子數比成為10對1的方式調節蒸鍍速度，並以蒸鍍速度自0.1 nm/秒變成10 nm/秒的方式形成陰極，從而獲得有機電場發光元件。 Then, the vapor deposition boat to which Liq was added was heated, and vapor deposition was performed at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1 nm. Then, the boat to which magnesium was added and the boat to which silver was added were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm, and the cathode was formed. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver became 10 to 1, and the cathode was formed so that the vapor deposition rate was changed from 0.1 nm/sec to 10 nm/sec to obtain an organic electroluminescence device.

若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.145,0.110)的藍色發光。另外，實施30 mA/cm2 的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為110小時。 When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.145, 0.110) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 110 hours.

<實例2> <Example 2> <將化合物(1-1-54)用於發光層的元件> <Component for using the compound (1-1-54) for the light-emitting layer>

將化合物(1-1-24)替換成化合物(1-1-54)，除此以外，以根據實例1的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.146,0.105)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為40小時。 An organic EL device was obtained by the method according to Example 1, except that the compound (1-1-24) was replaced with the compound (1-1-54). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a direct current voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.146, 0.105) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 40 hours.

<實例3> <Example 3> <將化合物(1-1-84)用於發光層的元件> <Component for using the compound (1-1-84) for the light-emitting layer>

將化合物(1-1-24)替換成化合物(1-1-84)，除此以外，以根據實例1的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.147,0.112)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為80小時。 An organic EL device was obtained by the method according to Example 1, except that the compound (1-1-24) was replaced with the compound (1-1-84). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.147, 0.112) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 80 hours.

<實例4> <Example 4> <將化合物(1-2-121)用於發光層的元件> <Component for using compound (1-2-121) for light-emitting layer>

將化合物(1-1-24)替換成化合物(1-2-121)，除此以外，以根據實例1的方法獲得有機EL元件。若將ITO電 極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.143,0.102)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為113小時。 An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-24) was replaced by the compound (1-2-121). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.143, 0.102) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 113 hours.

<比較例1> <Comparative Example 1>

將化合物(1-1-24)替換成化合物(B)，除此以外，以根據實例1的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.145,0.092)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為14小時。 An organic EL element was obtained by the method according to Example 1, except that the compound (1-1-24) was replaced with the compound (B). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.145, 0.092) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 14 hours.

<比較例2> <Comparative Example 2>

將化合物(1-1-24)替換成化合物(C)，除此以外，以根據實例1的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.149,0.135)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為55小時。 An organic EL element was obtained by the method according to Example 1, except that the compound (1-1-24) was replaced with the compound (C). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.149, 0.135) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 55 hours.

將以上的結果匯總於表2。 The above results are summarized in Table 2.

其次，製作實例5~實例13及比較例3~比較例4的電場發光元件，分別確認發光及其色度，繼而測定以30 mA/cm2的恆定電流進行驅動時亮度衰減至初始值的90%為止的時間(hr)。 Next, the electroluminescent light-emitting elements of Example 5 to Example 13 and Comparative Example 3 to Comparative Example 4 were produced, and the luminescence and the chromaticity thereof were confirmed, respectively, and then the luminance was attenuated to the initial value when driven at a constant current of 30 mA/cm 2 . Time until % (hr).

將所製作的實例5~實例13及比較例3~比較例4的元件中的各層的材料構成示於下述表3。 The material compositions of the respective layers of the produced Examples 5 to 13 and Comparative Examples 3 to 4 are shown in Table 3 below.

表3中，HT為N-([1,1'-聯苯]-4-基)-9,9-二甲基-N-(4-(9-苯基-9H-咔唑-3-基)苯基)-9H-茀-2-胺，化合物(E)為9-苯基-10-(4-苯基萘-1-基)蒽，化合物(F)為4,4'-((2-苯基蒽-9,10-二基)雙(4,1-伸苯基))二吡啶。以下表示化學結構。 In Table 3, HT is N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3- (phenyl)-9H-indol-2-amine, compound (E) is 9-phenyl-10-(4-phenylnaphthalen-1-yl)anthracene, and compound (F) is 4,4'-( (2-Phenylpurine-9,10-diyl)bis(4,1-phenylene)dipyridine. The chemical structure is shown below.

