TWI473790B

TWI473790B - Organic electroluminescent elements

Info

Publication number: TWI473790B
Application number: TW99123968A
Authority: TW
Inventors: Chihaya Adachi; Denghui Xu; Shuzo Hirata; Osamu Hirata; Yuki Shinbano
Original assignee: Kyushu University Mational University Corp; Nissan Chemical Ind Ltd
Priority date: 2009-07-21
Filing date: 2010-07-21
Publication date: 2015-02-21
Also published as: WO2011010656A1; KR20120042938A; CN102473853A; KR101704774B1; TW201120005A; JPWO2011010656A1; JP5686379B2; CN102473853B

Description

Organic electroluminescent element

本發明係關於一種有機電致發光元件，更詳細描述時，為有關在常溫下具備液體之發光層的有機電致發光元件。The present invention relates to an organic electroluminescence device, and more specifically describes an organic electroluminescence device having a liquid light-emitting layer at normal temperature.

有機電激發光元件(Organic Electro-Luminescence)(以下稱為有機EL元件)，為具有在陰極與陽極之間挾持至少含有1種發光性有機化合物之薄膜的有機層(發光層)構造，將電子及電洞注入‧輸送於此薄膜中，使再結合產生激子(exciton)，為利用此激子去活化之際所放出的光(螢光‧燐光)來發光之元件。Organic Electro-Luminescence (hereinafter referred to as an organic EL element) is an organic layer (light-emitting layer) having a film containing at least one type of luminescent organic compound between a cathode and an anode, and an electron And the hole injection ‧ is transported to the film, and recombines to generate an exciton, which is an element that emits light (fluorescence ‧ 燐 light) emitted by the exciton deactivation

此有機EL元件，因使用發光性有機化合物作為發光層之發光元件，對於應用於作為輕量且可撓，並以廉價之大面積可全彩顯示之顯示器之應用，被受期待。This organic EL device is expected to be used as a light-emitting element using a light-emitting organic compound as a light-emitting layer, and is applied to a display which is lightweight and flexible and can be displayed in a large area at a low cost and in a full-color display.

此有機EL元件所使用的發光層為藉由電洞及電子雙方載體(電荷)之輸送、經由此等載體之再結合之激子之形成、然而放出光的3個步驟予以驅動。The light-emitting layer used in the organic EL device is driven by three steps of transporting a carrier (charge) of a hole and an electron, forming excitons via recombination of the carriers, and emitting light.

因此，對與發光層，能滿足此等3機能之材料為必要且不可或缺的，通常作為此材料，為使用發揮此等3機能之載體輸送性發光材料、或為補償3機能之將複數種有機物混合之載體輸送材料/發光材料。Therefore, it is necessary and indispensable for the material to satisfy the three functions of the light-emitting layer, and it is generally used as a material for the carrier-transmitting luminescent material that exhibits these three functions, or for the compensation of the three functions. A carrier transport material/luminescent material mixed with organic matter.

使用上述載體輸送材料/發光材料作為發光層時，藉由以載體輸送材料使發光材料予以稀釋之動作，可抑制濃度消光(concentration quenching)，被期待可得到具有高發光效率之有機EL元件。因此，發光材料與載體輸送材間之各式各樣的組合正被集中精力的研究著。When the carrier transport material/light-emitting material is used as the light-emitting layer, the concentration of the light-emitting material can be suppressed by the operation of diluting the light-emitting material with the carrier transport material, and an organic EL element having high light-emitting efficiency can be expected. Therefore, various combinations between the luminescent material and the carrier transport material are being studied with great concentration.

然而，發光層用之發光材料，並不只是單純地使用具有欲得到螢光波長及高量子收率者即可，而是必須進行適合於特定螢光色素之載體輸送材料之選定。此理由為在載體輸送材料中所輸送的載體會進行再結合，所以此時所產生的激發能會誘發載體輸送材料中所摻雜的螢光色素發光。However, the luminescent material for the luminescent layer is not limited to the one having the desired wavelength of the fluorescent light and the high quantum yield, but the carrier transporting material suitable for the specific fluorescent pigment must be selected. The reason for this is that the carrier transported in the carrier transport material is recombined, so that the excitation energy generated at this time induces luminescence of the fluorescent pigment doped in the carrier transport material.

