TW201402549A - Light emitting element material and light emitting element - Google Patents

Light emitting element material and light emitting element Download PDF

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TW201402549A
TW201402549A TW102121831A TW102121831A TW201402549A TW 201402549 A TW201402549 A TW 201402549A TW 102121831 A TW102121831 A TW 102121831A TW 102121831 A TW102121831 A TW 102121831A TW 201402549 A TW201402549 A TW 201402549A
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emitting element
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Shinichi Matsuki
Kazumasa Nagao
Takeshi Arai
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Toray Industries
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Abstract

An organic thin film light emitting element is provided. By using a light emitting element material containing a compound having a specific carbazole skeleton, the organic thin film light emitting element can have both high luminous efficiency and durability.

Description

發光元件材料及發光元件 Light-emitting element material and light-emitting element

本發明是有關於一種可將電能(electric energy)轉換為光的發光元件及用於該發光元件的發光元件材料。更詳細而言，本發明是有關於一種可利用於顯示元件、平板顯示器(flat panel display)、背光裝置(back light)、照明、室內裝飾(interior)、標識、廣告牌、電子照相機及光訊號產生器等領域的發光元件及用於該發光元件的發光元件材料。 The present invention relates to a light-emitting element that can convert electric energy into light and a light-emitting element material for the light-emitting element. More specifically, the present invention relates to a display element, a flat panel display, a backlight, an illumination, an interior, a logo, a billboard, an electronic camera, and an optical signal. A light-emitting element in the field of a generator or the like and a light-emitting element material for the light-emitting element.

近年來，正積極地進行於自陰極注入的電子與自陽極注入的電洞在夾持於兩極的有機螢光體內再結合時發光的有機薄膜發光元件的研究。該發光元件以薄型且低驅動電壓下的高亮度發光、及利用選擇螢光材料的多色發光為特徵而備受矚目。 In recent years, studies have been actively conducted on an organic thin film light-emitting element in which electrons injected from a cathode and a hole injected from an anode are recombined in an organic phosphor sandwiched between two electrodes. This light-emitting element has been attracting attention by its high-brightness light emission at a thin and low driving voltage and multi-color light emission using a selective fluorescent material.

關於該研究，自由柯達(Kodak)公司的C.W.Tang等人揭示出有機薄膜元件以高亮度發光以來，進行了眾多實用化研討，有機薄膜發光元件於行動電話的主顯示器(main display)等中被採用等實用化著實地不斷推進。但是，技術性課題亦仍然很 多，其中元件的高效率化與長壽命化的同時實現為重大課題之一。 Regarding this research, CWTang et al. of Kodak Co., Ltd. revealed that many organic thin film elements have been used for high-intensity illumination, and many organic thin-film light-emitting elements have been used in the main display of mobile phones. The use of practical and practical on the ground continues to advance. However, technical issues are still very Many of them are one of the major issues at the same time as the high efficiency and long life of components.

元件的驅動電壓受將電洞或電子等載子(carrier)傳輸至發光層的載子傳輸材料很大影響。其中，傳輸電洞的材料(電洞傳輸材料)已知有具有咔唑骨架的材料(例如，參照專利文獻1~專利文獻2)。另外，已知上述具有咔唑骨架的材料具有高三重態能階(triplet level)(例如，參照專利文獻3)，尤其提出有用作封閉來自磷光發光層的三重態激子的材料(例如，參照專利文獻4)。 The driving voltage of the element is greatly affected by the carrier transport material that transports carriers such as holes or electrons to the light-emitting layer. Among them, a material having a carbazole skeleton is known as a material for transporting a hole (a hole transporting material) (for example, refer to Patent Document 1 to Patent Document 2). Further, it is known that the above-mentioned material having a carbazole skeleton has a high triplet level (for example, refer to Patent Document 3), and in particular, a material for blocking triplet excitons from a phosphorescent emitting layer is proposed (for example, reference) Patent Document 4).

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

專利文獻1：日本專利特開平8-3547號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 8-3547

專利文獻2：韓國專利申請案公開第2010-0079458號公報 Patent Document 2: Korean Patent Application Publication No. 2010-0079458

專利文獻3：國際公開第2011/024451號 Patent Document 3: International Publication No. 2011/024451

專利文獻4：國際公開第2012/001986號 Patent Document 4: International Publication No. 2012/001986

然而，先前技術中難以充分地降低元件的驅動電壓，另外，即便可降低驅動電壓，元件的發光效率、耐久壽命的同時實現亦不充分。如此，尚未發現使高發光效率與耐久壽命同時實現的技術。 However, in the prior art, it is difficult to sufficiently reduce the driving voltage of the element, and even if the driving voltage can be lowered, the luminous efficiency and the endurance life of the element are not sufficiently realized. Thus, techniques for achieving high luminous efficiency and durable life have not been found at the same time.

本發明的目的在於解決上述先前技術的問題，提供一種改善了發光效率及耐久壽命的有機薄膜發光元件。 An object of the present invention is to solve the above problems of the prior art and to provide an organic thin film light-emitting element having improved luminous efficiency and durability.

本發明是一種發光元件材料，其特徵在於：含有下述通式(1)所表示的化合物。 The present invention is a light-emitting device material comprising a compound represented by the following formula (1).

R1~R16可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R17R18所組成的組群。R17及R18為芳基或雜芳基。其中，於R1~R8的任一位置及R9~R16的任一位置兩個咔唑骨架連結。Ar1及Ar3可分別相同亦可不同，表示經取代或未經取代的苯基。Ar2表示經取代或未經取代的伸苯基。Ar4為下述式(A)或下述式(B)所表示的基團。 R 1 to R 16 may be the same or different and are selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine carbhydryl groups. a group consisting of decyl, and -P(=O)R 17 R 18 . R 17 and R 18 are aryl or heteroaryl. Here, the two carbazole skeletons are bonded at any position of R 1 to R 8 and at any position of R 9 to R 16 . Ar 1 and Ar 3 may be the same or different and each represents a substituted or unsubstituted phenyl group. Ar 2 represents a substituted or unsubstituted phenylene group. Ar 4 is a group represented by the following formula (A) or the following formula (B).

R19~R36可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R37R38所組成的組群。R37及R38為芳基或雜芳基。其中，式(A)中於R19~R28中的任一位置與氮原子連結，式(B)中於R29~R36中的任一位置與氮原子連結。X為氧原子、或硫原子、或N-Ar5。Ar5表示經取代或未經取代的苯基。Y表示碳原子，n為0或1。於n為1時，Y亦可經烷基取代。 R 19 to R 36 may be the same or different and are selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine methyl fluorenyl. a group consisting of decyl, and -P(=O)R 37 R 38 . R 37 and R 38 are aryl or heteroaryl. Wherein, in any one of R 19 to R 28 in the formula (A), it is bonded to a nitrogen atom, and in any one of R 29 to R 36 in the formula (B), it is bonded to a nitrogen atom. X is an oxygen atom, or a sulfur atom, or N-Ar 5 . Ar 5 represents a substituted or unsubstituted phenyl group. Y represents a carbon atom and n is 0 or 1. When n is 1, Y may also be substituted by an alkyl group.

根據本發明，可提供一種具有高發光效率，進而亦兼具充分的耐久壽命的有機電場發光元件。 According to the present invention, it is possible to provide an organic electroluminescence element having high luminous efficiency and further sufficient durability.

對本發明中的通式(1)所表示的化合物進行詳細說明。 The compound represented by the formula (1) in the present invention will be described in detail.

R1~R16可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R17R18所組成的組群。R17及R18為芳基或雜芳基。其中，於R1~R8的任一位置及R9~R16的任一位置兩個咔唑骨架連結。Ar1及Ar3可分別相同亦可不同，表示經取代或未經取代的苯基。Ar2表示經取代或未經取代的伸苯基。Ar4為下述式(A)或下述式(B)所表示的基團。 R 1 to R 16 may be the same or different and are selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine carbhydryl groups. a group consisting of decyl, and -P(=O)R 17 R 18 . R 17 and R 18 are aryl or heteroaryl. Here, the two carbazole skeletons are bonded at any position of R 1 to R 8 and at any position of R 9 to R 16 . Ar 1 and Ar 3 may be the same or different and each represents a substituted or unsubstituted phenyl group. Ar 2 represents a substituted or unsubstituted phenylene group. Ar 4 is a group represented by the following formula (A) or the following formula (B).

R19~R36可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R37R38所組成的組群。R37及R38為芳基或雜芳基。其中，式(A)中於R19~R28中的任一位置與氮原子連結，式(B)中於R29~R36中的任一位置與氮原子連結。X為氧原子、或硫原子、或N-Ar5。Ar5表示經取代或未經取代的苯基。Y表示碳原子，n為0或1。於n為1時，Y亦可經烷基取代。 R 19 to R 36 may be the same or different and are selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine methyl fluorenyl. a group consisting of decyl, and -P(=O)R 37 R 38 . R 37 and R 38 are aryl or heteroaryl. Wherein, in any one of R 19 to R 28 in the formula (A), it is bonded to a nitrogen atom, and in any one of R 29 to R 36 in the formula (B), it is bonded to a nitrogen atom. X is an oxygen atom, or a sulfur atom, or N-Ar 5 . Ar 5 represents a substituted or unsubstituted phenyl group. Y represents a carbon atom and n is 0 or 1. When n is 1, Y may also be substituted by an alkyl group.

該些取代基之中，氫亦可為氘。另外，未經取代的苯基等中的氫亦可為氘。 Among these substituents, hydrogen may also be ruthenium. Further, the hydrogen in the unsubstituted phenyl group or the like may be ruthenium.

烷基是表示例如甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等飽和脂肪族烴基，該烷基可具有取代基亦可不具有取代基。烷基的碳數並無特別限定，就獲取的容易性或 成本(cost)的方面而言，通常為1以上、20以下，更佳為1以上、8以下的範圍。 The alkyl group is a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a t-butyl group, and the alkyl group may have a substituent or may have no substituent. . The carbon number of the alkyl group is not particularly limited, and the ease of acquisition or In terms of cost, it is usually 1 or more and 20 or less, and more preferably 1 or more and 8 or less.

環烷基是表示例如環丙基、環己基、降莰基、金剛烷基等飽和脂環式烴基，該環烷基可具有取代基亦可不具有取代基。烷基部分的碳數並無特別限定，通常為3以上、20以下的範圍。 The cycloalkyl group means a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a decyl group or an adamantyl group, and the cycloalkyl group may or may not have a substituent. The carbon number of the alkyl moiety is not particularly limited, and is usually in the range of 3 or more and 20 or less.

雜環基是表示例如吡喃環、哌啶環、環狀醯胺等環內具有碳以外的原子的脂肪族環，該雜環基可具有取代基亦可不具有取代基。雜環基的碳數並無特別限定，通常為2以上、20以下的範圍。 The heterocyclic group is an aliphatic ring having an atom other than carbon in a ring such as a pyran ring, a piperidine ring or a cyclic decylamine, and the heterocyclic group may have a substituent or a substituent. The carbon number of the heterocyclic group is not particularly limited, but is usually in the range of 2 or more and 20 or less.

烯基是表示例如乙烯基、烯丙基、丁二烯基等含有雙鍵的不飽和脂肪族烴基，該烯基可具有取代基亦可不具有取代基。烯基的碳數並無特別限定，通常為2以上、20以下的範圍。 The alkenyl group is an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group or a butadienyl group, and the alkenyl group may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, and is usually in the range of 2 or more and 20 or less.

環烯基是表示例如環戊烯基、環戊二烯基、環己烯基等含有雙鍵的不飽和脂環式烴基，該環烯基可具有取代基亦可不具有取代基。環烯基的碳數並無特別限定，通常為2以上、20以下的範圍。 The cycloalkenyl group is an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group or a cyclohexenyl group, and the cycloalkenyl group may or may not have a substituent. The carbon number of the cycloalkenyl group is not particularly limited, and is usually in the range of 2 or more and 20 or less.

炔基是表示例如乙炔基等含有三鍵的不飽和脂肪族烴基，該炔基可具有取代基亦可不具有取代基。炔基的碳數並無特別限定，通常為2以上、20以下的範圍。 The alkynyl group is an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, and the alkynyl group may have a substituent or may have no substituent. The carbon number of the alkynyl group is not particularly limited, and is usually in the range of 2 or more and 20 or less.

鹵素是表示氟、氯、溴、碘。 Halogen means fluorine, chlorine, bromine or iodine.

羰基、羧基、氧羰基、胺甲醯基可具有取代基亦可不具 有取代基。 The carbonyl group, the carboxyl group, the oxycarbonyl group, the amine carbenyl group may have a substituent or may not have There are substituents.

矽烷基是表示例如三甲基矽烷基等具有與矽原子的鍵的官能基，該矽烷基可具有取代基亦可不具有取代基。矽烷基的碳數並無特別限定，通常為3以上、20以下的範圍。另外，矽數通常為1以上、6以下的範圍。 The decyl group is a functional group having a bond with a ruthenium atom such as a trimethyl decyl group, and the decyl group may have a substituent or may have no substituent. The carbon number of the decyl group is not particularly limited, and is usually in the range of 3 or more and 20 or less. Further, the number of turns is usually in the range of 1 or more and 6 or less.

-P(=O)R17R18可具有取代基亦可不具有取代基。 -P(=O)R 17 R 18 may have a substituent or may have no substituent.

芳基是表示例如苯基、聯苯基、茀基、菲基、聯三伸苯基(triphenylenyl)、聯三苯基等芳香族烴基。芳基可具有取代基亦可不具有取代基。芳基的碳數並無特別限定，通常為6以上、40以下的範圍。 The aryl group means an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group or a terphenyl group. The aryl group may have a substituent or may have no substituent. The carbon number of the aryl group is not particularly limited, and is usually in the range of 6 or more and 40 or less.

雜芳基是表示呋喃基、苯硫基(thiophenyl)、吡啶基、吡嗪基、嘧啶基、三嗪基、苯并呋喃基、苯并苯硫基、吲哚基等於一個或多個環內具有碳以外的原子的環狀芳香族基，該雜芳基可未經取代亦可經取代。雜芳基的碳數並無特別限定，通常為2以上、30以下的範圍。 A heteroaryl group means a furanyl group, a thiophenyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a triazinyl group, a benzofuranyl group, a benzophenylthio group, a fluorenyl group, and one or more rings. A cyclic aromatic group having an atom other than carbon, and the heteroaryl group may be unsubstituted or substituted. The carbon number of the heteroaryl group is not particularly limited, and is usually in the range of 2 or more and 30 or less.

伸芳基是表示由芳基衍生的二價基團，例如可例示：伸苯基、伸萘基、伸聯苯基、伸茀基、伸菲基、伸聯三苯基、伸蒽基、伸芘基等。該些伸芳基可具有取代基亦可不具有取代基。伸芳基的碳數並無特別限定，通常為6以上、40以下的範圍。另外，在伸芳基具有取代基的情況下，亦包括取代基在內的碳數較佳為6以上、60以下的範圍。 The aryl group is a divalent group derived from an aryl group, and examples thereof include a phenyl group, a naphthyl group, a phenylene group, a fluorenyl group, a phenanthrenyl group, a stilbene group, and a fluorenyl group. Stretching the base and so on. The extended aryl groups may have a substituent or may have no substituent. The carbon number of the aryl group is not particularly limited, and is usually in the range of 6 or more and 40 or less. Further, when the exoaryl group has a substituent, the number of carbon atoms including the substituent is preferably in the range of 6 or more and 60 or less.