<實例5> <Example 5> <將化合物(1-1-70)用於發光層的元件> <Component for using the compound (1-1-70) for the light-emitting layer>

以將藉由濺鍍來製成180 nm的厚度的ITO膜研磨至150 nm為止的26 mm×28 mm×0.7 mm的玻璃基板(Opto Science(股份)製造)作為透明支撐基板。將該透明支撐基板固定於市售的蒸鍍裝置(昭和真空(股份)製造)的基板保持器上，然後安裝添加有HI的鉬製蒸鍍用舟皿、添加有HT的鉬製蒸鍍用舟皿、添加有化合物(E)的鉬製蒸鍍用舟皿、添加有化合物(1-1-70)的鉬製蒸鍍用舟皿、添加有化合物(F)的鉬製蒸鍍用舟皿、添加有Liq的鉬製蒸鍍用舟皿、添加有鎂的鉬舟及添加有銀的鎢製蒸鍍用舟皿。 A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science Co., Ltd.) in which an ITO film having a thickness of 180 nm was formed by sputtering to a thickness of 150 nm was used as a transparent supporting substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and then a molybdenum vapor deposition boat to which HI is added and a molybdenum vapor deposition plate to which HT is added are used. Boat, vapor-deposited boat for molybdenum to which compound (E) is added, boat for vapor deposition made of molybdenum to which compound (1-1-70) is added, and boat for vapor deposition of molybdenum to which compound (F) is added A dish, a molybdenum vapor deposition boat to which Liq is added, a molybdenum boat to which magnesium is added, and a tungsten vapor deposition boat to which silver is added.

於透明支撐基板的ITO膜上依次形成下述各層。將真空槽減壓至5×10-4 Pa為止，首先，對添加有HI的蒸鍍用 舟皿進行加熱、且以使膜厚成為40 nm的方式進行蒸鍍來形成電洞注入層，繼而，對添加有HT的蒸鍍用舟皿進行加熱、且以使膜厚成為30 nm的方式進行蒸鍍來形成電洞傳輸層。繼而，對添加有化合物(E)的蒸鍍用舟皿與添加有化合物(1-1-70)的蒸鍍用舟皿同時進行加熱、且以使膜厚成為35 nm的方式進行蒸鍍來形成發光層。以使化合物(E)與化合物(1-1-70)的重量比大致成為95對5的方式調節蒸鍍速度。繼而，對添加有化合物(F)的蒸鍍用舟皿進行加熱、且以使膜厚成為20 nm的方式進行蒸鍍來形成電子傳輸層。各層的蒸鍍速度為0.01 nm/秒~1 nm/秒。 The following layers were sequentially formed on the ITO film of the transparent supporting substrate. When the vacuum chamber is depressurized to 5 × 10 -4 Pa, first, the boat for vapor deposition to which HI is added is heated, and vapor deposition is performed so that the film thickness becomes 40 nm to form a hole injection layer, and then the hole injection layer is formed. The vapor deposition boat to which HT was added was heated, and vapor deposition was performed so that the film thickness became 30 nm to form a hole transport layer. Then, the vapor deposition boat to which the compound (E) was added and the vapor deposition boat to which the compound (1-1-70) was added were simultaneously heated and vapor-deposited so that the film thickness became 35 nm. A light emitting layer is formed. The vapor deposition rate was adjusted so that the weight ratio of the compound (E) to the compound (1-1-70) was approximately 95 to 5. Then, the vapor deposition boat to which the compound (F) was added was heated and vapor-deposited so as to have a film thickness of 20 nm to form an electron transport layer. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

其後，對添加有Liq的蒸鍍用舟皿進行加熱、且以使膜厚成為1 nm的方式以0.01 nm/秒~0.1 nm/秒的蒸鍍速度進行蒸鍍。繼而，對添加有鎂的舟皿與添加有銀的舟皿同時進行加熱、且以使膜厚成為100 nm的方式進行蒸鍍而形成陰極。此時，以使鎂與銀的原子數比成為10對1的方式調節蒸鍍速度，且以蒸鍍速度變成0.1 nm/秒~10 nm/秒的方式形成陰極，從而獲得有機電場發光元件。 Then, the vapor deposition boat to which Liq was added was heated, and vapor deposition was performed at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1 nm. Then, the boat to which magnesium was added and the boat to which silver was added were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm, and the cathode was formed. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver became 10 to 1, and the cathode was formed so that the vapor deposition rate became 0.1 nm/sec to 10 nm/sec, thereby obtaining an organic electroluminescent device.