因此，發光材料/載體輸送材料各成分之HOMO/LUMO能階之相互關係，或者是此等之有效率性的能量轉移之組合選定會變得必要且不可或缺。Therefore, the correlation of the HOMO/LUMO energy levels of the components of the luminescent material/carrier transport material, or the combination of such efficient energy transfer, becomes necessary and indispensable.

現在，有機EL元件中重要問題之一為存在著所謂的烙印(image sticking)之劣化。此現象為有機EL元件在長時間的外加電壓下，起因可能是由於雜質將構成有機EL元件之材料分解或改性。Now, one of the important problems in organic EL elements is the deterioration of so-called image sticking. This phenomenon is caused by a long-term applied voltage of the organic EL element, which may be due to impurities decomposing or modifying the material constituting the organic EL element.

為防止此劣化，將電極表面之水分、氧或構成有機薄膜時所含有的僅有雜質等除去為必要的。In order to prevent such deterioration, it is necessary to remove moisture, oxygen, or only impurities contained in the surface of the electrode when the electrode is formed.

作為此具體之手法，已有利用提高構成有機EL元件有機物之純度及安定性，或為防止由外部之氧及水分之混入，將乾燥劑等封裝之方法。As a specific method, a method of improving the purity and stability of the organic material constituting the organic EL element or sealing the desiccant or the like from the external oxygen and moisture has been used.

然而，由實用面之考量，有機EL元件之壽命在100cd/m² 時至少必須具有10萬小時，其間有機物之分解或由於產生之雜質導致元件之劣化可以說是為無法避免的。However, from the viewpoint of practical use, the lifetime of the organic EL element must be at least 100,000 hours at 100 cd/m ² , and the decomposition of the organic substance or the deterioration of the element due to the generated impurities can be said to be unavoidable.

上述之既存有機EL元件，此等各有機層之烙印已成為元件劣化之原因，構成有機EL元件之具有複數有機層當中只要有一層產生劣化，對於元件整體之壽命影響甚大。In the above-described existing organic EL element, the imprinting of these organic layers has become a cause of deterioration of the element, and if one of the plurality of organic layers constituting the organic EL element is deteriorated, the life of the entire element is greatly affected.

假設，將此已劣化之有機層製作成例如以匣(cartridge)等可交換之構造時，即可持續供給新的有機層，結果使可半永久的驅動之有機EL元件為可能的。It is assumed that when the deteriorated organic layer is formed into an exchangeable structure such as a cartridge, that is, a new organic layer can be continuously supplied, and as a result, a semi-permanently driven organic EL element is possible.

但，幾乎所有上述既存有機EL元件為使用固體的有機薄膜，僅交換已劣化之有機層為非常的困難。However, almost all of the above-mentioned existing organic EL elements are organic thin films using solids, and it is extremely difficult to exchange only the deteriorated organic layers.

然而，在專利文獻1中已揭示使用液狀或半固形狀載體輸送材料之有機EL元件，但發光層本身並不具有流動性。However, in Patent Document 1, an organic EL element using a liquid or semi-solid carrier transport material has been disclosed, but the light-emitting layer itself does not have fluidity.

又，在專利文獻2及非專利文獻1中已揭示在液晶性有機化合物中溶解螢光色素所得到具有發光層之有機EL元件。Further, in Patent Document 2 and Non-Patent Document 1, an organic EL device having a light-emitting layer obtained by dissolving a fluorescent dye in a liquid crystalline organic compound has been disclosed.

此等元件為在液晶之相轉移溫度以上使其發光驅動，但在相轉移溫度以下時，發光層為固體不具有流動性。These elements are driven to emit light above the phase transition temperature of the liquid crystal, but when the phase transition temperature is lower than the phase transition temperature, the light-emitting layer is solid and does not have fluidity.

更，在非專利文獻2中揭示液體之咔唑為具有電荷輸送能，但並未對於含有此的有機EL元件予以揭示。Further, Non-Patent Document 2 discloses that a liquid carbazole has charge transporting ability, but it is not disclosed for an organic EL device containing the same.