所謂於R1~R8的任一位置及R9~R16的任一位置兩個咔唑骨架連結，例如若舉出於R6的位置與R10的位置連結的情況為例，則是指R6所鍵結的部分的碳原子與R10所鍵結的部分的碳原子直接鍵結。同樣地，所謂於R19~R28中的任一位置與氮原子連結，例如若舉出於R21的位置與氮原子連結的情況為例，則是指R21所鍵結的部分的碳原子與氮原子直接鍵結。 The carbazole skeleton is linked at any position of R 1 to R 8 and at any position of R 9 to R 16 . For example, the case where the position of R 6 is linked to the position of R 10 is as an example. It is meant that the carbon atom of the moiety to which R 6 is bonded is directly bonded to the carbon atom of the moiety to which R 10 is bonded. Similarly, any position of R 19 to R 28 is bonded to a nitrogen atom, and for example, a case where the position of R 21 is bonded to a nitrogen atom is taken as an example of the carbon bonded to R 21 . The atom is directly bonded to the nitrogen atom.

先前具有咔唑骨架的化合物作為發光元件材料未必具有充分的性能。例如，9,9'-二苯基-9H,9'H-3,3'-聯咔唑或1,3-二(9H-咔唑-9-基)苯(簡稱：mCP)的三重態能階高，作為激子阻斷材料為通用的材料，但存在電離電位(ionization potential)大，電洞注入．傳輸性缺乏，驅動電壓變高的問題。另外，亦存在對元件的耐久性造成影響的玻璃轉變溫度(glass transition temperature)亦低的問題。 A compound having a carbazole skeleton previously does not necessarily have sufficient properties as a material of a light-emitting element. For example, the triplet state of 9,9'-diphenyl-9H,9'H-3,3'-bicarbazole or 1,3-bis(9H-carbazol-9-yl)benzene (abbreviation: mCP) The energy level is high, and it is a general-purpose material as an exciton blocking material, but there is a large ionization potential and a hole injection. The problem of lack of transmission and high driving voltage. In addition, there is also a problem that the glass transition temperature which affects the durability of the element is also low.

本發明者等人於上述化合物的改良的研討中著眼於具有咔唑骨架的化合物的電洞傳輸能的強度與三重態能量的高度。通常，具有咔唑骨架的化合物具有傳輸電洞與電子兩種電荷的特性。本發明者等人考慮或許由於先前具有咔唑骨架的化合物的電洞傳輸能小，故而進入發光層中的電洞的比率小於自電子傳輸層進入的電子，發光層中的電荷的平衡(balance)被破壞，從而導致元件性能的降低。 The inventors of the present invention have focused on the improvement of the strength of the hole transport energy and the height of the triplet energy of the compound having a carbazole skeleton in the improvement of the above compound. Generally, a compound having a carbazole skeleton has a property of transmitting both a hole and an electron. The inventors of the present invention considered that the ratio of the holes entering the light-emitting layer is smaller than that of the electrons entering the light-emitting layer, and the balance of the charges in the light-emitting layer is balanced because the hole transporting energy of the compound having the previous carbazole skeleton is small. ) is destroyed, resulting in a decrease in component performance.

因此，若如本發明的化合物般使咔唑二聚化，則共軛擴 展，電洞傳輸性提高。但是，於氮原子上存在取代基時，根據其種類而亦有電洞傳輸能受到阻礙之虞，未必全部的咔唑二聚物的電洞傳輸性均高。 Therefore, if the carbazole is dimerized as in the compound of the present invention, the conjugate is expanded. Exhibition, hole transmission improved. However, when a substituent is present on a nitrogen atom, there is a possibility that the hole transport energy is hindered depending on the type thereof, and the hole transport properties of all the carbazole dimers are not necessarily high.

此處，在咔唑二聚物的氮原子上的取代基具有先前以來作為電洞傳輸性取代基顯示出優異特性的胺骨架的情況下，可具有更高的電洞傳輸性。但是，即便在該情況下，根據胺骨架中的取代基而亦有三重態能量降低的可能性。 Here, in the case where the substituent on the nitrogen atom of the carbazole dimer has an amine skeleton which has previously exhibited excellent characteristics as a hole transporting substituent, it has higher hole transportability. However, even in this case, there is a possibility that the triplet energy is lowered depending on the substituent in the amine skeleton.

例如，可知如韓國專利申請案公開第2010-0079458號公報的化合物33或化合物36(以下所示的結構)所具有的萘基其本身的三重態能階低，使化合物的三重態能階降低。若使用三重態能階低的化合物作為激子阻斷材料而製成發光元件，則發光效率會因自發光層洩漏出來的激子而降低。 For example, it is known that the compound 33 or the compound 36 (structure shown below) of the Korean Patent Application Publication No. 2010-0079458 has a naphthyl group having a low triplet energy level, which lowers the triplet energy level of the compound. . When a compound having a low triplet energy level is used as an exciton blocking material to form a light-emitting element, the light-emitting efficiency is lowered by excitons leaking from the light-emitting layer.

另一方面，如國際公開第2006/61759號的Table1所示的化合物般，咔唑二聚物的鄰位上具有取代基的化合物中分子歪曲。因此，即便使咔唑二聚化，共軛亦不會擴展，可維持咔唑本 身的三重態能階，作為化合物的三重態能階亦顯示高的值。然而，如上所述，由於共軛不擴展，故而無法獲得提高電洞傳輸性的效果。 On the other hand, as in the compound shown in Table 1 of International Publication No. 2006/61759, the compound having a substituent in the ortho position of the carbazole dimer has a molecular distortion. Therefore, even if the carbazole is dimerized, the conjugate will not expand and the carbazole can be maintained. The triplet energy level of the body also shows a high value as the triplet energy level of the compound. However, as described above, since the conjugate does not spread, the effect of improving the hole transportability cannot be obtained.

如上所述，維持高的三重態能階與發揮出高的電洞傳輸性處於取捨(trade-off)的關係，尚未發現於實用化階段可同時實現高的三重態能階與高的電洞傳輸性的材料。本發明者等人進行努力研討，結果發現氮原子上的胺骨架具有式(A)或式(B)所表示的基團作為胺骨架上的取代基的化合物維持高的三重態能階且具有高的電洞傳輸性，從而完成了本發明。 As described above, maintaining a high triplet energy level is in a trade-off relationship with a high hole transmission property, and it has not been found that a high triplet energy level and a high hole can be simultaneously realized in the practical stage. Transmissive material. As a result of intensive studies, the inventors of the present invention have found that a compound having a group represented by formula (A) or formula (B) on a nitrogen atom as a substituent on an amine skeleton maintains a high triplet energy level and has The high hole transportability thus completes the present invention.

通式(1)所表示的化合物較佳為於分子中含有2個或3個咔唑骨架，藉此具有高薄膜穩定性與優異的耐熱性。 The compound represented by the formula (1) preferably contains two or three carbazole skeletons in the molecule, thereby having high film stability and excellent heat resistance.

另外，通式(1)所表示的化合物藉由使咔唑骨架中的一個氮原子上的取代基具有胺骨架而顯示出優異的電洞傳輸能。進而，Ar4為式(A)或式(B)所表示的基團的化合物中共軛系不易擴展至必要以上。因此，可於不使三重態能量降低的情況下增大分子量，故而玻璃轉變溫度增加。另外，由於可形成穩定的薄膜，故而會使元件的耐久性提高。 Further, the compound represented by the formula (1) exhibits excellent hole transport energy by giving a substituent on one nitrogen atom in the carbazole skeleton an amine skeleton. Further, in the compound in which Ar 4 is a group represented by the formula (A) or the formula (B), the conjugated system is not easily extended to more than necessary. Therefore, the molecular weight can be increased without lowering the triplet energy, and thus the glass transition temperature is increased. Further, since a stable film can be formed, the durability of the element is improved.

進而，較佳為式(A)或式(B)所表示的基團中的X相對於經取代的氮原子鍵結於對位上，即式(A)中於R21的位置與氮原子連結，式(B)中於R31的位置與氮原子連結。其原因在於，可進一步減小電離電位，進一步提高電洞注入能。 Further, it is preferred that X in the group represented by the formula (A) or the formula (B) is bonded to the para position with respect to the substituted nitrogen atom, that is, the position of R 21 in the formula (A) and the nitrogen atom. In the formula, the position of R 31 in the formula (B) is bonded to a nitrogen atom. The reason is that the ionization potential can be further reduced, and the hole injection energy can be further improved.

通式(1)中的Ar1及Ar3為經取代或未經取代的苯基，Ar2為經取代或未經取代的伸苯基。該情況的取代基較佳為烷基或鹵素。烷基或鹵素幾乎不會對共軛造成影響，可維持高的三重態能階。 Ar 1 and Ar 3 in the formula (1) are a substituted or unsubstituted phenyl group, and Ar 2 is a substituted or unsubstituted phenyl group. The substituent in this case is preferably an alkyl group or a halogen. The alkyl or halogen hardly affects the conjugation and maintains a high triplet energy level.

通式(1)所表示的化合物的咔唑二聚物骨架較佳為如通式(2)所表示的形態般氮原子位於對位上。其原因在於，由於該結構具有與聯苯胺骨架相同的部位，故而電離電位變得更小，電洞注入能及電洞傳輸能進一步提高。 The carbazole dimer skeleton of the compound represented by the formula (1) is preferably in the para position such that the nitrogen atom is in the form represented by the formula (2). The reason for this is that since the structure has the same portion as the benzidine skeleton, the ionization potential becomes smaller, and the hole injection energy and the hole transport can be further improved.

R39~R52可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R53R54所組成的組群。R53及R54為芳基或雜芳基。Ar6及Ar8可分別相同亦可不同，表示經取代或未經取代的苯基。Ar7表示經取代或未經取代的伸苯基。Ar9為上述式 (A)或上述式(B)所表示的基團。 R 39 to R 52 may be the same or different and are selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine carbhydryl groups. a group consisting of decyl, and -P(=O)R 53 R 54 . R 53 and R 54 are aryl or heteroaryl. Ar 6 and Ar 8 may be the same or different and each represents a substituted or unsubstituted phenyl group. Ar 7 represents a substituted or unsubstituted stretched phenyl group. Ar 9 is a group represented by the above formula (A) or the above formula (B).

該些取代基的說明與上述通式(1)的說明相同。 The description of these substituents is the same as the description of the above formula (1).

在電洞傳輸層直接接觸於含有三重態發光性摻雜劑(dopant)的發光層的情況下，較佳為通式(1)或通式(2)所表示的化合物的三重態能量為2.70eV以上。其原因在於，可以高水準(high level)抑制三重態激發能量自發光層的洩漏，可進一步提高發光元件的發光效率，進一步延長壽命。 In the case where the hole transport layer is in direct contact with the light-emitting layer containing a triplet luminescent dopant, it is preferred that the compound represented by the formula (1) or the formula (2) has a triplet energy of 2.70. More than eV. This is because the leakage of the triplet excitation energy from the light-emitting layer can be suppressed at a high level, and the light-emitting efficiency of the light-emitting element can be further improved, and the lifetime can be further extended.

此外，本發明中的三重態能量為將磷光光譜(phosphorescence spectrum)的短波長的上升位置的波長換算為光能(optical energy)而獲得的值。 Further, the triplet energy in the present invention is a value obtained by converting the wavelength of the rising position of the short wavelength of the phosphorescence spectrum into optical energy.

進而，通式(1)所表示的化合物的Ar1、及通式(2)所表示的化合物的Ar6較佳為未經取代的苯基。其原因在於，藉此可更長期地維持高的三重態能階，可使容易失活得到抑制，因此可達成更高的發光效率。就相同理由而言，通式(1)所表示的化合物的Ar2、及通式(2)所表示的化合物的Ar7較佳為未經取代的伸苯基，通式(1)所表示的化合物的Ar3及Ar5較佳為未經取代的苯基。另外，式(B)的n較佳為0。其原因在於，蒸鍍通式(1)所表示的化合物時的熱穩定性進一步提高。 Further, Ar 1 of the compound represented by the formula (1) and Ar 6 of the compound represented by the formula (2) are preferably an unsubstituted phenyl group. This is because the high triplet energy level can be maintained for a longer period of time, and the easy deactivation can be suppressed, so that higher luminous efficiency can be achieved. For the same reason, Ar 2 of the compound represented by the formula (1) and Ar 7 of the compound represented by the formula (2) are preferably an unsubstituted phenyl group, represented by the formula (1). Ar 3 and Ar 5 of the compound are preferably unsubstituted phenyl groups. Further, n of the formula (B) is preferably 0. This is because the thermal stability when the compound represented by the formula (1) is vapor-deposited is further improved.

關於R1~R54，若考慮原料獲取的容易性或合成成本，則最佳為其全部為氫。在R1~R54為氫以外的基團的情況下，不使三重態能階降低，使電離電位增大的效果小的基團較佳為烷基、環 烷基、烷氧基。該些基團亦可進而經取代。 Regarding R 1 to R 54 , it is preferable to use all of them as hydrogen in consideration of easiness in obtaining raw materials or synthesis cost. When R 1 to R 54 are a group other than hydrogen, the group having a small effect of increasing the ionization potential without lowering the triplet energy level is preferably an alkyl group, a cycloalkyl group or an alkoxy group. These groups may also be substituted.

上述通式(1)所表示的化合物並無特別限定，具體而言可列舉如下例子。此外，以下為例示，即便為此處所寫明的化合物以外的化合物但只要為通式(1)所表示的化合物，則可同樣較佳地使用。 The compound represented by the above formula (1) is not particularly limited, and specific examples thereof include the following. In addition, the following is exemplified, and a compound other than the compound described herein can be used in the same manner as long as it is a compound represented by the formula (1).

如上所述的具有咔唑骨架的化合物的合成可使用公知的方法。合成咔唑二聚物的方法例如可列舉利用使用鈀觸媒或銅觸媒的咔唑衍生物與鹵化物或三氟甲磺酸鹽化體的偶合反應(coupling reaction)的方法，但並不限定於此。作為一例，將使 用9-苯基咔唑-3-硼酸的例子示於以下。 A known method can be used for the synthesis of the compound having a carbazole skeleton as described above. The method for synthesizing the carbazole dimer includes, for example, a method using a coupling reaction of a carbazole derivative using a palladium catalyst or a copper catalyst with a halide or a triflate compound, but it is not Limited to this. As an example, it will make Examples of 9-phenylcarbazole-3-boronic acid are shown below.

此外，上述反應中使用9-苯基咔唑-2-硼酸酯代替9-苯基咔唑-3-硼酸而反應亦同樣進行。該情況下，可合成咔唑二聚物的位置異構物。 Further, in the above reaction, 9-phenylcarbazole-2-borate was used instead of 9-phenylcarbazole-3-boronic acid, and the reaction was also carried out in the same manner. In this case, a positional isomer of the carbazole dimer can be synthesized.

另外，於咔唑的N上導入取代基的方法例如可列舉利用使用鈀觸媒或銅觸媒的咔唑衍生物與鹵化物的偶合反應的方法，但並不限定於此。作為一例，將使用N-(4-氯苯基)-N,9-二苯基-9H-咔唑基-3-胺的例子示於以下。 In addition, a method of introducing a substituent to N of carbazole is, for example, a method of coupling reaction of a carbazole derivative and a halide using a palladium catalyst or a copper catalyst, but is not limited thereto. As an example, an example using N-(4-chlorophenyl)-N,9-diphenyl-9H-carbazolyl-3-amine is shown below.