若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.148,0.067)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為53小時。 When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.148, 0.067) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 53 hours.

<實例6> <Example 6> <將化合物(1-1-84)用於發光層的元件> <Component for using the compound (1-1-84) for the light-emitting layer>

將化合物(1-1-70)替換成化合物(1-1-84)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.144,0.090)的藍色發光，且保持初始值的90%以上的亮度的時間為63小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced by the compound (1-1-84). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.144, 0.090) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 63 hours.

<實例7> <Example 7> <將化合物(1-1-113)用於發光層的元件> <Component for using compound (1-1-113) for light-emitting layer>

將化合物(1-1-70)替換成化合物(1-1-113)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.147,0.079)的藍色發光，且保持初始值的90%以上的亮度的時間為50小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced by the compound (1-1-113). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.147, 0.079) was obtained, and the time of maintaining the luminance of 90% or more of the initial value was 50 hours.

<實例8> <Example 8> <將化合物(1-2-85)用於發光層的元件> <Component for using compound (1-2-85) for light-emitting layer>

將化合物(1-1-70)替換成化合物(1-2-85)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.147,0.119)的藍色發光，且保持初始值的90%以上的亮度的時間為69小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced with the compound (1-2-85). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.147, 0.119) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 69 hours.

<實例9> <Example 9> <將化合物(1-1-101)用於發光層的元件> <Component for using compound (1-1-101) for light-emitting layer>

將化合物(1-1-70)替換成化合物(1-1-101)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的 試驗，結果可獲得CIE色度(x,y)=(0.151,0.061)的藍色發光，且保持初始值的90%以上的亮度的時間為19小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced by the compound (1-1-101). Carry out the same As a result, it was found that blue light emission of CIE chromaticity (x, y) = (0.151, 0.061) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 19 hours.

<實例10> <Example 10> <將化合物(1-1-1)用於發光層的元件> <Component for using the compound (1-1-1) for the light-emitting layer>

將化合物(1-1-70)替換成化合物(1-1-1)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.151,0.060)的藍色發光，且保持初始值的90%以上的亮度的時間為18小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced by the compound (1-1-1). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.151, 0.060) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 18 hours.

<實例11> <Example 11> <將化合物(1-1-140)用於發光層的元件> <Component for using compound (1-1-140) for light-emitting layer>

將化合物(1-1-70)替換成化合物(1-1-140)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.150,0.065)的藍色發光，且保持初始值的90%以上的亮度的時間為16小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced with the compound (1-1-140). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.150, 0.065) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 16 hours.

<實例12> <Example 12> <將化合物(1-1-10)用於發光層的元件> <Component for using compound (1-1-10) for light-emitting layer>

將化合物(1-1-70)替換成化合物(1-1-10)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.150,0.060)的藍色發光，且保持初始值的90%以上的亮度的時間為17小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced by the compound (1-1-10). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.150, 0.060) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 17 hours.

<實例13> <Example 13> <將化合物(1-2-174)用於發光層的元件> <Component for using compound (1-2-174) for light-emitting layer>

將化合物(1-1-70)替換成化合物(1-2-174)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.141,0.115)的藍色發光，且保持初始值的90%以上的亮度的時間為60小時。 An organic EL device was obtained by the method according to Example 5 except that the compound (1-1-70) was replaced with the compound (1-2-174). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.141, 0.115) was obtained, and the time of maintaining the luminance of 90% or more of the initial value was 60 hours.

<比較例3> <Comparative Example 3>

將化合物(1-1-70)替換成化合物(B)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.146,0.084)的藍色發光，且保持初始值的90%以上的亮度的時間為9小時。 An organic EL element was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced with the compound (B). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.146, 0.084) was obtained, and the time of maintaining the luminance of 90% or more of the initial value was 9 hours.