[先前技術文獻][Previous Technical Literature]

[專利文獻][Patent Literature]

[專利文獻1]國際公開第2007/034900號[Patent Document 1] International Publication No. 2007/034900

[專利文獻2]特開2003-308970號公報[Patent Document 2] JP-A-2003-308970

[非專利文獻][Non-patent literature]

[非專利文獻1]Appl.Phys.Lett.,73,1595(1998)[Non-Patent Document 1] Appl. Phys. Lett., 73, 1595 (1998)

[非專利文獻2]Organic Electronics,9(2008)396-400[Non-Patent Document 2] Organic Electronics, 9 (2008) 396-400

本發明為有鑑於此等情事者，係以提供具備液體發光層，且於驅動時及非驅動時均能維持發光層為液狀之有機EL元件為目的。In view of the above, the present invention has an object of providing an organic EL device having a liquid light-emitting layer and maintaining the light-emitting layer in a liquid state during both driving and non-driving.

本發明者們為達成上述目的，經由專心重複檢討之結果，發現於常溫下為液體且於驅動時及非驅動時均能維持液狀之發光層，遂完成本發明。In order to achieve the above object, the inventors of the present invention have found that a liquid light-emitting layer can be maintained at a normal temperature and can be maintained at a normal temperature and at the time of driving and non-driving, and the present invention has been completed.

亦即，本發明係提供That is, the present invention provides

1.一種有機電致發光元件，其特徵係具備有陽極與陰極，及介於此等各極間之於常溫下為液體之發光層。An organic electroluminescence device comprising an anode and a cathode, and a light-emitting layer interposed between the electrodes at a normal temperature.

2.如第1項之有機電致發光元件，其中，前述發光層為含有具有載體輸送能及發光能之材料。2. The organic electroluminescence device according to Item 1, wherein the light-emitting layer contains a material having a carrier transport energy and a light-emitting energy.

3.　如第1項之有機電致發光元件，其中，前述發光層為含有載體輸送材料及發光材料。3. The organic electroluminescence device according to Item 1, wherein the light-emitting layer contains a carrier transport material and a light-emitting material.

4.如第3項之有機電致發光元件，其中，前述發光層為含有於常溫下為液體之載體輸送材料。4. The organic electroluminescence device according to Item 3, wherein the light-emitting layer is a carrier transport material containing a liquid at a normal temperature.

5.　如第3或4項之有機電致發光元件，其中，前述發光層為於常溫下為液體之發光材料。5. The organic electroluminescence device according to Item 3 or 4, wherein the luminescent layer is a luminescent material that is liquid at normal temperature.

6.　如第4項之有機電致發光元件，其中，前述載體輸送材料為以式(1)所示之化合物，6. The organic electroluminescence device according to Item 4, wherein the carrier transport material is a compound represented by the formula (1),

【化1】【化1】

X─Y　(1)X-Y (1)

(式中，X為電荷輸送部，示為咔唑、三唑、咪唑、二唑、2,5-二苯-1,3,4-二唑、芳基環烷烴、三芳胺、苯二胺、二苯乙烯、唑、三苯基甲烷、吡唑啉系化合物、蔥、茀酮、聚苯胺、矽烷、吡咯、茀、紫質、喹吖酮、氧化三苯膦、碳縮合環系色素、金屬或無金屬之酞青素、金屬或無金屬之萘酞青、或聯苯胺；Y為連結於前述電荷輸送部X之至少1個的取代基，示為可含有醚鍵、硫醚鍵、酯鍵、碳酸酯鍵或醯胺鍵之碳數1～30之烷基)。(wherein X is a charge transporting moiety, shown as carbazole, triazole, imidazole, Diazole, 2,5-diphenyl-1,3,4- Diazole, arylcycloalkane, triarylamine, phenylenediamine, stilbene, Azole, triphenylmethane, pyrazoline compound, onion, fluorenone, polyaniline, decane, pyrrole, indole, purpurin, quinophthalone, triphenylphosphine oxide, carbon condensation ring dye, metal or metal free Anthraquinone, a metal or a metal-free naphthoquinone, or a benzidine; and Y is a substituent bonded to at least one of the charge transporting portions X, and is an ether bond, a thioether bond, an ester bond, or a carbonate. A bond or a hydrazine bond having an alkyl group having 1 to 30 carbon atoms).

7.如第3項之有機電致發光元件，其中，前述發光材料為碳縮合環系色素、苝衍生物、系色素、花青系色素、香豆素系色素、喹吖酮系色素、方酸(squarylium)系色素、苯乙烯基系色素、吡唑哢衍生物、吩噁嗪酮(phenoxazon)系色素、咔唑、三芳胺、銥錯合物、或者是由Al、Zn、Be或稀土金屬所成的中心金屬及配位基所構成的金屬錯合物色素。7. The organic electroluminescence device according to Item 3, wherein the luminescent material is a carbon condensed ring-based dye, an anthracene derivative, a pigment, a cyanine dye, a coumarin dye, a quinophthalone dye, a squarylium dye, a styrene dye, a pyrazole derivative, a phenoxazon dye, A carbazole, a triarylamine, a ruthenium complex, or a metal complex dye composed of a central metal and a ligand composed of Al, Zn, Be or a rare earth metal.