通式(1)所表示的化合物可用作發光元件材料。此處本發明中的發光元件材料是表示發光元件的任意層中所使用的材料，如下所述，除電洞注入層、電洞傳輸層、發光層及/或電子傳輸層中所使用的材料以外，亦包含陰極的保護膜中所使用的材料。藉由將本發明中的通式(1)所表示的化合物用於發光元件的任意層，可獲得可實現高發光效率且耐久性優異的發光元件。 The compound represented by the formula (1) can be used as a material for a light-emitting element. Here, the light-emitting element material in the present invention is a material used in any layer of the light-emitting element, as described below, except for materials used in the hole injection layer, the hole transport layer, the light-emitting layer, and/or the electron transport layer. Also included is the material used in the protective film of the cathode. By using the compound represented by the formula (1) in the present invention for any layer of a light-emitting element, a light-emitting element which can achieve high light-emitting efficiency and is excellent in durability can be obtained.

其次，對本發明的發光元件的實施方式進行詳細說明。本發明的發光元件具有陽極與陰極、及介存於該些陽極與陰極之間的有機層，該有機層藉由電能而發光。 Next, an embodiment of the light-emitting element of the present invention will be described in detail. The light-emitting element of the present invention has an anode and a cathode, and an organic layer interposed between the anode and the cathode, and the organic layer emits light by electric energy.

此種發光元件中的陽極與陰極之間的層構成除僅包含發光層的構成以外，亦可列舉：1)發光層/電子傳輸層、2)電洞傳輸層/發光層、3)電洞傳輸層/發光層/電子傳輸層、4)電洞注入層/電洞傳輸層/發光層/電子傳輸層、5)電洞傳輸層/發光層/電子傳輸層/電子注入層、6)電洞注入層/電洞傳輸層/發光層/電子傳輸層/電子注入層等積層構成。另外，上述各層可分別為單一層、多 層的任一種，亦可經摻雜。 The layer configuration between the anode and the cathode in such a light-emitting element may be, in addition to the configuration including only the light-emitting layer, 1) a light-emitting layer/electron transport layer, 2) a hole transport layer/light-emitting layer, and 3) a hole Transport layer/light-emitting layer/electron transport layer, 4) hole injection layer/hole transport layer/light-emitting layer/electron transport layer, 5) hole transport layer/light-emitting layer/electron transport layer/electron injection layer, 6) electricity The hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer is laminated. In addition, each of the above layers may be a single layer or more Any of the layers may also be doped.

通式(1)所表示的化合物於發光元件中可用於上述任一層，可尤佳地用於電洞傳輸層。 The compound represented by the formula (1) can be used in any of the above layers in the light-emitting element, and can be preferably used for the hole transport layer.

於本發明的發光元件中，理想的是陽極與陰極具有用以供給充分的電流以使元件發光的作用，且至少一者為透明或半透明以提取光。通常，使形成於基板上的陽極為透明電極。 In the light-emitting element of the present invention, it is desirable that the anode and the cathode have a function of supplying a sufficient current to cause the element to emit light, and at least one of them is transparent or translucent to extract light. Usually, the anode formed on the substrate is a transparent electrode.

陽極中所使用的材料只要為可將電洞效率良好地注入至有機層中的材料且為透明或半透明以提取光，則並不特別限定於氧化鋅、氧化錫、氧化銦、氧化銦錫(ITO)、氧化銦鋅(IZO)等導電性金屬氧化物，或金、銀、鉻等金屬，碘化銅、硫化銅等無機導電性物質，聚噻吩、聚吡咯、聚苯胺等導電性聚合物等，但尤其理想的是使用ITO玻璃或奈塞玻璃(NESA glass)。該些電極材料可單獨使用，亦可積層或混合多種材料而使用。透明電極的電阻只要可供給對元件的發光充分的電流即可，因此並無限定，但就元件的消耗電力的觀點而言理想的是低電阻。例如若為300Ω/□以下的ITO基板，則作為元件電極而發揮功能，由於目前亦可供給10Ω/□左右的基板，故而尤其理想的是使用20Ω/□以下的低電阻的基板。ITO的厚度可根據電阻值而任意選擇，但多數情況下通常是使用45nm~300nm之間的厚度。 The material used in the anode is not particularly limited to zinc oxide, tin oxide, indium oxide, or indium tin oxide as long as it is a material that can efficiently inject holes into the organic layer and is transparent or translucent to extract light. Conductive metal oxides such as (ITO) and indium zinc oxide (IZO), metals such as gold, silver, and chromium, inorganic conductive materials such as copper iodide and copper sulfide, and conductive polymerization such as polythiophene, polypyrrole, and polyaniline. Etc., but it is especially desirable to use ITO glass or NESA glass. The electrode materials may be used singly or in combination of a plurality of materials. The electric resistance of the transparent electrode is not limited as long as it can supply a current sufficient for light emission of the element, but it is preferably low resistance from the viewpoint of power consumption of the element. For example, an ITO substrate of 300 Ω/□ or less functions as an element electrode, and a substrate of about 10 Ω/□ can be supplied at present. Therefore, it is particularly preferable to use a substrate having a low resistance of 20 Ω/□ or less. The thickness of the ITO can be arbitrarily selected according to the resistance value, but in many cases, a thickness of between 45 nm and 300 nm is usually used.

另外，為了保持發光元件的機械強度，較佳為於基板上形成發光元件。基板可較佳地使用鈉玻璃(soda glass)或無鹼玻 璃(non-alkali glass)等玻璃基板。玻璃基板的厚度只要為對保持機械強度而言充分的厚度即可，因此若為0.5mm以上則充分。關於玻璃的材質，由於自玻璃溶出的離子以少為佳，故而較佳為無鹼玻璃。或者，由於實施有SiO2等的障壁塗層(barrier coat)的鈉鈣玻璃(soda lime glass)亦於市場上有售，故而亦可使用該鈉鈣玻璃。進而，若第一電極穩定地發揮功能，則基板無需為玻璃，例如亦可於塑膠基板上形成陽極。ITO膜形成方法並不受電子束法(electron beam method)、濺鍍法(sputtering method)及化學反應法等特別限制。 Further, in order to maintain the mechanical strength of the light-emitting element, it is preferable to form a light-emitting element on the substrate. As the substrate, a glass substrate such as soda glass or non-alkali glass can be preferably used. The thickness of the glass substrate is sufficient as long as it is sufficient to maintain mechanical strength. Therefore, it is sufficient if it is 0.5 mm or more. Regarding the material of the glass, since the ions eluted from the glass are less preferred, the alkali-free glass is preferred. Alternatively, since soda lime glass which is provided with a barrier coat of SiO 2 or the like is also commercially available, the soda lime glass can also be used. Further, when the first electrode stably functions, the substrate does not need to be glass, and for example, an anode can be formed on the plastic substrate. The ITO film formation method is not particularly limited by an electron beam method, a sputtering method, a chemical reaction method, or the like.

陰極中所使用的材料只要為可將電子效率良好地注入至發光層中的物質，則並無特別限定。通常較佳為鉑、金、銀、銅、鐵、錫、鋁、銦等金屬，或該些金屬與鋰、鈉、鉀、鈣、鎂等低功函數金屬的合金或多層積層等。其中，就電阻值或製膜容易性、膜的穩定性、發光效率等方面而言，主成分較佳為鋁、銀、鎂。尤其若由鎂與銀構成，則本發明中的向電子傳輸層及電子注入層中的電子注入變得容易，可以低電壓驅動，故而較佳。 The material used in the cathode is not particularly limited as long as it can inject electrons into the light-emitting layer efficiently. Generally, metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys or multilayers of low-work function metals such as lithium, sodium, potassium, calcium, and magnesium are laminated. Among them, the main component is preferably aluminum, silver or magnesium in terms of resistance value, easiness of film formation, stability of film, luminous efficiency and the like. In particular, when it is composed of magnesium and silver, electron injection into the electron transport layer and the electron injection layer in the present invention is easy, and it can be driven at a low voltage, which is preferable.

進而，為了保護陰極，可列舉將鉑、金、銀、銅、鐵、錫、鋁及銦等金屬，或使用該些金屬的合金，二氧化矽、二氧化鈦及氮化矽等無機物，聚乙烯醇、聚氯乙烯、烴系高分子化合物等有機高分子化合物積層於陰極上作為保護膜層作為較佳例。其中，在自陰極側提取光的元件構造(頂部發光構造(top emission structure))的情況下，保護膜層可自於可見光區域具有透光性的材料中選擇。該些電極的製作法並不特別限制於電阻加熱、電子束、濺鍍、離子鍍覆(ion plating)及塗佈(coating)等。 Further, in order to protect the cathode, metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys using the metals, inorganic substances such as cerium oxide, titanium oxide, and tantalum nitride, and polyvinyl alcohol may be mentioned. An organic polymer compound such as a polyvinyl chloride or a hydrocarbon-based polymer compound is laminated on the cathode as a protective film layer. Among them, the element structure for extracting light from the cathode side (top emission structure (top emission) In the case of structure)), the protective film layer can be selected from materials having light transmissivity in the visible light region. The method of producing the electrodes is not particularly limited to resistance heating, electron beam, sputtering, ion plating, and coating.

電洞注入層為***至陽極與電洞傳輸層之間的層。電洞注入層可為一層，亦可積層多層，任一種均可。若於電洞傳輸層與陽極之間存在電洞注入層，則不僅可以更低電壓驅動，耐久壽命亦提高，而且進而元件的載子平衡提高，發光效率亦提高，故而較佳。 The hole injection layer is a layer interposed between the anode and the hole transport layer. The hole injection layer may be one layer or a plurality of layers, and any one of them may be used. If a hole injection layer is provided between the hole transport layer and the anode, not only can the voltage be driven at a lower voltage, but also the durability life is improved, and the carrier balance of the element is improved, and the luminous efficiency is also improved, which is preferable.

電洞注入層中所使用的材料並無特別限定，例如可使用4,4'-雙(N-(3-甲基苯基)-N-苯基胺基)聯苯(TPD)、4,4'-雙(N-(1-萘基)-N-苯基胺基)聯苯(NPD)、4,4'-雙(N,N-雙(4-聯苯基)胺基)聯苯(TBDB)、雙(N,N'-二苯基-4-胺基苯基)-N,N-二苯基-4,4'-二胺基-1,1'-聯苯(TPD232)等聯苯胺衍生物，4,4',4"-三(3-甲基苯基(苯基)胺基)三苯基胺(m-MTDATA)、4,4',4"-三(1-萘基(苯基)胺基)三苯基胺(1-TNATA)等稱作星爆狀(starburst)芳基胺的材料組群，雙(N-芳基咔唑)或雙(N-烷基咔唑)等雙咔唑衍生物，吡唑啉(pyrazoline)衍生物、均二苯乙烯(stilbene)系化合物、腙系化合物、苯并呋喃衍生物、噻吩衍生物、噁二唑衍生物、酞菁衍生物、卟啉衍生物等雜環化合物，聚合物系中側鏈上具有上述單體的聚碳酸酯或苯乙烯衍生物，聚噻吩、聚苯胺、聚茀、聚乙烯基咔唑及聚矽烷等。另外，亦可使用通式(1)所表示的化合物。其 中，就具有低於通式(1)所表示的化合物的最高佔有分子軌道(Highest Occupied Molecular Orbital，HOMO)能階，自陽極向電洞傳輸層順利地注入傳輸電洞的觀點而言，可更佳地使用聯苯胺衍生物、星爆狀芳基胺系材料組群。 The material used in the hole injection layer is not particularly limited, and for example, 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl (TPD), 4, can be used. 4'-bis(N-(1-naphthyl)-N-phenylamino)biphenyl (NPD), 4,4'-bis(N,N-bis(4-biphenyl)amino) Benzene (TBDB), bis(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl (TPD232 Equivalent benzidine derivative, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine (m-MTDATA), 4,4',4"-three ( a material group called 1-naphthyl(phenyl)amino)triphenylamine (1-TNATA), etc., called starburst arylamine, bis(N-arylcarbazole) or double (N) Bicarbazole derivatives such as -alkylcarbazole, pyrazoline derivatives, stilbene compounds, lanthanide compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives a heterocyclic compound such as a phthalocyanine derivative or a porphyrin derivative, a polycarbonate or a styrene derivative having a monomer as described above in a side chain of a polymer, polythiophene, polyaniline, polyfluorene, polyvinyl fluorene Oxazole and polydecane. Further, a compound represented by the formula (1) can also be used. its In the meantime, it has a higher-order Occupied Molecular Orbital (HOMO) energy level than the compound represented by the general formula (1), and is capable of smoothly injecting a transmission hole from the anode to the hole transport layer. More preferably, a benzidine derivative or a starburst arylamine-based material group is used.

該些材料可單獨使用，亦可混合兩種以上的材料而使用。另外，亦可積層多種材料而製成電洞注入層。進而，若該電洞注入層單獨由受體(acceptor)性化合物構成，或於如上所述的電洞注入材料中摻雜使用受體性化合物，則可更顯著地獲得上述效果，故而更佳。所謂受體性化合物，在用作單層膜的情況下是指與所接觸的電洞傳輸層形成電荷轉移錯合物的材料，及於摻雜使用的情況下是指與構成電洞注入層的材料形成電荷轉移錯合物的材料。若使用此種材料，則電洞注入層的導電性提高，有助於元件的驅動電壓的進一步降低，可獲得發光效率的提高、耐久壽命的提高等效果。 These materials may be used singly or in combination of two or more materials. In addition, a plurality of materials may be laminated to form a hole injection layer. Further, if the hole injection layer is composed of an acceptor compound alone or an acceptor compound is doped into the hole injection material as described above, the above effect can be more remarkably obtained, and thus it is more preferable. . The term "receptor compound" as used in the case of a single layer film means a material which forms a charge transfer complex with the hole transport layer to be contacted, and in the case of doping, refers to and constitutes a hole injection layer. The material forms a material for the charge transfer complex. When such a material is used, the conductivity of the hole injection layer is improved, which contributes to further reduction in the driving voltage of the element, and effects such as improvement in luminous efficiency and improvement in durability life can be obtained.