<比較例4> <Comparative Example 4>

將化合物(1-1-70)替換成化合物(C)，除此以外，以根據實例5的方法獲得有機EL元件。進行相同的試驗，結果可獲得CIE色度(x,y)=(0.144,0.126)的藍色發光，且保持初始值的90%以上的亮度的時間為40小時。 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was replaced by the compound (C). The same test was carried out, and as a result, blue light emission of CIE chromaticity (x, y) = (0.144, 0.126) was obtained, and the time of maintaining the luminance of 90% or more of the initial value was 40 hours.

將以上的結果匯總於表4。 The above results are summarized in Table 4.

其次，製作實例14~實例18及比較例5的電場發光元件，分別確認發光及其色度，繼而測定以30 mA/cm2的恆定電流進行驅動時亮度衰減至初始值的90%為止的時間(hr)。 Next, the electroluminescent elements of Examples 14 to 18 and Comparative Example 5 were produced, and the luminescence and the chromaticity thereof were confirmed, respectively, and then the time until the luminance was attenuated to 90% of the initial value when driving at a constant current of 30 mA/cm 2 was measured. (hr).

將所製作的實例14~實例18及比較例5的元件中的各層的材料構成示於下述表5。 The material compositions of the respective layers of the produced Examples 14 to 18 and Comparative Example 5 are shown in Table 5 below.

表5中，化合物(G)為9-(4-(萘-1-基)苯基)-10-苯基蒽。以下表示化學結構。 In Table 5, the compound (G) is 9-(4-(naphthalen-1-yl)phenyl)-10-phenylindole. The chemical structure is shown below.

<實例14> <Example 14> <將化合物(1-1-123)用於發光層的元件> <Component for using compound (1-1-123) for light-emitting layer>

以將藉由濺鍍來製成180 nm的厚度的ITO膜研磨至150 nm為止的26 mm×28 mm×0.7 mm的玻璃基板(Opto Science(股份)製造)作為透明支撐基板。將該透明支撐 基板固定於市售的蒸鍍裝置(昭和真空(股份)製造)的基板保持器上，然後安裝添加有HI的鉬製蒸鍍用舟皿、添加有HT的鉬製蒸鍍用舟皿、添加有化合物(G)的鉬製蒸鍍用舟皿、添加有化合物(1-1-123)的鉬製蒸鍍用舟皿、添加有化合物(F)的鉬製蒸鍍用舟皿、添加有Liq的鉬製蒸鍍用舟皿、添加有鎂的鉬舟及添加有銀的鎢製蒸鍍用舟皿。 A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Opto Science Co., Ltd.) in which an ITO film having a thickness of 180 nm was formed by sputtering to a thickness of 150 nm was used as a transparent supporting substrate. The transparent support The substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and then a molybdenum vapor deposition boat to which HI is added, and a molybdenum vapor deposition boat to which HT is added are added. a boat for vapor deposition of molybdenum having a compound (G), a boat for vapor deposition made of molybdenum containing a compound (1-1-123), and a boat for vapor deposition of molybdenum to which a compound (F) is added, Liq molybdenum vapor deposition boat, molybdenum boat with magnesium added, and tungsten vapor deposition boat with silver added.

於透明支撐基板的ITO膜上依次形成下述各層。將真空槽減壓至5×10-4 Pa為止，首先，對添加有HI的蒸鍍用舟皿進行加熱、且以使膜厚成為40 nm的方式進行蒸鍍來形成電洞注入層，進而對添加有HT的蒸鍍用舟皿進行加熱、且以使膜厚成為30 nm的方式進行蒸鍍來形成電洞傳輸層。繼而，對添加有化合物(G)的蒸鍍用舟皿與添加有化合物(1-1-123)的蒸鍍用舟皿同時進行加熱、且以使膜厚成為35 nm的方式進行蒸鍍來形成發光層。以使化合物(G)與化合物(1-1-123)的重量比大致成為95對5的方式調節蒸鍍速度。繼而，對添加有化合物(F)的蒸鍍用舟皿進行加熱、且以使膜厚成為20 nm的方式進行蒸鍍來形成電子傳輸層。各層的蒸鍍速度為0.01 nm/秒~1 nm/秒。 The following layers were sequentially formed on the ITO film of the transparent supporting substrate. When the vacuum chamber is depressurized to 5 × 10 -4 Pa, first, the boat for vapor deposition to which HI is added is heated, and vapor deposition is performed so as to have a film thickness of 40 nm to form a hole injection layer. The vapor deposition boat to which HT was added was heated and vapor-deposited so that the film thickness became 30 nm, and the hole transport layer was formed. Then, the vapor deposition boat to which the compound (G) was added and the vapor deposition boat to which the compound (1-1-123) was added were simultaneously heated and vapor-deposited so that the film thickness became 35 nm. A light emitting layer is formed. The vapor deposition rate was adjusted so that the weight ratio of the compound (G) to the compound (1-1-123) was approximately 95 to 5. Then, the vapor deposition boat to which the compound (F) was added was heated and vapor-deposited so as to have a film thickness of 20 nm to form an electron transport layer. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

其後，對添加有Liq的蒸鍍用舟皿進行加熱、且以使膜厚成為1 nm的方式以0.01 nm/秒~0.1 nm/秒的蒸鍍速度進行蒸鍍。繼而，對添加有鎂的舟皿與添加有銀的舟皿同時進行加熱、且以使膜厚成為100 nm的方式進行蒸鍍 而形成陰極。此時，以使鎂與銀的原子數比成為10對1的方式調節蒸鍍速度，且以蒸鍍速度變成0.1 nm/秒~10 nm/秒的方式形成陰極，從而獲得有機電場發光元件。 Then, the vapor deposition boat to which Liq was added was heated, and vapor deposition was performed at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1 nm. Then, the boat to which magnesium was added and the boat to which silver was added were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm. The cathode is formed. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver became 10 to 1, and the cathode was formed so that the vapor deposition rate became 0.1 nm/sec to 10 nm/sec, thereby obtaining an organic electroluminescent device.

若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.147,0.076)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為66小時。 When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a direct current voltage is applied, blue light having a CIE chromaticity (x, y) = (0.147, 0.076) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 66 hours.

<實例15> <Example 15> <將化合物(1-1-61)用於發光層的元件> <Component for using compound (1-1-61) for light-emitting layer>

將化合物(1-1-123)替換成化合物(1-1-61)，除此以外，以根據實例14的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.146,0.076)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為53小時。 An organic EL device was obtained by the method according to Example 14 except that the compound (1-1-123) was replaced by the compound (1-1-61). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.146, 0.076) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 53 hours.

<實例16> <Example 16> <將化合物(1-1-76)用於發光層的元件> <Component for using the compound (1-1-76) for the light-emitting layer>

將化合物(1-1-123)替換成化合物(1-1-76)，除此以外，以根據實例14的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.144,0.100)的藍色發光。另外，實施30 mA/cm2的恆定電流驅 動試驗，結果保持初始值的90%以上的亮度的時間為60小時。 An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was replaced by the compound (1-1-76). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.144, 0.100) can be obtained. . Further, a constant current driving test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 60 hours.

<實例17> <Example 17> <將化合物(1-1-103)用於發光層的元件> <Component for using compound (1-1-103) for light-emitting layer>

將化合物(1-1-123)替換成化合物(1-1-103)，除此以外，以根據實例14的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.144,0.095)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為67小時。 An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was replaced by the compound (1-1-103). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.144, 0.095) can be obtained. . Further, a constant current driving test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 67 hours.

<實例18> <Example 18> <將化合物(1-1-154)用於發光層的元件> <Component for using the compound (1-1-154) for the light-emitting layer>

將化合物(1-1-123)替換成化合物(1-1-154)，除此以外，以根據實例14的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極，並施加直流電壓，則可獲得CIE色度(x,y)=(0.144,0.094)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為93小時。 An organic EL device was obtained by the method according to Example 14 except that the compound (1-1-123) was replaced by the compound (1-1-154). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a DC voltage is applied, blue light emission of CIE chromaticity (x, y) = (0.144, 0.094) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 93 hours.