受體性化合物的例子可列舉：如氯化鐵(III)、氯化鋁、氯化鎵、氯化銦、氯化銻的金屬氯化物，如氧化鉬、氧化釩、氧化鎢、氧化釕的金屬氧化物，如三(4-溴苯基)銨六氯銻酸鹽(TBPAH)的電荷轉移錯合物。另外，亦可較佳地使用分子內具有硝基、氰基、鹵素或三氟甲基的有機化合物，或醌系化合物、酸酐系化合物、富勒烯(fullerene)等。該些化合物的具體例可列舉：六氰基丁二烯、六氰基苯、四氰基乙烯、四氰基醌二甲烷 (TCNQ)、四氟四氰基醌二甲烷(F4-TCNQ)、軸烯(radialene)衍生物、四氟對苯醌(p-fluoranil)、四氯對苯醌(p-chloranil)、四溴對苯醌(p-bromanil)、對苯醌、2,6-二氯苯醌、2,5-二氯苯醌、四甲基苯醌、1,2,4,5-四氰基苯、鄰二氰基苯、對二氰基苯、1,4-二氰基四氟苯、2,3-二氯-5,6-二氰基苯醌、對二硝基苯、間二硝基苯、鄰二硝基苯、對氰基硝基苯、間氰基硝基苯、鄰氰基硝基苯、1,4-萘醌、2,3-二氯萘醌、1-硝基萘、2-硝基萘、1,3-二硝基萘、1,5-二硝基萘、9-氰基蒽、9-硝基蒽、9,10-蒽醌、1,3,6,8-四硝基咔唑、2,4,7-三硝基-9-茀酮、2,3,5,6-四氰基吡啶、順丁烯二酸酐、鄰苯二甲酸酐、C60、及C70等。 Examples of the acceptor compound include metal chlorides such as iron (III) chloride, aluminum chloride, gallium chloride, indium chloride, and ruthenium chloride, such as molybdenum oxide, vanadium oxide, tungsten oxide, and ruthenium oxide. A metal oxide such as a charge transfer complex of tris(4-bromophenyl)ammonium hexachloroantimonate (TBPAH). Further, an organic compound having a nitro group, a cyano group, a halogen or a trifluoromethyl group in the molecule, or an anthraquinone compound, an acid anhydride compound, a fullerene or the like can be preferably used. Specific examples of such compounds include hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, and tetracyanoquinodimethane. (TCNQ), tetrafluorotetracyanoquinodimethane (F4-TCNQ), radialene derivative, p-fluoranil, p-chloranil, tetrabromo P-bromanil, p-benzoquinone, 2,6-dichlorophenylhydrazine, 2,5-dichlorophenylhydrazine, tetramethylphenylhydrazine, 1,2,4,5-tetracyanobenzene, O-dicyanobenzene, p-dicyanobenzene, 1,4-dicyanotetrafluorobenzene, 2,3-dichloro-5,6-dicyanobenzoquinone, p-dinitrobenzene, m-dinitro Benzene, o-dinitrobenzene, p-cyanonitrobenzene, m-cyanonitrobenzene, o-cyanonitrobenzene, 1,4-naphthoquinone, 2,3-dichloronaphthylquinone, 1-nitronaphthalene , 2-nitronaphthalene, 1,3-dinitronaphthalene, 1,5-dinitronaphthalene, 9-cyanoindole, 9-nitroindole, 9,10-fluorene, 1,3,6, 8-tetranitrocarbazole, 2,4,7-trinitro-9-fluorenone, 2,3,5,6-tetracyanopyridine, maleic anhydride, phthalic anhydride, C60, And C70 and so on.

該些之中，金屬氧化物或含氰基的化合物由於容易操作，亦容易蒸鍍而可容易地獲得上述效果，故而較佳。在電洞注入層單獨由受體性化合物構成的情況、或於電洞注入層中摻雜受體性化合物的情況的任一情況下，電洞注入層均可為一層，亦可積層多層而構成。 Among these, a metal oxide or a cyano group-containing compound is preferable because it is easy to handle and is easily vapor-deposited, and the above effects can be easily obtained. In either case where the hole injection layer is composed of an acceptor compound alone or when the hole injection layer is doped with an acceptor compound, the hole injection layer may be one layer or a plurality of layers may be stacked. Composition.

電洞傳輸層為將自陽極注入的電洞傳輸至發光層的層。電洞傳輸層可為單層，亦可積層多層而構成，任一種均可。 The hole transport layer is a layer that transports holes injected from the anode to the light emitting layer. The hole transport layer may be a single layer or a plurality of layers, and any of them may be used.

通式(1)所表示的化合物具有5.1eV~6.0eV的電離電位(蒸鍍膜的AC-2(理研計器)測定值)、高的三重態能階(triplet energy level)、高電洞傳輸性及薄膜穩定性，因此較佳為用於發光元件的電洞注入層及電洞傳輸層。另外，通式(1)所表示的化合 物的能隙(energy gap)大於先前具有聯苯胺骨架的電洞傳輸材料，因此最低未佔分子軌道(Lowest Unoccupied Molecular Orbital，LUMO)能階高，電子阻斷性優異。進而，通式(1)所表示的化合物較佳為用作使用三重態發光材料的元件的電洞傳輸材料。其原因在於，先前具有聯苯胺骨架的電洞傳輸材料的三重態能階低，若直接接觸於含有三重態發光材料的發光層，則會產生三重態能量的洩漏，發光效率降低，但通式(1)所表示的化合物具有高的三重態能量，不會產生此種問題。 The compound represented by the formula (1) has an ionization potential of 5.1 eV to 6.0 eV (AC-2 (measured value) of a vapor deposition film), a high triplet energy level, and high hole transportability. And film stability, it is preferably used for the hole injection layer and the hole transport layer of the light-emitting element. In addition, the compound represented by the formula (1) The energy gap of the object is larger than that of the hole transport material previously having a benzidine skeleton, so the lowest unoccupied Molecular Orbital (LUMO) has a high energy level and excellent electron blocking property. Further, the compound represented by the formula (1) is preferably used as a hole transporting material for an element using a triplet luminescent material. The reason is that the hole transport material having the benzidine skeleton has a low triplet energy level, and if it is directly in contact with the light-emitting layer containing the triplet light-emitting material, triplet energy leakage occurs, and the luminous efficiency is lowered, but the general formula (1) The compound represented has a high triplet energy and does not cause such a problem.

在包含多層電洞傳輸層的情況下，含有通式(1)所表示的化合物的電洞傳輸層較佳為直接接觸於發光層。其原因在於，通式(1)所表示的化合物具有高電子阻斷性，可防止自發光層流出的電子的侵入。進而，通式(1)所表示的化合物具有高的三重態能階，因此亦具有將三重態發光材料的激發能量封閉的效果。因此，在發光層中含有三重態發光材料的情況下，含有通式(1)所表示的化合物的電洞傳輸層亦較佳為直接接觸於發光層。 In the case where the multilayer hole transport layer is included, the hole transport layer containing the compound represented by the general formula (1) is preferably in direct contact with the light-emitting layer. The reason for this is that the compound represented by the formula (1) has high electron blocking property and can prevent entry of electrons flowing out of the light-emitting layer. Further, since the compound represented by the formula (1) has a high triplet energy level, it also has an effect of blocking the excitation energy of the triplet luminescent material. Therefore, in the case where the light-emitting layer contains a triplet light-emitting material, the hole transport layer containing the compound represented by the general formula (1) is also preferably in direct contact with the light-emitting layer.

電洞傳輸層可僅包含通式(1)所表示的化合物，於不損及本發明的效果的範圍內亦可混合其他材料。該情況下，所使用的其他材料例如可列舉：4,4'-雙(N-(3-甲基苯基)-N-苯基胺基)聯苯(TPD)、4,4'-雙(N-(1-萘基)-N-苯基胺基)聯苯(NPD)、4,4'-雙(N,N-雙(4-聯苯基)胺基)聯苯(TBDB)、雙(N,N'-二苯基-4-胺基苯基)-N,N-二苯基-4,4'-二胺基-1,1'-聯苯(TPD232)等聯苯胺衍生 物，4,4',4"-三(3-甲基苯基(苯基)胺基)三苯基胺(m-MTDATA)、4,4',4"-三(1-萘基(苯基)胺基)三苯基胺(1-TNATA)等稱作星爆狀芳基胺的材料組群，雙(N-芳基咔唑)或雙(N-烷基咔唑)等雙咔唑衍生物，吡唑啉衍生物、均二苯乙烯系化合物、腙系化合物、苯并呋喃衍生物、噻吩衍生物、噁二唑衍生物、酞菁衍生物、卟啉衍生物等雜環化合物，聚合物系中側鏈上具有上述單體的聚碳酸酯或苯乙烯衍生物，聚噻吩、聚苯胺、聚茀、聚乙烯基咔唑及聚矽烷等。 The hole transport layer may contain only the compound represented by the formula (1), and other materials may be mixed within a range not impairing the effects of the present invention. In this case, other materials used may, for example, be 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl (TPD), 4,4'-double (N-(1-naphthyl)-N-phenylamino)biphenyl (NPD), 4,4'-bis(N,N-bis(4-biphenyl)amino)biphenyl (TBDB) Biphenylamine such as bis(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl (TPD232) derivative , 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine (m-MTDATA), 4,4',4"-tris(1-naphthyl) a group of materials called phenyl)amino)triphenylamine (1-TNATA), etc., known as starburst arylamine, bis(N-arylcarbazole) or bis(N-alkylcarbazole) a heterocyclic ring such as a carbazole derivative, a pyrazoline derivative, a stilbene compound, an anthraquinone compound, a benzofuran derivative, a thiophene derivative, an oxadiazole derivative, a phthalocyanine derivative, or a porphyrin derivative A compound, a polycarbonate or a styrene derivative having a monomer described above in a side chain, a polythiophene, a polyaniline, a polyfluorene, a polyvinylcarbazole, a polydecane, or the like.

發光層可為單一層、多層中的任一種，分別由發光材料(主體材料(host material)、摻雜劑材料(dopant material))所形成，發光材料可為主體材料與摻雜劑材料的混合物，可為單獨的主體材料，亦可為兩種主體材料與一種摻雜劑材料的混合物，任一種均可。即，於本發明的發光元件中，各發光層中可僅主體材料或可僅摻雜劑材料發光，亦可主體材料與摻雜劑材料均發光。就效率良好地利用電能，獲得高色純度的發光的觀點而言，發光層較佳為包含主體材料與摻雜劑材料的混合材料。另外，主體材料與摻雜劑材料可分別為一種，亦可為多種的組合，任一種均可。摻雜劑材料可含有於主體材料的整體中，亦可部分性地含有，任一種均可。摻雜劑材料可積層，亦可分散，任一種均可。摻雜劑材料可控制發光色。摻雜劑材料的量若過多，則會引起濃度淬滅現象，因此較佳為相對於主體材料以30重量%以下使用，進而較 佳為20重量%以下。摻雜方法可藉由與主體材料的共蒸鍍法而形成，但亦可與主體材料預先混合後同時蒸鍍。 The luminescent layer may be any one of a single layer and a plurality of layers, respectively formed of a luminescent material (host material, dopant material), and the luminescent material may be a mixture of the host material and the dopant material. It may be a single host material or a mixture of two host materials and one dopant material. That is, in the light-emitting element of the present invention, only the host material or the dopant-only material may be emitted in each of the light-emitting layers, or both the host material and the dopant material may emit light. From the viewpoint of efficiently utilizing electric energy and obtaining light of high color purity, the light-emitting layer is preferably a mixed material containing a host material and a dopant material. In addition, the host material and the dopant material may be one type or a combination of any of a plurality of types. The dopant material may be contained in the entirety of the host material, or may be partially contained, either. The dopant material may be laminated or dispersed, either of them. The dopant material controls the luminescent color. If the amount of the dopant material is too large, the concentration quenching phenomenon is caused. Therefore, it is preferably used in an amount of 30% by weight or less based on the host material. Preferably it is 20% by weight or less. The doping method can be formed by co-evaporation with a host material, but can also be vapor-deposited simultaneously with pre-mixing with the host material.

發光材料除通式(1)所表示的化合物以外，亦可使用先前以來作為發光體而為大眾所知的蒽或芘等的縮合環衍生物、以三(8-羥基喹啉)鋁為代表的金屬螯合化8-羥基喹啉酮(oxinoid)化合物、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、四苯基丁二烯衍生物、茚衍生物、香豆素衍生物、噁二唑衍生物、吡咯并吡啶衍生物、哌瑞酮(perinone)衍生物、環戊二烯衍生物、噁二唑衍生物、噻二唑并吡啶衍生物、二苯并呋喃衍生物、咔唑衍生物、吲哚并咔唑衍生物、聚合物系中的聚苯乙炔(phenylenevinylene)衍生物、聚對苯衍生物、以及聚噻吩衍生物等，但並無特別限定。 In addition to the compound represented by the formula (1), the luminescent material may be a condensed ring derivative such as ruthenium or osmium which has been known as an illuminant, and is represented by tris(8-hydroxyquinoline)aluminum. Metal chelating bisstyryl derivative such as oxinoid compound, bisstyryl fluorene derivative or distyrylbenzene derivative, tetraphenylbutadiene derivative, hydrazine derivative , coumarin derivative, oxadiazole derivative, pyrrolopyridine derivative, perinone derivative, cyclopentadiene derivative, oxadiazole derivative, thiadiazole pyridine derivative, a dibenzofuran derivative, a carbazole derivative, an indolocarbazole derivative, a polyphenylenevinylene derivative in a polymer system, a polyparaphenylene derivative, and a polythiophene derivative, but not Specially limited.

發光材料中所含的主體材料無需僅限於一種化合物，亦可混合使用本發明的多種化合物，或混合使用其他主體材料的一種以上。另外，亦可積層而使用。主體材料並無特別限定，可使用萘、蒽、菲、芘、(chrysene)、稠四苯、聯三伸苯(triphenylene)、苝、熒蒽、茀、茚等具有縮合芳基環的化合物或其衍生物，N,N'-二萘基-N,N'-二苯基-4,4'-二苯基-1,1'-二胺等芳香族胺衍生物，以三(8-羥基喹啉)鋁(III)為代表的金屬螯合化8-羥基喹啉酮化合物，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、茚衍生物、香豆素衍生物、噁二唑衍生物、吡咯并吡啶衍 生物、哌瑞酮衍生物、環戊二烯衍生物、吡咯并吡咯衍生物、噻二唑并吡啶衍生物、二苯并呋喃衍生物、咔唑衍生物、吲哚并咔唑衍生物、三嗪衍生物，聚合物系中的聚苯乙炔衍生物、聚對苯衍生物、聚茀衍生物、聚乙烯基咔唑衍生物、聚噻吩衍生物等，但並無特別限定。其中，發光層進行三重態發光(磷光發光)時所使用的主體可較佳地使用金屬螯合化8-羥基喹啉酮化合物、二苯并呋喃衍生物、二苯并噻吩衍生物、咔唑衍生物、吲哚并咔唑衍生物、三嗪衍生物、聯三伸苯衍生物等。 The host material contained in the luminescent material is not limited to one type of compound, and a plurality of compounds of the present invention may be used in combination or one or more kinds of other host materials may be used in combination. In addition, it can also be used in layers. The main material is not particularly limited, and naphthalene, anthracene, phenanthrene, anthracene, (chrysene), fused tetraphenyl, triphenylene, fluorene, fluoranthene, anthracene, anthracene, etc., or a derivative thereof having a condensed aryl ring, N,N'-dinaphthyl-N,N' -Aromatic amine derivative such as diphenyl-4,4'-diphenyl-1,1'-diamine, metal chelate represented by tris(8-hydroxyquinoline)aluminum (III) 8- a bis-styryl derivative such as a hydroxyquinolinone compound or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, an anthracene derivative, a coumarin derivative, an oxadiazole derivative, or a pyrrolopyridine derivative. , piperidone derivative, cyclopentadiene derivative, pyrrolopyrrole derivative, thiadiazolopyridine derivative, dibenzofuran derivative, carbazole derivative, indolocarbazole derivative, three The azine derivative is a polyphenylacetylene derivative, a polyparaphenylene derivative, a polyfluorene derivative, a polyvinylcarbazole derivative or a polythiophene derivative in the polymer system, but is not particularly limited. Among them, the host used in the triplet emission (phosphorescence) of the light-emitting layer can preferably use a metal chelate compound of 8-hydroxyquinolinone, a dibenzofuran derivative, a dibenzothiophene derivative, or a carbazole. Derivatives, indolocarbazole derivatives, triazine derivatives, triazine derivatives, and the like.

發光材料中所含的摻雜劑材料並無特別限定，可列舉：萘、蒽、菲、芘、聯三伸苯、苝、茀、茚等具有芳基環的化合物或其衍生物(例如2-(苯并噻唑-2-基)-9,10-二苯基蒽或5,6,11,12-四苯基稠四苯等)，呋喃、吡咯、噻吩、矽羅(silole)、9-矽茀(silafluorene)、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、噻噸等具有雜芳基環的化合物或其衍生物，二苯乙烯基苯衍生物、4,4'-雙(2-(4-二苯基胺基苯基)乙烯基)聯苯、4,4'-雙(N-(均二苯乙烯-4-基)-N-苯基胺基)均二苯乙烯等胺基苯乙烯基衍生物，芳香族乙炔衍生物、四苯基丁二烯衍生物、均二苯乙烯衍生物、醛連氮衍生物、吡咯亞甲基衍生物、二酮吡咯并[3,4-c]吡咯衍生物、2,3,5,6-1H,4H-四氫-9-(2'-苯并噻唑基)喹嗪并[9,9a,1-gh]香豆素等香豆素衍生物，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。 The dopant material contained in the luminescent material is not particularly limited, and examples thereof include a compound having an aryl ring such as naphthalene, anthracene, phenanthrene, anthracene, hydrazine, anthracene, anthracene, anthracene or the like (for example, 2) -(Benzothiazol-2-yl)-9,10-diphenylanthracene or 5,6,11,12-tetraphenyltetracycline, etc., furan, pyrrole, thiophene, silole, 9 -silafluorene, 9,9'-spirobifluorene, benzothiophene, benzofuran, anthracene, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine a compound having a heteroaryl ring such as quinoxaline, pyrrolopyridine or thioxanthene or a derivative thereof, a distyrylbenzene derivative, 4,4'-bis(2-(4-diphenylaminobenzene) Alkyl styrene-based derivatives such as vinyl)biphenyl, 4,4'-bis(N-(stilbene-4-yl)-N-phenylamino) stilbene, aromatic An acetylene derivative, a tetraphenylbutadiene derivative, a stilbene derivative, an aldehyde nitrogen derivative, a pyrromethene derivative, a diketopyrrolo[3,4-c]pyrrole derivative, 2, 3,5,6-1H,4H-tetrahydro-9-(2'-benzothiazolyl)quinazino[9,9a,1-gh]coumarin derivatives , imidazole, thiazole, thiadiazole, carbazole, Oxazole derivatives such as oxazole, oxadiazole and triazole, and metal complexes thereof, and N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'- An aromatic amine derivative represented by diphenyl-1,1'-diamine or the like.

其中，發光層進行三重態發光(磷光發光)時所使用的摻雜劑較佳為含有選自由銥(Ir)、釕(Ru)、鈀(Pd)、鉑(Pt)、鋨(Os)、及錸(Re)所組成的組群中的至少一種金屬的金屬錯合物化合物。配位子較佳為具有苯基吡啶骨架或苯基喹啉骨架或碳烯骨架等含氮芳香族雜環。然而，並不限定於該些化合物，可根據所要求的發光色、元件性能、與主體化合物的關係而選擇適當的錯合物。具體而言，可列舉：三(2-苯基吡啶基)銥錯合物、三{2-(2-苯硫基)吡啶基}銥錯合物、三{2-(2-苯并苯硫基)吡啶基}銥錯合物、三(2-苯基苯并噻唑)銥錯合物、三(2-苯基苯并噁唑)銥錯合物、三苯并喹啉銥錯合物、雙(2-苯基吡啶基)(乙醯丙酮酸)銥錯合物、雙{2-(2-苯硫基)吡啶基}銥錯合物、雙{2-(2-苯并苯硫基)吡啶基}(乙醯丙酮酸)銥錯合物、雙(2-苯基苯并噻唑)(乙醯丙酮酸)銥錯合物、雙(2-苯基苯并噁唑)(乙醯丙酮酸)銥錯合物、雙苯并喹啉(乙醯丙酮酸)銥錯合物、雙{2-(2,4-二氟苯基)吡啶基}(乙醯丙酮酸)銥錯合物、四乙基卟啉鉑錯合物、{三(噻吩甲醯基(thenoyl)三氟丙酮)單(1,10-啡啉)}銪錯合物、{三(噻吩甲醯基三氟丙酮)單(4,7-二苯基-1,10-啡啉)}銪錯合物、{三(1,3-二苯基-1,3-丙二酮)單(1,10-啡啉)}銪錯合物、三乙醯丙酮鋱錯合物等。另外，亦可較佳地使用 日本專利特開2009-130141號中所記載的磷光摻雜劑。並不限定於該些錯合物，就容易獲得高效率發光而言，可較佳地使用銥錯合物或鉑錯合物。 The dopant used in the triplet light emission (phosphorescence) of the light-emitting layer preferably contains a group selected from the group consisting of iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), and osmium (Os). And a metal complex compound of at least one metal in the group consisting of 铼 (Re). The ligand is preferably a nitrogen-containing aromatic heterocyclic ring having a phenylpyridine skeleton, a phenylquinoline skeleton or a carbene skeleton. However, it is not limited to these compounds, and an appropriate complex compound can be selected according to the required luminescent color, element performance, and the relationship with a host compound. Specifically, a tris(2-phenylpyridyl) ruthenium complex, a tri{2-(2-phenylthio)pyridinyl} ruthenium complex, and a tri-{2-(2-benzobenzene) Thio)pyridinyl}oxime complex, tris(2-phenylbenzothiazole) oxime complex, tris(2-phenylbenzoxazole) ruthenium complex, tribenzoquinoline 铱 complex , bis(2-phenylpyridyl)(acetylpyruvyl) ruthenium complex, bis{2-(2-phenylthio)pyridinyl} ruthenium complex, bis{2-(2-benzo Phenylthio)pyridinyl}(acetylpyruvate) ruthenium complex, bis(2-phenylbenzothiazole)(acetylpyruvate) ruthenium complex, bis(2-phenylbenzoxazole) (acetyl acetonate) ruthenium complex, bisbenzoquinoline (acetyl acetonate) ruthenium complex, bis{2-(2,4-difluorophenyl)pyridinyl}(acetylpyruvate)铱 complex, tetraethylporphyrin platinum complex, {tris(thenoyl trifluoroacetone) mono(1,10-morpholine)} ruthenium complex, {three (thiophene guanidine) Trifluoroacetone) mono(4,7-diphenyl-1,10-morpholine)} ruthenium complex, {tris(1,3-diphenyl-1,3-propanedione) mono(1) , 10-morpholine)} hydrazine complex, triacetyl acetonide hydrazine complex, and the like. In addition, it can also be preferably used A phosphorescent dopant described in Japanese Laid-Open Patent Publication No. 2009-130141. It is not limited to these complexes, and in order to obtain high-efficiency luminescence, a ruthenium complex or a platinum complex can be preferably used.

用作摻雜劑材料的上述三重態發光材料於發光層中可分別僅含有一種，亦可混合使用兩種以上。於使用兩種以上的三重態發光材料時，摻雜劑材料的總重量相對於主體材料較佳為30重量%以下，進而較佳為20重量%以下。 The above-mentioned triplet light-emitting material used as a dopant material may be contained in only one type in the light-emitting layer, or two or more types may be used in combination. When two or more kinds of triplet light-emitting materials are used, the total weight of the dopant material is preferably 30% by weight or less, and more preferably 20% by weight or less based on the host material.

另外，發光層中除上述主體材料及三重態發光材料以外，亦可進而含有用以調整發光層內的載子平衡或用以使發光層的層構造穩定化的第3成分。其中，第3成分是選擇於包含通式(1)所表示的具有咔唑骨架的化合物的主體材料及包含三重態發光材料的摻雜劑材料之間不會引起相互作用的材料。 Further, the light-emitting layer may further contain, in addition to the host material and the triplet light-emitting material, a third component for adjusting the balance of the carrier in the light-emitting layer or for stabilizing the layer structure of the light-emitting layer. Among them, the third component is a material selected to contain no interaction between a host material containing a compound having a carbazole skeleton represented by the general formula (1) and a dopant material containing a triplet light-emitting material.

三重態發光系中較佳的主體及摻雜劑並無特別限定，具體而言可列舉如下例子。 The preferred host and dopant in the triplet light-emitting system are not particularly limited, and specific examples thereof include the following.

於本發明中，電子傳輸層是指自陰極注入電子、進而傳輸電子的層。對於電子傳輸層，理想的是電子注入效率高，且效率良好地傳輸所注入的電子。因此，要求電子傳輸層為電子親和力大，而且電子移動率(electron mobility)大，進而穩定性優異， 於製造時及使用時不易產生成為陷阱(trap)的雜質的物質。尤其在將膜厚積層為較厚的情況下，低分子量的化合物發生結晶化等而膜質容易劣化，因此較佳為保持穩定的膜質的分子量為400以上的化合物。然而，在考慮電洞與電子的傳輸平衡的情況下，若電子傳輸層主要發揮可效率良好地阻止來自陽極的電洞不再結合而流向陰極側的作用，則即便由電子傳輸能力沒那麼高的材料構成，提高發光效率的效果亦與由電子傳輸能力高的材料構成的情況同等。因此，本發明中的電子傳輸層中亦以相同含義含有可效率良好地阻止電洞的轉移的電洞阻擋層。 In the present invention, the electron transport layer refers to a layer which injects electrons from the cathode and further transports electrons. For the electron transport layer, it is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. Therefore, the electron transport layer is required to have a large electron affinity, and the electron mobility is large, and the stability is excellent. A substance that is not easily trapped as a trap at the time of manufacture or use. In particular, when the film thickness is thick, the low molecular weight compound is crystallized or the like, and the film quality is likely to be deteriorated. Therefore, a compound having a stable film quality of 400 or more is preferable. However, in consideration of the balance of transmission between the hole and the electron, if the electron transport layer mainly functions to efficiently prevent the holes from the anode from being combined and flowing to the cathode side, even if the electron transport capability is not so high The material composition and the effect of improving the luminous efficiency are also equivalent to those of a material having a high electron transporting ability. Therefore, the electron transport layer in the present invention also contains a hole blocking layer which can efficiently prevent the transfer of holes in the same meaning.

電子傳輸層中所使用的電子傳輸材料可列舉：萘、蒽等縮合多環芳香族衍生物，以4,4'-雙(二苯基乙烯基)聯苯為代表的苯乙烯基系芳香環衍生物，蒽醌或聯對苯醌等醌衍生物，磷氧化物衍生物、三(8-羥基喹啉)鋁(III)等羥基喹啉錯合物、苯并羥基喹啉錯合物、羥唑(hydroxyazole)錯合物、次甲基偶氮錯合物、艸卓酚酮(tropolone)金屬錯合物及黃酮醇金屬錯合物等各種金屬錯合物，但就降低驅動電壓，獲得高效率發光而言，較佳為使用由選自碳、氫、氮、氧、矽、磷中的元素構成，且具有含有電子接受性(electron acceptability)氮的雜芳基環結構的化合物。 Examples of the electron transporting material used in the electron transporting layer include a condensed polycyclic aromatic derivative such as naphthalene or an anthracene, and a styryl aromatic ring represented by 4,4'-bis(diphenylvinyl)biphenyl. a derivative, an anthracene derivative such as hydrazine or a para-p-benzoquinone, a phosphorus oxide derivative, a hydroxyquinoline complex such as tris(8-hydroxyquinoline)aluminum (III), a benzohydroxyquinoline complex, Various metal complexes such as hydroxyazole complex, methine azo complex, tropolone metal complex and flavonol metal complex, but reduce the driving voltage and obtain For high-efficiency luminescence, it is preferred to use a compound composed of an element selected from the group consisting of carbon, hydrogen, nitrogen, oxygen, hydrazine, and phosphorus, and having a heteroaryl ring structure containing electron acceptability nitrogen.

此處所謂的電子接受性氮是表示於與鄰接原子之間形成多重鍵的氮原子。由於氮原子具有高的電子陰性度，故而該多重鍵具有吸電子的性質。此外，含有電子接受性氮的芳香族雜環具 有高電子親和性。具有電子接受性氮的電子傳輸材料容易接受來自具有高電子親和力的陰極的電子，可以更低電壓驅動。另外，電子對發光層的供給增多，再結合概率變高，因此發光效率提高。 The electron-accepting nitrogen referred to herein is a nitrogen atom represented by a multiple bond with an adjacent atom. Since the nitrogen atom has a high electron-negative degree, the multiple bond has an electron-withdrawing property. In addition, an aromatic heterocyclic device containing electron-accepting nitrogen Have high electron affinity. An electron transporting material having electron-accepting nitrogen readily accepts electrons from a cathode having high electron affinity and can be driven at a lower voltage. Further, since the supply of electrons to the light-emitting layer is increased and the recombination probability is increased, the light-emitting efficiency is improved.

含有電子接受性氮的雜芳基環例如可列舉：吡啶環、吡嗪環、嘧啶環、喹啉環、喹噁啉環、萘啶環、嘧啶并嘧啶環、苯并喹啉環、啡啉環、咪唑環、噁唑環、噁二唑環、***環、噻唑環、噻二唑環、苯并噁唑環、苯并噻唑環、苯并咪唑環、菲并(phenanthro)咪唑環等。 Examples of the heteroaryl ring containing an electron-accepting nitrogen include a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring, a naphthyridine ring, a pyrimidopyrimidine ring, a benzoquinoline ring, and a phenanthroline. Ring, imidazole ring, oxazole ring, oxadiazole ring, triazole ring, thiazole ring, thiadiazole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, phenanthro imidazole ring, etc. .