<比較例5> <Comparative Example 5>

將化合物(1-1-123)替換成化合物(C)，除此以外，以根據實例14的方法獲得有機EL元件。若將ITO電極作為陽極，將包含Liq/鎂與銀的共蒸鍍物的電極作為陰極， 並施加直流電壓，則可獲得CIE色度(x,y)=(0.148,0.132)的藍色發光。另外，實施30 mA/cm2的恆定電流驅動試驗，結果保持初始值的90%以上的亮度的時間為31小時。 An organic EL element was obtained by the method according to Example 14 except that the compound (1-1-123) was replaced with the compound (C). When an ITO electrode is used as an anode and an electrode including a co-evaporated material of Liq/magnesium and silver is used as a cathode, and a direct current voltage is applied, blue light having a CIE chromaticity (x, y) = (0.148, 0.132) can be obtained. . Further, a constant current drive test of 30 mA/cm 2 was carried out, and as a result, the time for maintaining the luminance of 90% or more of the initial value was 31 hours.

將以上的結果匯總於表6。 The above results are summarized in Table 6.

如根據上述實例及比較例的電場發光元件的性能評價可知般，實例的電場發光元件顯示與比較例的電場發光元件同等或其以上的優異的色純度，並且壽命特性提昇。 As can be seen from the performance evaluation of the electric field light-emitting element of the above examples and comparative examples, the electric field light-emitting element of the example exhibits excellent color purity equivalent to or higher than that of the electric field light-emitting element of the comparative example, and the life characteristics are improved.

[產業上之可利用性] [Industrial availability]

根據本發明的較佳的形態，可提供一種顯示優異的色純度、且元件壽命優異的有機電場發光元件、具備其的顯示裝置及具備其的照明裝置等。 According to a preferred embodiment of the present invention, an organic electroluminescence device which exhibits excellent color purity and excellent device life, a display device including the same, and an illumination device including the same can be provided.

100‧‧‧有機電場發光元件 100‧‧‧Organic electric field light-emitting elements

101‧‧‧基板 101‧‧‧Substrate

102‧‧‧陽極 102‧‧‧Anode

103‧‧‧電洞注入層 103‧‧‧ hole injection layer

104‧‧‧電洞傳輸層 104‧‧‧ hole transport layer

105‧‧‧發光層 105‧‧‧Lighting layer

106‧‧‧電子傳輸層 106‧‧‧Electronic transport layer

107‧‧‧電子注入層 107‧‧‧Electronic injection layer

108‧‧‧陰極 108‧‧‧ cathode

圖1是表示本實施形態的有機電場發光元件的概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an organic electroluminescence device of the embodiment.

100‧‧‧有機電場發光元件 100‧‧‧Organic electric field light-emitting elements

101‧‧‧基板 101‧‧‧Substrate

102‧‧‧陽極 102‧‧‧Anode

103‧‧‧電洞注入層 103‧‧‧ hole injection layer

104‧‧‧電洞傳輸層 104‧‧‧ hole transport layer

105‧‧‧發光層 105‧‧‧Lighting layer

106‧‧‧電子傳輸層 106‧‧‧Electronic transport layer

107‧‧‧電子注入層 107‧‧‧Electronic injection layer

108‧‧‧陰極 108‧‧‧ cathode

Claims (19)