該些具有雜芳基環結構的化合物例如可列舉：苯并咪唑衍生物、苯并噁唑衍生物、苯并噻唑衍生物、噁二唑衍生物、噻二唑衍生物、***衍生物、吡嗪衍生物、啡啉衍生物、喹噁啉衍生物、喹啉衍生物、苯并喹啉衍生物、聯吡啶或三聯吡啶等低聚吡啶(oligopyridine)衍生物、喹噁啉衍生物及萘啶衍生物等作為較佳的化合物。其中，就電子傳輸能的觀點而言，可較佳地使用三(N-苯基苯并咪唑-2-基)苯等咪唑衍生物、1,3-雙[(4-第三丁基苯基)1,3,4-噁二唑基]伸苯等噁二唑衍生物、N-萘基-2,5-二苯基-1,3,4-***等***衍生物、2,9-二甲基-4,7-聯苯-1,10-鄰二氮雜菲(bathocuproine)或1,3-雙(1,10-啡啉-9-基)苯等啡啉衍生物、2,2'-雙(苯并[h]喹啉-2-基)-9,9'-螺二茀等苯并喹啉衍生物、2,5-雙(6'-(2',2"-聯吡啶基))-1,1-二甲基-3,4-二苯基矽羅等聯吡啶衍生物、1,3-雙(4'-(2,2'：6'2"-三聯吡啶基))苯等三聯吡啶衍生物、雙(1- 萘基)-4-(1,8-萘啶-2-基)苯基氧化膦(phosphine oxide)等萘啶衍生物。另外，若該些衍生物具有縮合多環芳香族骨架，則玻璃轉變溫度提高，並且電子移動率亦增大，發光元件的低電壓化的效果大，故而更佳。進而，若考慮元件耐久壽命提高，合成的容易性，原料獲取容易，則縮合多環芳香族骨架尤佳為蒽骨架、芘骨架或啡啉骨架。上述電子傳輸材料可單獨使用，亦可將上述電子傳輸材料的兩種以上混合使用，或將其他電子傳輸材料的一種以上混合於上述電子傳輸材料中而使用。 Examples of the compound having a heteroaryl ring structure include a benzimidazole derivative, a benzoxazole derivative, a benzothiazole derivative, an oxadiazole derivative, a thiadiazole derivative, and a triazole derivative. Oligopyridine derivatives such as pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, bipyridine or terpyridine, quinoxaline derivatives and naphthalene A pyridine derivative or the like is preferred as the compound. Among them, from the viewpoint of electron transport energy, an imidazole derivative such as tris(N-phenylbenzimidazol-2-yl)benzene or 1,3-bis[(4-tert-butylbenzene) can be preferably used. (1,3,4-oxadiazolyl) oxadiazole derivatives such as benzene, triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, 2 , 9-dimethyl-4,7-biphenyl-1,10-phenhocuproine or 1,3-bis(1,10-morpholin-9-yl)benzene and other phenanthroline derivatives , 2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene and other benzoquinoline derivatives, 2,5-bis (6'-(2', 2"-bipyridyl)-1,1-dimethyl-3,4-diphenylindene and other bipyridine derivatives, 1,3-bis(4'-(2,2':6'2 "-Tripyridyl") pyridine and other terpyridine derivatives, double (1- Naphthyridine derivatives such as naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide. Further, when the derivatives have a condensed polycyclic aromatic skeleton, the glass transition temperature is increased, and the electron mobility is also increased, and the effect of lowering the voltage of the light-emitting element is larger, which is more preferable. Further, in consideration of improvement in durability of the element, ease of synthesis, and easy acquisition of the raw material, the condensed polycyclic aromatic skeleton is preferably an anthracene skeleton, an anthracene skeleton or a phenanthroline skeleton. The above-mentioned electron transporting material may be used singly or in combination of two or more kinds of the above electron transporting materials or one or more kinds of other electron transporting materials may be used in the above-mentioned electron transporting material.

較佳的電子傳輸材料並無特別限定，具體而言可列舉如下例子。 The preferred electron transporting material is not particularly limited, and specific examples thereof are as follows.

上述電子傳輸材料可單獨使用，亦可將上述電子傳輸材料的兩種以上混合使用，或將其他電子傳輸材料的一種以上混合於上述電子傳輸材料中而使用。另外，亦可含有施體性化合物。此處，施體性化合物是指藉由改善電子注入障壁，而使自陰極或電子注入層向電子傳輸層的電子注入變得容易，進而使電子傳輸層的導電性提高的化合物。 The above-mentioned electron transporting material may be used singly or in combination of two or more kinds of the above electron transporting materials or one or more kinds of other electron transporting materials may be used in the above-mentioned electron transporting material. Further, a donor compound may also be contained. Here, the donor compound is a compound which facilitates electron injection from the cathode or the electron injection layer to the electron transport layer by improving the electron injection barrier, and further improves the conductivity of the electron transport layer.

施體性化合物的較佳例可列舉：鹼金屬、含有鹼金屬的無機鹽、鹼金屬與有機物的錯合物、鹼土金屬、含有鹼土金屬的無機鹽或鹼土金屬與有機物的錯合物等。鹼金屬、鹼土金屬的較佳種類可列舉：低功函數且提高電子傳輸能的效果大的鋰、鈉、鉀、銣、銫等鹼金屬，或鎂、鈣、鈰、鋇等鹼土金屬。 Preferable examples of the donor compound include an alkali metal, an inorganic salt containing an alkali metal, a complex of an alkali metal and an organic compound, an alkaline earth metal, an inorganic salt containing an alkaline earth metal, or a complex of an alkaline earth metal and an organic compound. Preferred examples of the alkali metal and the alkaline earth metal include alkali metals such as lithium, sodium, potassium, rubidium, and cesium having a low work function and high electron transport energy, or alkaline earth metals such as magnesium, calcium, strontium, and barium.

另外，就真空中的蒸鍍容易且操作優異而言，無機鹽、或與有機物的錯合物的狀態優於金屬單體。進而，就使大氣中的操作變得容易，控制添加濃度的容易性的方面而言，更佳為處於與有機物的錯合物的狀態。無機鹽的例子可列舉：LiO、Li2O等氧化物，氮化物，LiF、NaF、KF等氟化物，Li2CO3、Na2CO3、K2CO3、Rb2CO3、Cs2CO3等碳酸鹽等。另外，作為鹼金屬或鹼土金屬的較佳例，就獲得大的低電壓驅動效果的觀點而言，可列舉鋰、銫。另外，與有機物的錯合物中的有機物的較佳例可列舉：羥基喹啉、苯并羥基喹啉、吡啶基苯酚、黃酮醇、羥基咪唑并吡啶、羥基苯并唑、羥基***等。其中，就發光元件的進一步低電壓化的效果大的觀點而言，較佳為鹼金屬與有機物的錯合物，進而就合成的容易性、熱穩定性的觀點而言，更佳為鋰與有機物的錯合物，尤佳為可以相對較低廉的價格獲取的羥基喹啉鋰。 Further, in the case where vapor deposition in a vacuum is easy and the operation is excellent, the state of the inorganic salt or the complex with the organic substance is superior to that of the metal monomer. Further, in terms of facilitating the operation in the atmosphere and controlling the easiness of the concentration, it is more preferable to be in a state of being in a complex with the organic substance. Examples of the inorganic salt include oxides such as LiO and Li 2 O, nitrides, fluorides such as LiF, NaF, and KF, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , and Cs 2 . Carbonate such as CO 3 or the like. Further, as a preferred example of the alkali metal or alkaline earth metal, lithium or ruthenium is used from the viewpoint of obtaining a large low-voltage driving effect. Further, preferred examples of the organic substance in the complex with the organic substance include hydroxyquinoline, benzohydroxyquinoline, pyridylphenol, flavonol, hydroxyimidazopyridine, hydroxybenzoxazole, hydroxytriazole and the like. In view of the fact that the effect of further lowering the voltage of the light-emitting element is large, it is preferably a complex of an alkali metal and an organic substance, and further preferably lithium and hydrogen from the viewpoint of easiness of synthesis and thermal stability. A complex of an organic compound is particularly preferably a lithium hydroxyquinolate which can be obtained at a relatively low price.

電子傳輸層的電離電位並無特別限定，較佳為5.6eV以上、8.0eV以下，更佳為5.6eV以上、7.0eV以下。 The ionization potential of the electron transport layer is not particularly limited, but is preferably 5.6 eV or more and 8.0 eV or less, more preferably 5.6 eV or more and 7.0 eV or less.

構成發光元件的上述各層的形成方法並不特別限定於電 阻加熱蒸鍍、電子束蒸鍍、濺鍍、分子積層法、塗佈法等，通常就元件特性的方面而言，較佳為電阻加熱蒸鍍或電子束蒸鍍。 The method of forming each of the above layers constituting the light-emitting element is not particularly limited to electricity Resistance heating vapor deposition, electron beam evaporation, sputtering, molecular layering, coating, and the like are generally preferably resistance heating deposition or electron beam evaporation in terms of device characteristics.

有機層的厚度亦取決於發光物質的電阻值，因此無法限定，但較佳為1nm~1000nm。發光層、電子傳輸層、電洞傳輸層的膜厚分別較佳為1nm以上、200nm以下，進而較佳為5nm以上、100nm以下。 The thickness of the organic layer is also dependent on the resistance value of the luminescent material, and therefore it is not limited, but is preferably 1 nm to 1000 nm. The film thickness of the light-emitting layer, the electron transport layer, and the hole transport layer is preferably 1 nm or more and 200 nm or less, and more preferably 5 nm or more and 100 nm or less.

本發明的發光元件具有可將電能轉換為光的功能。此處電能主要是使用直流電流，但亦可使用脈衝電流(pulse current)或交流電流。電流值及電壓值並無特別限定，但若考慮元件的消耗電力或壽命，則應以可以儘可能低的能量獲得最大的亮度的方式選擇。 The light-emitting element of the present invention has a function of converting electric energy into light. Here, the electric energy is mainly a direct current, but a pulse current or an alternating current can also be used. The current value and the voltage value are not particularly limited, but in consideration of the power consumption or life of the element, the maximum brightness can be selected with the lowest possible energy.

本發明的發光元件例如可較佳地用作以矩陣(matrix)及/或片段(segment)方式顯示的顯示器(display)。 The light-emitting element of the present invention can be preferably used, for example, as a display that is displayed in a matrix and/or a segment.

矩陣方式是指用以顯示的像素呈格子狀或馬賽克狀等二維地配置，以像素的集合顯示文字或圖像。像素的形狀或尺寸(size)可根據用途而決定。例如，個人電腦(personal computer)、監視器、電視(television)的圖像及文字顯示中通常是使用一邊為300μm以下的四邊形的像素，另外，在如顯示面板(display panel)的大型顯示器的情況下，使用一邊為毫米級(mm order)的像素。在單色顯示(monochrome display)的情況下，只要排列相同顏色的像素即可，但在彩色顯示的情況下，使紅、綠、藍的 像素一併顯示。該情況下，典型的有三角型(delta type)與條紋型(stripe type)。並且，該矩陣的驅動方法可為線序驅動方法或主動矩陣(active matrix)的任一種。線序驅動的構造簡單，但在考慮動作特性的情況下，有主動矩陣優異的情況，因此驅動方法亦需要根據用途而區分使用。 The matrix method means that pixels to be displayed are two-dimensionally arranged in a lattice shape or a mosaic shape, and characters or images are displayed in a collection of pixels. The shape or size of the pixel can be determined depending on the use. For example, in the case of a personal computer, a monitor, a television, and a character display, a quadrangular 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. Next, use pixels with one side of mm order. In the case of a monochrome display, it is only necessary to arrange pixels of the same color, but in the case of color display, red, green, and blue The pixels are displayed together. In this case, a typical delta type and a stripe type are typical. Moreover, the driving method of the matrix may be any one of a line sequential driving method or an active matrix. The structure of the line sequential drive is simple, but in the case of considering the operational characteristics, there is a case where the active matrix is excellent, and therefore the driving method needs to be used depending on the use.

本發明中的片段方式是指以顯示預先決定的資訊的方式形成圖案，使由該圖案的配置決定的區域發光的方式。例如可列舉：數位時鐘(digital clock)或溫度計中的時刻顯示或溫度顯示、音訊設備(audio equipment)或電磁調理器(electromagnetic cooker)等的動作狀態顯示及汽車的面板顯示(panel display)等。並且，上述矩陣顯示與片段顯示亦可於同一面板中共存。 The segment method in the present invention refers to a method in which a pattern is formed so as to display predetermined information, and an area determined by the arrangement of the pattern is illuminated. For example, a digital clock or a time display or a temperature display in a thermometer, an operation state display such as an audio equipment or an electromagnetic cooker, and a panel display of a car can be cited. Moreover, the matrix display and the segment display may coexist in the same panel.

本發明的發光元件亦可較佳地用作各種機器等的背光裝置。背光裝置主要以提高不自發光的顯示裝置的視認性為目的而使用，可用於液晶顯示裝置、時鐘、音訊裝置、汽車面板、顯示板及標識等。尤其本發明的發光元件可較佳地用於液晶顯示裝置、其中可較佳地用於不斷研討薄型化的個人電腦用途的背光裝置，可提供較先前更薄型且輕量的背光裝置。 The light-emitting element of the present invention can also be preferably used as a backlight of various machines and the like. The backlight device is mainly used for the purpose of improving the visibility of a display device that does not emit light, and can be 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, the light-emitting element of the present invention can be preferably used for a liquid crystal display device, a backlight device which can be preferably used for the purpose of continuously researching a thinned personal computer, and can provide a backlight device which is thinner and lighter than before.

[實施例] [Examples]

以下，列舉實施例對本發明進行說明，但本發明並不受該些實施例限定。此外，下述各實施例中的化合物的編號是指上述所記載的化合物的編號。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples. Further, the numbers of the compounds in the following examples refer to the numbers of the compounds described above.

另外，關於各化合物的最低激發三重態能量的測定，將本發明的化合物製備為1.0×10-5mol/l的2-甲基四氫呋喃溶液。將所製備的溶液添入至專用的石英管(quartz tube)中，進行氮氣起泡(nitrogen bubbling)，藉此去除溶存氧，進而為了防止氧氣的混入而利用隔離栓(septum plug)進行封蓋(cap)。利用液態氮將該樣品(sample)冷卻至77K附近後，使用螢光磷光分光光度計(堀場製作所製造，FluoroMax-4P)，測定磷光光譜(spectrum)。讀取磷光光譜的短波長的上升位置的波長，將該波長值換算為光能，算出三重態能量(T1)。 Further, regarding the measurement of the lowest excited triplet energy of each compound, the compound of the present invention was prepared into a 1.0 × 10 -5 mol/l 2-methyltetrahydrofuran solution. The prepared solution is added to a dedicated quartz tube, and nitrogen bubbling is performed, thereby removing dissolved oxygen, and further sealing with a septum plug to prevent oxygen from entering. (cap). The sample was cooled to about 77 K with liquid nitrogen, and a phosphorescence spectrum was measured using a fluorescent phosphorescence spectrophotometer (FluoroMax-4P, manufactured by Horiba, Ltd.). The wavelength of the short-wavelength rising position of the phosphorescence spectrum is read, and the wavelength value is converted into light energy, and the triplet energy (T1) is calculated.

化合物[1]的合成 Synthesis of Compound [1]

將3-溴咔唑20.9g、9-苯基咔唑-3-硼酸15.0g、乙酸鈀366mg、三(2-甲基苯基)膦300mg、2M碳酸鉀水溶液105ml、二甲氧基乙烷260ml的混合溶液於氮氣氣流下回流6小時。冷卻至室溫後，利用四氫呋喃500ml進行萃取。利用飽和食鹽水100ml將有機層清洗2次，利用硫酸鎂乾燥後進行蒸發(evaporate)。藉由鄰二甲苯再結晶將所獲得的濃縮物純化，並真空乾燥後，獲得9-苯基-9H,9'H-3,3'-聯咔唑13.5g。 20.9 g of 3-bromocarbazole, 15.0 g of 9-phenylcarbazole-3-boronic acid, 366 mg of palladium acetate, 300 mg of tris(2-methylphenyl)phosphine, 105 ml of 2M potassium carbonate aqueous solution, dimethoxyethane A mixed solution of 260 ml was refluxed for 6 hours under a nitrogen stream. After cooling to room temperature, extraction was carried out using 500 ml of tetrahydrofuran. The organic layer was washed twice with 100 ml of saturated brine, dried over magnesium sulfate, and evaporated. The obtained concentrate was purified by recrystallization from o-xylene, and dried in vacuo to give 13.5 g of 9-phenyl-9H,9'H-3,3'-bicarbazole.

其次，將苯胺4.32g、4-溴三苯基胺15.0g、雙(二亞苄基丙酮)鈀267mg、三-第三丁基膦四氟硼酸鹽270mg、第三丁醇鈉6.25g與鄰二甲苯232ml的混合溶液於氮氣氣流下、回流下加熱攪拌1小時。冷卻至室溫後，利用甲苯50ml進行萃取。利用水 30ml將有機層清洗3次，利用硫酸鎂乾燥後進行蒸發。藉由矽膠管柱層析法(silica gel column chromatography)將所獲得的濃縮物純化並蒸發，將所獲得的固體真空乾燥後，獲得N1,N1,N4-三苯基苯-1,4-二胺9.33g。 Next, 4.32 g of aniline, 15.0 g of 4-bromotriphenylamine, 267 mg of bis(dibenzylideneacetone)palladium, 270 mg of tri-t-butylphosphine tetrafluoroborate, and 6.25 g of sodium butoxide. A mixed solution of 232 ml of xylene was heated and stirred under a nitrogen stream under reflux for 1 hour. After cooling to room temperature, extraction was carried out with 50 ml of toluene. The organic layer was washed three times with 30 ml of water, dried over magnesium sulfate and evaporated. The obtained concentrate was purified and evaporated by silica gel column chromatography, and the obtained solid was vacuum dried to obtain N 1 ,N 1 ,N 4 -triphenylbenzene-1. 4-diamine 9.33 g.

其次，將N1,N1,N4-三苯基苯-1,4-二胺9.33g、1-溴-4-氯苯5.83g、乙酸鈀62mg、三-第三丁基膦四氟硼酸鹽161mg、第三丁醇鈉3.72g與鄰二甲苯134ml的混合溶液於氮氣氣流下、回流下加熱攪拌1.5小時。冷卻至室溫後，利用甲苯50ml進行萃取。利用水30ml將有機層清洗3次，利用硫酸鎂乾燥後進行蒸發。藉由矽膠管柱層析法將所獲得的濃縮物純化並進行蒸發，將所獲得的固體真空乾燥後，獲得N1-(4-氯苯基)-N1,N4,N4-三苯基苯-1,4-二胺5.72g。 Next, 9.13 g of N 1 , N 1 , N 4 -triphenylbenzene-1,4-diamine, 5.83 g of 1-bromo-4-chlorobenzene, 62 mg of palladium acetate, and tetra-tertiary phosphine tetrafluoro A mixed solution of 161 mg of borate, 3.72 g of sodium butoxide, and 134 ml of o-xylene was heated and stirred under a nitrogen stream for 1.5 hours under reflux. After cooling to room temperature, extraction was carried out with 50 ml of toluene. The organic layer was washed three times with 30 ml of water, dried over magnesium sulfate and evaporated. The obtained concentrate was purified by oxime column chromatography and evaporated, and the obtained solid was vacuum dried to obtain N 1 -(4-chlorophenyl)-N 1 , N 4 , N 4 - Phenylbenzene-1,4-diamine 5.72 g.

其次，將N1-(4-氯苯基)-N1,N4,N4-三苯基苯-1,4-二胺5.72g、9-苯基-9H,9'H-3,3'-聯咔唑4.75g、雙(二亞苄基丙酮)鈀67mg、二-第三丁基(2,2-二苯基-1-甲基-1-環丙基)膦82mg、第三丁醇鈉1.56g與鄰二甲苯58ml的混合溶液於氮氣氣流下、回流下加熱攪拌2小時。冷卻至室溫後，利用甲苯50ml進行萃取。利用水30ml將有機層清洗3次，利用硫酸鎂乾燥後進行蒸發。藉由矽膠管柱層析法將所獲得的濃縮物純化並進行蒸發，將所獲得的固體真空乾燥後，獲得化合物[1]4.0g。 Next, N 1 -(4-chlorophenyl)-N 1 , N 4 , N 4 -triphenylbenzene-1,4-diamine 5.72 g, 9-phenyl-9H, 9'H-3, 3'-bicarbazole 4.75 g, bis(dibenzylideneacetone)palladium 67 mg, di-t-butyl (2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine 82 mg, A mixed solution of 1.56 g of sodium tributolate and 58 ml of o-xylene was heated and stirred under a nitrogen stream for 2 hours under reflux. After cooling to room temperature, extraction was carried out with 50 ml of toluene. The organic layer was washed three times with 30 ml of water, dried over magnesium sulfate and evaporated. The obtained concentrate was purified by oxime column chromatography and evaporated, and the obtained solid was dried in vacuo to give the compound [1] 4.0 g.

所獲得的粉末的1H-NMR分析結果如下所述，可確認上 述所獲得的白色固體為化合物[1]。 The results of 1 H-NMR analysis of the obtained powder were as follows, and it was confirmed that the white solid obtained above was the compound [1].

1H-NMR(CDCl3(d=ppm))：7.25-7.79(t,36H),8.22-8.25(m,3H),8.45(s,3H)。 1 H-NMR (CDCl 3 (d=ppm)): 7.25-7.79 (t, 36H), 8.22 - 8.25 (m, 3H), 8.45 (s, 3H).

此外，該化合物[1]是使用油擴散泵於1×10-3Pa的壓力下、約290℃下進行昇華純化後用作發光元件材料。關於高效液相層析法(High Performance Liquid Chromatography，HPLC)純度(測定波長254nm下的面積%)，昇華純化前為99.8%，昇華純化後為99.9%。 Further, the compound [1] was used as a light-emitting device material by sublimation purification at a pressure of 1 × 10 -3 Pa at about 290 ° C using an oil diffusion pump. The purity of High Performance Liquid Chromatography (HPLC) (area % at a measurement wavelength of 254 nm) was 99.8% before sublimation purification and 99.9% after sublimation purification.

另外，化合物[1]的最低激發三重態能階T1為2.72eV。 Further, the lowest excited triplet energy level T1 of the compound [1] was 2.72 eV.

合成例2 Synthesis Example 2

化合物[13]的合成 Synthesis of Compound [13]

將3-溴咔唑20.9g、9-苯基咔唑-3-硼酸15.0g、乙酸鈀366mg、三(2-甲基苯基)膦300mg、2M碳酸鉀水溶液105ml、二甲氧基乙烷260ml的混合溶液於氮氣氣流下回流6小時。冷卻至室溫後，利用四氫呋喃500ml進行萃取。利用飽和食鹽水100ml將有機層清洗2次，利用硫酸鎂乾燥後進行蒸發。藉由鄰二甲苯再結晶將所獲得的濃縮物純化，並真空乾燥後，獲得9-苯基-9H,9'H-3,3'-聯咔唑13.5g。 20.9 g of 3-bromocarbazole, 15.0 g of 9-phenylcarbazole-3-boronic acid, 366 mg of palladium acetate, 300 mg of tris(2-methylphenyl)phosphine, 105 ml of 2M potassium carbonate aqueous solution, dimethoxyethane A mixed solution of 260 ml was refluxed for 6 hours under a nitrogen stream. After cooling to room temperature, extraction was carried out using 500 ml of tetrahydrofuran. The organic layer was washed twice with 100 ml of saturated brine, dried over magnesium sulfate, and evaporated. The obtained concentrate was purified by recrystallization from o-xylene, and dried in vacuo to give 13.5 g of 9-phenyl-9H,9'H-3,3'-bicarbazole.

其次，將苯胺2.89g、3-溴苯基咔唑10.0g、乙酸鈀139mg、三-第三丁基膦四氟硼酸鹽360mg、第三丁醇鈉4.18mg與鄰二甲苯155ml的混合溶液於氮氣氣流下、回流下加熱攪拌1小時。冷卻至室溫後，利用甲苯50ml進行萃取。利用水30ml將有機層 清洗3次，利用硫酸鎂乾燥後進行蒸發。藉由矽膠管柱層析法將所獲得的濃縮物純化並進行蒸發，將所獲得的固體真空乾燥後，獲得N,9-二苯基-9H-咔唑-3-胺4.33g。 Next, a mixed solution of 2.89 g of aniline, 10.0 g of 3-bromophenyloxazole, 139 mg of palladium acetate, 360 mg of tri-tert-butylphosphine tetrafluoroborate, 4.18 mg of sodium butoxide, and 155 ml of o-xylene. The mixture was stirred under heating with a nitrogen stream for 1 hour under reflux. After cooling to room temperature, extraction was carried out with 50 ml of toluene. Use 30ml of water to layer the organic layer It was washed 3 times, dried with magnesium sulfate, and evaporated. The obtained concentrate was purified by oxime column chromatography and evaporated, and the obtained solid was dried in vacuo to give 4.33 g of N,9-diphenyl-9H-indazole-3-amine.

其次，將N,9-二苯基-9H-咔唑-3-胺4.33g、1-溴-4-氯苯2.73g、乙酸鈀29mg、三-第三丁基膦四氟硼酸鹽75mg、第三丁醇鈉1.74g與鄰二甲苯65ml的混合溶液於氮氣氣流下、回流下加熱攪拌1小時。冷卻至室溫後，利用甲苯50ml進行萃取。利用水30ml將有機層清洗3次，利用硫酸鎂乾燥後進行蒸發。藉由矽膠管柱層析法將所獲得的濃縮物純化並進行蒸發，將所獲得的固體真空乾燥後，獲得N-(4-氯苯基)-N,9-二苯基-9H-咔唑-3-胺3.65g。 Next, 4.33 g of N,9-diphenyl-9H-carbazol-3-amine, 2.73 g of 1-bromo-4-chlorobenzene, 29 mg of palladium acetate, and 75 mg of tri-t-butylphosphine tetrafluoroborate. A mixed solution of 1.74 g of sodium butoxide sodium and 65 ml of o-xylene was heated and stirred under a nitrogen stream for 1 hour under reflux. After cooling to room temperature, extraction was carried out with 50 ml of toluene. The organic layer was washed three times with 30 ml of water, dried over magnesium sulfate and evaporated. The obtained concentrate was purified by oxime column chromatography and evaporated, and the obtained solid was dried in vacuo to give N-(4-chlorophenyl)-N,9-diphenyl-9H-indole. Zylin-3-amine 3.65 g.

其次，將N-(4-氯苯基)-N,9-二苯基-9H-咔唑-3-胺3.65g、9-苯基-9H,9'H-3,3'-聯咔唑3.05g、雙(二亞苄基丙酮)鈀43mg、二-第三丁基(2,2-二苯基-1-甲基-1-環丙基)膦52mg、第三丁醇鈉1.0g與鄰二甲苯37ml的混合溶液於氮氣氣流下、回流下加熱攪拌2小時。冷卻至室溫後，利用甲苯50ml進行萃取。利用水30ml將有機層清洗3次，利用硫酸鎂乾燥後進行蒸發。藉由矽膠管柱層析法將所獲得的濃縮物純化並進行蒸發，將所獲得的固體真空乾燥後，獲得化合物[13]4.72g。 Next, N-(4-chlorophenyl)-N,9-diphenyl-9H-indazole-3-amine 3.65 g, 9-phenyl-9H, 9'H-3, 3'-linked oxime 3.05 g of azole, 43 mg of bis(dibenzylideneacetone)palladium, 52 mg of di-t-butyl (2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine, sodium 1.0-butoxide A mixed solution of g and o-xylene (37 ml) was heated and stirred under a nitrogen stream for 2 hours under reflux. After cooling to room temperature, extraction was carried out with 50 ml of toluene. The organic layer was washed three times with 30 ml of water, dried over magnesium sulfate and evaporated. The obtained concentrate was purified by oxime column chromatography and evaporated, and the obtained solid was dried in vacuo to give compound [13] 4.72 g.

所獲得的粉末的質子核磁共振(Proton Nuclear Magnetic Resonance，1H-NMR)分析結果如下所述，可確認上述所獲得的 白色固體為化合物[13]。 Proton NMR of the obtained powder (Proton Nuclear Magnetic Resonance, 1 H -NMR) analysis described below, confirmed that the white solid obtained above was the compound [13].

1H-NMR(CDCl3(d=ppm))：7.28-7.66(t,32H),7.75-7.80(m,2H),8.06-8.09(d,2H,J=7.56),8.21-8.25(m,2H),8.44-8.46(m,2H)。 1 H-NMR (CDCl 3 (d=ppm)): 7.28-7.66 (t, 32H), 7.75-7.80 (m, 2H), 8.06-8.09 (d, 2H, J = 7.56), 8.21-8.25 (m) , 2H), 8.44 - 8.46 (m, 2H).

此外，該化合物[13]是使用油擴散泵於1×10-3Pa的壓力下、約290℃下進行昇華純化後用作發光元件材料。關於HPLC純度(測定波長254nm下的面積%)，昇華純化前為99.8%，昇華純化後為99.9%。另外，化合物[13]的最低激發三重態能階T1為2.75eV。 Further, the compound [13] was used as a light-emitting device material by sublimation purification at a pressure of 1 × 10 -3 Pa at about 290 ° C using an oil diffusion pump. Regarding the HPLC purity (area % at a measurement wavelength of 254 nm), it was 99.8% before sublimation purification and 99.9% after sublimation purification. Further, the lowest excited triplet energy level T1 of the compound [13] was 2.75 eV.

實施例1 Example 1

將堆積有ITO透明導電膜50nm的玻璃基板(吉奧馬(GEOMATEC)股份有限公司製造，11Ω/□，濺鍍品)切斷成38mm×46mm，進行蝕刻(etching)。利用“Semico Clean 56”(商品名，古內化學(Furuuchi Chemical)股份有限公司製造)對所獲得的基板進行15分鐘超音波清洗後，利用超純水進行清洗。於即將製作元件之前對該基板進行1小時UV-臭氧處理(ultraviolet-ozone treatment)，設置於真空蒸鍍裝置內，進行排氣直至裝置內的真空度成為5×10-4Pa以下為止。藉由電阻加熱法，蒸鍍10nm的化合物HI-1作為電洞注入層。其次，蒸鍍80nm的化合物HT-6作為第一電洞傳輸層。其次，蒸鍍10nm的化合物[1]作為第二電洞傳輸層。其次，使用化合物H-1作為主體材料，使用化合物D-1作為摻雜劑材料，以使摻雜劑材料的摻雜濃度(doped density)成為 10重量%的方式蒸鍍成30nm的厚度作為發光層。其次，將化合物E-1積層為35nm的厚度作為電子傳輸層。 A glass substrate (11 Ω/□, sputtered product manufactured by GEOMATEC Co., Ltd.) having an ITO transparent conductive film of 50 nm was cut into 38 mm × 46 mm, and etching was performed. The obtained substrate was subjected to ultrasonic cleaning for 15 minutes using "Semico Clean 56" (trade name, manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water. The substrate was subjected to an ultraviolet-ozone treatment for 1 hour immediately before the device was fabricated, and was placed in a vacuum vapor deposition apparatus and evacuated until the degree of vacuum in the apparatus was 5 × 10 -4 Pa or less. 10 nm of the compound HI-1 was vapor-deposited as a hole injection layer by a resistance heating method. Next, 80 nm of the compound HT-6 was vapor-deposited as the first hole transport layer. Next, 10 nm of the compound [1] was vapor-deposited as the second hole transport layer. Next, using compound H-1 as a host material and using compound D-1 as a dopant material, a thickness of 30 nm was vapor-deposited as a dopant so that the doped density of the dopant material was 10% by weight. Floor. Next, a layer of the compound E-1 was laminated to have a thickness of 35 nm as an electron transport layer.