一種苯并茀化合物，其由下述式(1)表示： 式中，R分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、可由碳數為1~4的烷基取代的碳數為6~24的芳基、或可由碳數為1~4的烷基取代的碳數為5~24的雜芳基，A及B的任一者為9-咔唑基，另一者為二芳基胺基，9-咔唑基及二芳基胺基的芳基分別獨立，可由選自由碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、及由碳數為1~4的烷基取代的矽烷基所組成的組群中的至少1種基取代，當2個以上的基鄰接並進行取代時，該些可鍵結而形成脂肪族環或苯環，且由式(1)所表示的化合物中的至少1個氫可由重氫取代。 A benzofluorene compound represented by the following formula (1): In the formula, R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 24 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms, Or a heteroaryl group having a carbon number of 5 to 24 substituted with an alkyl group having 1 to 4 carbon atoms, and any of A and B is a 9-carbazolyl group, and the other is a diarylamine group, 9- The aryl group of the carbazolyl group and the diarylamino group are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and At least one group in the group consisting of an alkyl group substituted with an alkyl group having 1 to 4 carbon atoms is substituted, and when two or more groups are adjacent to each other and substituted, the groups may bond to form an aliphatic ring or A benzene ring, and at least one hydrogen in the compound represented by the formula (1) may be substituted with a heavy hydrogen. 如申請專利範圍第1項所述之苯并茀化合物，其由下述式(1-1)表示： 式中，R分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、或可由碳數為1~4的烷基取代的碳數為6~12的芳基，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 The benzofluorene compound according to claim 1, which is represented by the following formula (1-1): In the formula, R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms. R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The alkyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, and n is independently An integer of 0 to 5, when two or more R 1 are adjacent to each other and substituted on one benzene ring, these may be bonded to form a cyclohexane ring or a benzene ring. 如申請專利範圍第1項所述之苯并茀化合物，其由下述式(1-2)表示： 式中，R分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、或可由碳數為1~4的烷基取代的碳數為6~12的芳基，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 The benzofluorene compound according to claim 1, which is represented by the following formula (1-2): In the formula, R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms. R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The alkyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, and n is independently An integer of 0 to 5, when two or more R 1 are adjacent to each other and substituted on one benzene ring, these may be bonded to form a cyclohexane ring or a benzene ring. 如申請專利範圍第2項或第3項所述之苯并茀化合物，其中R分別獨立為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、環己基、苯基或萘基，R1分別獨立為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、環己基、苯基、萘基、三甲基矽烷基、三乙基矽烷基或二甲基單第三丁基矽烷基，且m分別獨立為0~2的整數，n分別獨立為0~2的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成苯環。 A benzofluorene compound as described in claim 2 or 3, wherein R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl Or a cyclohexyl group, a phenyl group or a naphthyl group, and R 1 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, cyclohexyl, phenyl, Naphthyl, trimethyldecyl, triethyldecyl or dimethylmono-tert-butylalkyl, and m is independently an integer of 0 to 2, and n is independently an integer of 0 to 2, when 2 When R 1 is adjacent to and substituted on one benzene ring, the bonds may be bonded to form a benzene ring. 如申請專利範圍第2項或第3項所述之苯并茀化合物，其中R分別獨立為甲基、乙基、異丙基、第二丁基、第三丁基、或苯基，R1分別獨立為甲基、乙基、異丙基、第三丁基、環己 基、苯基或三甲基矽烷基，m及n分別獨立為0~2的整數。 A benzofluorene compound as described in claim 2 or 3, wherein R is independently methyl, ethyl, isopropyl, t-butyl, t-butyl or phenyl, R 1 Each is independently methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl or trimethyldecyl, and m and n are each independently an integer of 0-2. 