其次，將羥基喹啉鋰蒸鍍1nm後，將鎂與銀的共蒸鍍膜以蒸鍍速度比為鎂：銀=10：1(=0.5nm/s：0.05nm/s)蒸鍍100nm而製成陰極，製作5mm×5mm見方的元件。此處所謂的膜厚為石英振盪式膜厚監視器的顯示值。使該發光元件以10mA/cm2直流進行驅動，結果獲得發光效率46.0Im/W的高效率綠色發光。將該發光元件以10mA/cm2的直流連續驅動，結果於3050小時亮度半衰。此外，化合物HI-1、化合物HT-6、化合物H-1、化合物D-1、化合物E-1為以下所示的化合物。 Next, after vapor deposition of lithium hydroxyquinolate 1 nm, a vapor-deposited film of magnesium and silver was vapor-deposited at a plating rate of magnesium: silver = 10:1 (=0.5 nm/s: 0.05 nm/s) to a thickness of 100 nm. As a cathode, a 5 mm × 5 mm square element was fabricated. The film thickness referred to here is a display value of a quartz oscillation type film thickness monitor. The light-emitting element was driven at 10 mA/cm 2 of direct current, and as a result, high-efficiency green light emission having a luminous efficiency of 46.0 μm/W was obtained. The light-emitting element was continuously driven at a direct current of 10 mA/cm 2 , and as a result, the luminance was half-decayed at 3050 hours. Further, the compound HI-1, the compound HT-6, the compound H-1, the compound D-1, and the compound E-1 are the compounds shown below.

實施例2~實施例4、比較例1~比較例8 Example 2 to Example 4, Comparative Example 1 to Comparative Example 8

使用表2中所記載的材料作為第二電洞傳輸層，除此以外，以與實施例1相同的方式製作發光元件。將結果示於表2。此外，HT-1~HT-8為以下所示的化合物，該些化合物的最低激發三重態能階(T1)如表1所示。 A light-emitting element was produced in the same manner as in Example 1 except that the material described in Table 2 was used as the second hole transport layer. The results are shown in Table 2. Further, HT-1 to HT-8 are compounds shown below, and the lowest excited triplet energy level (T1) of these compounds is shown in Table 1.

實施例5~實施例8 Embodiment 5 to Embodiment 8

以蒸鍍速度比1：1的比率使用化合物H-1與化合物H-2的混合主體代替化合物H-1作為主體材料，除此以外，以與實施例1相同的方式製作發光元件。將結果示於表2。此外，H-2為以下所示的化合物。 A light-emitting device was produced in the same manner as in Example 1 except that the mixed host of the compound H-1 and the compound H-2 was used instead of the compound H-1 as a host material at a ratio of a vapor deposition rate of 1:1. The results are shown in Table 2. Further, H-2 is a compound shown below.

實施例9 Example 9

將堆積有ITO透明導電膜50nm的玻璃基板(吉奧馬股份有限公司製造，11Ω/□，濺鍍品)切斷成38mm×46mm，進行蝕刻。利用“Semico Clean 56”(商品名，古內化學股份有限公司製造)對所獲得的基板進行15分鐘超音波清洗後，利用超純水進行清洗。於即將製作元件之前對該基板進行1小時UV-臭氧處理，設置於真空蒸鍍裝置內，進行排氣直至裝置內的真空度成為5×10-4Pa以下為止。藉由電阻加熱法，蒸鍍10nm的化合物HI-1作為電洞注 入層。其次，蒸鍍50nm的化合物HT-6作為第一電洞傳輸層。其次，蒸鍍40nm的化合物[1]作為第二電洞傳輸層。其次，使用化合物H-3作為主體材料，使用化合物D-2作為摻雜劑材料，以使摻雜劑材料的摻雜濃度成為5重量%的方式蒸鍍成30nm的厚度作為發光層。其次，將化合物E-1積層為35nm的厚度作為電子傳輸層。 A glass substrate (11 Ω/□, sputtered product manufactured by Geoma Co., Ltd.) having an ITO transparent conductive film deposited thereon was cut into 38 mm × 46 mm, and etched. The obtained substrate was subjected to ultrasonic cleaning for 15 minutes using "Semico Clean 56" (trade name, manufactured by Gunei Chemical Co., Ltd.), and then washed with ultrapure water. The substrate was subjected to UV-ozone treatment for 1 hour immediately before the device was fabricated, and was placed in a vacuum vapor deposition apparatus, and evacuated until the degree of vacuum in the apparatus was 5 × 10 -4 Pa or less. 10 nm of the compound HI-1 was vapor-deposited as a hole injection layer by a resistance heating method. Next, 50 nm of the compound HT-6 was evaporated as the first hole transport layer. Next, a compound [1] of 40 nm was evaporated as a second hole transport layer. Next, using compound H-3 as a host material and using compound D-2 as a dopant material, a thickness of 30 nm was vapor-deposited as a light-emitting layer so that the doping concentration of the dopant material was 5% by weight. Next, a layer of the compound E-1 was laminated to have a thickness of 35 nm as an electron transport layer.

其次，將氟化鋰蒸鍍0.5nm後，將鋁蒸鍍1000nm而製成陰極，製作5mm×5mm見方的元件。此處所謂的膜厚為石英振盪式膜厚監視器顯示值。將該發光元件以10mA/cm2直流進行驅動，結果獲得發光效率13.0Im/W的高效率紅色發光。將該發光元件以10mA/cm2的直流連續驅動，結果於3000小時亮度半衰。此外，化合物H-3、化合物D-2為以下所示的化合物。 Next, after depositing 0.5 nm of lithium fluoride, aluminum was vapor-deposited by 1000 nm to prepare a cathode, and a 5 mm × 5 mm square element was produced. The film thickness referred to here is a quartz oscillation type film thickness monitor display value. The light-emitting element was driven at 10 mA/cm 2 of direct current, and as a result, high-efficiency red light emission having a luminous efficiency of 13.0 μm/W was obtained. The light-emitting element was continuously driven at a direct current of 10 mA/cm 2 , and as a result, the luminance was half-decayed at 3000 hours. Further, the compound H-3 and the compound D-2 are the compounds shown below.

實施例10~實施例12 Embodiment 10 to Embodiment 12

使用表3中所記載的材料作為第二電洞傳輸層，除此以外，以與實施例9相同的方式製作發光元件並進行評價。將結果示於 表3。 A light-emitting device was produced and evaluated in the same manner as in Example 9 except that the material described in Table 3 was used as the second hole transport layer. Show results in table 3.

比較例9~比較例16 Comparative Example 9 to Comparative Example 16

使用表3中所記載的化合物作為第二電洞傳輸層，除此以外，以與實施例9相同的方式製作發光元件並進行評價。將結果示於表3。 A light-emitting device was produced and evaluated in the same manner as in Example 9 except that the compound described in Table 3 was used as the second hole transport layer. The results are shown in Table 3.

實施例13 Example 13

將堆積有ITO透明導電膜50nm的玻璃基板(吉奧馬股份有限公司製造，11Ω/□，濺鍍品)切斷成38mm×46mm，進行蝕刻。利用“Semico Clean 56”(商品名，古內化學股份有限公司製造)對所獲得的基板進行15分鐘超音波清洗後，利用超純水進行清洗。於即將製作元件之前對該基板進行1小時UV-臭氧處理，設置於真空蒸鍍裝置內，進行排氣直至裝置內的真空度成為5×10-4Pa以下為止。藉由電阻加熱法，蒸鍍10nm的化合物[1]作為電洞注入層。其次，蒸鍍90nm的化合物HT-6作為電洞傳輸層。其次，使用化合物H-3作為主體材料，使用化合物D-2作為摻雜劑材料，以使摻雜劑材料的摻雜濃度成為5重量%的方式蒸鍍成30nm的厚度作為發光層。其次，將化合物E-1積層為35nm的厚度作為電子傳輸層。 A glass substrate (11 Ω/□, sputtered product manufactured by Geoma Co., Ltd.) having an ITO transparent conductive film deposited thereon was cut into 38 mm × 46 mm, and etched. The obtained substrate was subjected to ultrasonic cleaning for 15 minutes using "Semico Clean 56" (trade name, manufactured by Gunei Chemical Co., Ltd.), and then washed with ultrapure water. The substrate was subjected to UV-ozone treatment for 1 hour immediately before the device was fabricated, and was placed in a vacuum vapor deposition apparatus, and evacuated until the degree of vacuum in the apparatus was 5 × 10 -4 Pa or less. 10 nm of the compound [1] was deposited as a hole injection layer by a resistance heating method. Next, 90 nm of the compound HT-6 was vapor-deposited as a hole transport layer. Next, using compound H-3 as a host material and using compound D-2 as a dopant material, a thickness of 30 nm was vapor-deposited as a light-emitting layer so that the doping concentration of the dopant material was 5% by weight. Next, a layer of the compound E-1 was laminated to have a thickness of 35 nm as an electron transport layer.

其次，將氟化鋰蒸鍍0.5nm後，將鋁蒸鍍1000nm而製成陰極，製作5mm×5mm見方的元件。此處所謂的膜厚為石英振盪式膜厚監視器顯示值。將該發光元件以10mA/cm2直流進行驅動，結果獲得發光效率13.0Im/W的高效率紅色發光。將該發光 元件以10mA/cm2的直流連續驅動，結果於2800小時亮度半衰。 Next, after depositing 0.5 nm of lithium fluoride, aluminum was vapor-deposited by 1000 nm to prepare a cathode, and a 5 mm × 5 mm square element was produced. The film thickness referred to here is a quartz oscillation type film thickness monitor display value. The light-emitting element was driven at 10 mA/cm 2 of direct current, and as a result, high-efficiency red light emission having a luminous efficiency of 13.0 μm/W was obtained. The light-emitting element was continuously driven at a direct current of 10 mA/cm 2 , and as a result, the luminance was half-decayed at 2,800 hours.

實施例14~實施例16 Embodiment 14 to Embodiment 16

使用表4中所記載的材料作為電洞注入層，除此以外，以與實施例13相同的方式製作發光元件並進行評價。將結果示於表4。 A light-emitting device was produced and evaluated in the same manner as in Example 13 except that the material described in Table 4 was used as the hole injection layer. The results are shown in Table 4.

比較例17 Comparative Example 17

使用表4中所記載的材料作為電洞注入層，除此以外，以與實施例13相同的方式製作發光元件並進行評價。將結果示於表4。 A light-emitting device was produced and evaluated in the same manner as in Example 13 except that the material described in Table 4 was used as the hole injection layer. The results are shown in Table 4.

Claims (5)

一種發光元件材料，其特徵在於：含有下述通式(1)所表示的化合物， (R1~R16可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R17R18所組成的組群；R17及R18為芳基或雜芳基；其中，於R1~R8的任一位置及R9~R16的任一位置兩個咔唑骨架連結；Ar1及Ar3可分別相同亦可不同，表示經取代或未經取代的苯基；Ar2表示經取代或未經取代的伸苯基；Ar4為下述式(A)或下述式(B)所表示的基團) (R19~R36可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R37R38所組成的組群；R37及R38為芳基或雜芳基；其中，式(A)中於R19~R28中的任一位置與氮原子連結，式(B)中於R29~R36中的任一位置與氮原子連結；X為氧原子、或硫原子、或N-Ar5；Ar5表示經取代或未經取代的苯基；Y表示碳原子，n為0或1；於n為1時，Y亦可經烷基取代)。 A light-emitting device material comprising a compound represented by the following formula (1), (R 1 to R 16 may be the same or different and are selected from hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine formazan. a group consisting of a decyl group, a decyl group, and a -P(=O)R 17 R 18 ; R 17 and R 18 are an aryl or heteroaryl group; wherein, at any position of R 1 to R 8 and R 9 Any one of -R 16 may be bonded to two carbazole skeletons; Ar 1 and Ar 3 may be the same or different, each represents a substituted or unsubstituted phenyl group; and Ar 2 represents a substituted or unsubstituted phenyl group; ; Ar 4 is a group represented by the following formula (A) or the following formula (B)) (R 19 to R 36 may be the same or different and are selected from hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine formazan. a group consisting of a decyl group, a decyl group, and a -P(=O)R 37 R 38 ; R 37 and R 38 are an aryl or heteroaryl group; wherein, in the formula (A), R 19 to R 28 Any position is bonded to a nitrogen atom, and in any one of R 29 to R 36 in the formula (B) is bonded to a nitrogen atom; X is an oxygen atom, or a sulfur atom, or N-Ar 5 ; Ar 5 represents a substitution or Unsubstituted phenyl; Y represents a carbon atom, n is 0 or 1; when n is 1, Y may also be substituted by an alkyl group). 如申請專利範圍第1項所述的發光元件材料，其中上述通式(1)所表示的化合物為下述通式(2)所表示的化合物， (R39~R52可分別相同亦可不同，選自由氫、烷基、環烷基、雜環基、烯基、環烯基、炔基、鹵素、羰基、羧基、氧羰基、胺甲醯基、矽烷基、及-P(=O)R53R54所組成的組群；R53及R54為芳基或雜芳基；Ar6及Ar8可分別相同亦可不同，表示經取代或未經取代的苯基；Ar7表示經取代或未經取代的伸苯基；Ar9為上述式(A)或上述式(B)所表示的基團)。 The light-emitting device material according to the above aspect of the invention, wherein the compound represented by the above formula (1) is a compound represented by the following formula (2), (R 39 ~ R 52 may be the same or different, selected from hydrogen, alkyl, cycloalkyl, heterocyclic, alkenyl, cycloalkenyl, alkynyl, halogen, carbonyl, carboxyl, oxycarbonyl, amine formazan a group consisting of a group, a decyl group, and a -P(=O)R 53 R 54 ; R 53 and R 54 are an aryl group or a heteroaryl group; and Ar 6 and Ar 8 may be the same or different, respectively, indicating a substitution. Or an unsubstituted phenyl group; Ar 7 represents a substituted or unsubstituted phenyl group; and Ar 9 is a group represented by the above formula (A) or the above formula (B). 一種發光元件，其是於陽極與陰極之間存在有機層，且藉由電能而發光的發光元件，其特徵在於：於上述陽極與上述陰極之間的任一層中含有如申請專利範圍第1項或第2項所述的發光元件材料。 A light-emitting element comprising an organic layer between an anode and a cathode and emitting light by electric energy, characterized in that: in any layer between the anode and the cathode, the first item of the patent application scope is included Or the light-emitting element material according to item 2. 如申請專利範圍第3項所述的發光元件，其中於上述有機層中至少存在電洞傳輸層，且於電洞傳輸層中含有如申請專利範圍第1項或第2項所述的發光元件材料。 The light-emitting element according to claim 3, wherein at least the hole transport layer is present in the organic layer, and the light-emitting element according to claim 1 or 2 is contained in the hole transport layer. material. 如申請專利範圍第3項所述的發光元件，其中於上述有機層中至少存在電洞注入層，且於電洞注入層中含有如申請專利範圍第1項或第2項所述的發光元件材料。 The light-emitting element according to claim 3, wherein at least the hole injection layer is present in the organic layer, and the light-emitting element according to claim 1 or 2 is contained in the hole injection layer. material.
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