如申請專利範圍第1項所述之苯并茀化合物，其由下述式(1-1-24)、式(1-1-54)或式(1-1-84)表示： The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-24), formula (1-1-54) or formula (1-1-84): 如申請專利範圍第1項所述之苯并茀化合物，其由下述式(1-1-1)、式(1-1-10)、式(1-1-70)、式(1-1-101)、式(1-1-113)、式(1-2-24)、式(1-2-84)或式(1-2-85)表示： The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-1), formula (1-1-10), formula (1-1-70), and formula (1- 1-101), Formula (1-1-113), Formula (1-2-24), Formula (1-2-84) or Formula (1-2-85) means: 如申請專利範圍第1項所述之苯并茀化合物，其由下述式(1-1-140)、式(1-2-121)或式(1-2-174)表示： The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-140), formula (1-2-121) or formula (1-2-174): 如申請專利範圍第1項所述之苯并茀化合物，其由下述式(1-1-61)、式(1-1-76)、式(1-1-103)、式(1-1-123)或式(1-1-154)表示： The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-61), formula (1-1-76), formula (1-1-103), and formula (1- 1-123) or (1-1-154) means: 一種苯并茀化合物，其由下述式(1'-1)表示： 式中，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環 烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 A benzofluorene compound represented by the following formula (1'-1): In the formula, R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The substituted decyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, respectively. An integer of 0 to 5 is independently independent. When two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring. 一種苯并茀化合物，其由下述式(1'-2)表示： 式中，R1分別獨立為碳數為1~6的烷基、碳數為3~6的環烷基、碳數為6~10的芳基、或由碳數為1~4的烷基取代的矽烷基，m分別獨立為0~4的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環，n分別獨立為0~5的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成環己烷環或苯環。 A benzofluorene compound represented by the following formula (1'-2): In the formula, R 1 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The substituted decyl group, m is independently an integer of 0 to 4, and when two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring, respectively. An integer of 0 to 5 is independently independent. When two or more R 1 are adjacent to each other and substituted on one benzene ring, the groups may bond to form a cyclohexane ring or a benzene ring. 如申請專利範圍第10項或第11項所述之苯并茀化合物，其中R1分別獨立為甲基、乙基、正丙基、異丙基、 正丁基、第二丁基、第三丁基、環己基、苯基、萘基、三甲基矽烷基、三乙基矽烷基或二甲基單第三丁基矽烷基，且m分別獨立為0~2的整數，n分別獨立為0~2的整數，當2個以上的R1鄰接並取代於1個苯環上時，該些可鍵結而形成苯環。 The benzofluorene compound according to claim 10 or 11, wherein R 1 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and third. Butyl, cyclohexyl, phenyl, naphthyl, trimethyldecyl, triethyldecyl or dimethylmono-tert-butylalkyl, and m is independently an integer from 0 to 2, and n is independently An integer of 0 to 2, when two or more R 1 are adjacent to each other and substituted on one benzene ring, these may be bonded to form a benzene ring. 如申請專利範圍第10項或第11項所述之苯并茀化合物，其中R1分別獨立為甲基、乙基、異丙基、第三丁基、環己基、苯基或三甲基矽烷基，m及n分別獨立為0~2的整數。 The benzofluorene compound according to claim 10 or 11, wherein R 1 is independently methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl or trimethyldecane. The base, m and n are each independently an integer of 0~2. 一種發光層用材料，其是發光元件的發光層用材料，其含有如申請專利範圍第1項至第13項中任一項所述之苯并茀化合物。 A material for a light-emitting layer, which is a material for a light-emitting layer of a light-emitting element, which contains the benzofluorene compound according to any one of claims 1 to 13. 一種有機電場發光元件，其包括：一對電極，包含陽極及陰極；以及發光層，配置於該一對電極間、且含有如申請專利範圍第14項所述之發光層用材料。 An organic electroluminescence device comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes and containing the material for a light-emitting layer according to claim 14 of the patent application. 如申請專利範圍第15項所述之有機電場發光元件，其更包括配置於上述陰極與上述發光層之間的電子傳輸層及/或電子注入層，上述電子傳輸層及上述電子注入層的至少1層含有選自由羥基喹啉系金屬錯合物、吡啶衍生物、啡啉衍生物、硼烷衍生物及苯并咪唑衍生物所組成的組群中的至少1種。 The organic electroluminescent device of claim 15, further comprising an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, at least the electron transport layer and the electron injection layer One layer contains at least one selected from the group consisting of a hydroxyquinoline metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. 如申請專利範圍第16項所述之有機電場發光元件，其中上述電子傳輸層及/或上述電子注入層進而含有選 自由鹼金屬、鹼土金屬、稀土金屬、鹼金屬的氧化物、鹼金屬的鹵化物、鹼土金屬的氧化物、鹼土金屬的鹵化物、稀土金屬的氧化物、稀土金屬的鹵化物、鹼金屬的有機錯合物、鹼土金屬的有機錯合物及稀土金屬的有機錯合物所組成的組群中的至少1種。 The organic electroluminescence device of claim 16, wherein the electron transport layer and/or the electron injection layer further comprises an option Free alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, rare earth metal halide, alkali metal organic At least one of a group consisting of a complex compound, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. 一種顯示裝置，其包括如申請專利範圍第15項至第17項中任一項所述之有機電場發光元件。 A display device comprising the organic electroluminescent device according to any one of claims 15 to 17. 一種照明裝置，其包括如申請專利範圍第15項至第17項中任一項所述之有機電場發光元件。 An illuminating device comprising the organic electroluminescent device according to any one of claims 15 to 17.
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