8.如第7項之有機電致發光元件，其中，前述發光材料為以式(2)所示之化合物，8. The organic electroluminescence device according to Item 7, wherein the luminescent material is a compound represented by the formula (2).

【化2】[Chemical 2]

Z─W　(2)Z-W (2)

(式中，Z為色素部，示為碳縮合環系色素、苝衍生物、系色素、花青系色素、香豆素系色素、喹吖酮系色素、方酸(squarylium)系色素、苯乙烯基系色素、吡唑哢衍生物、吩噁嗪酮(phenoxazon)系色素、咔唑、三芳胺、銥錯合物、或者是由Al、Zn、Be或稀土金屬所成的中心金屬及配位基所構成的金屬錯合物；W為連結於前述色素部Y之至少1個的取代基，示為可含有醚鍵、硫醚鍵、酯鍵、碳酸酯鍵或醯胺鍵之碳數1～30之烷基)。(In the formula, Z is a dye moiety, and is represented by a carbon condensed ring-based dye, an anthracene derivative, a pigment, a cyanine dye, a coumarin dye, a quinophthalone dye, a squarylium dye, a styrene dye, a pyrazole derivative, a phenoxazon dye, a carbazole, a triarylamine, a ruthenium complex, or a metal complex composed of a central metal and a ligand composed of Al, Zn, Be or a rare earth metal; and W is at least 1 bonded to the dye portion Y. The substituents are shown as an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether bond, an ester bond, a carbonate bond or a guanamine bond.

9.如第6項之有機電致發光元件，其中，前述電荷輸送部X為咔唑。9. The organic electroluminescence device according to Item 6, wherein the charge transporting portion X is carbazole.

10.如第6項之有機電致發光元件，其中，前述取代基Y為碳數1～30之烷基。10. The organic electroluminescence device according to Item 6, wherein the substituent Y is an alkyl group having 1 to 30 carbon atoms.

11.如第6項之有機電致發光元件，其中，前述電荷輸送部X為咔唑，前述取代基Y為碳數1～30之烷基。11. The organic electroluminescence device according to Item 6, wherein the charge transporting portion X is carbazole, and the substituent Y is an alkyl group having 1 to 30 carbon atoms.

12.如第6項之有機電致發光元件，其中，前述載體輸送材料為以式(3)所示，12. The organic electroluminescence device according to Item 6, wherein the carrier transport material is represented by the formula (3).

【化3】[化3]

(式中，Y與前述為相同意思)。(wherein Y has the same meaning as described above).

13.如第12項之有機電致發光元件，其中，前述載體輸送材料為以式(4)所示，[13] The organic electroluminescence device according to Item 12, wherein the carrier transport material is represented by the formula (4).

【化4】【化4】

14.如第12項之有機電致發光元件，其中，前述載體輸送材料為以式(5)所示，[14] The organic electroluminescence device according to Item 12, wherein the carrier transport material is represented by the formula (5).

【化5】【化5】

15.如第7及9～14項中任1項之有機電致發光元件，其中，前述發光材料為紅螢烯(rubrene)。The organic electroluminescence device according to any one of items 7 to 9, wherein the luminescent material is rubrene.

本發明之有機電致發光元件，為於驅動時及非驅動時發光層均可維持液狀者。因此，在發光層劣化之情況時，可製作成僅將發光層交換之構造(例如匣，經由循環之取出‧再注入)。The organic electroluminescence device of the present invention is capable of maintaining a liquid state during the driving and non-driving. Therefore, in the case where the light-emitting layer is deteriorated, a structure in which only the light-emitting layer is exchanged (for example, enthalpy, re-injection via circulation) can be produced.

又，因為發光層為液體，所以可利用塗佈法製程製造元件，可對應大面積之照明元件。Moreover, since the light-emitting layer is a liquid, the component can be manufactured by a coating method, and can correspond to a large-area illumination element.

再者，也可製作出比既存之固體有機薄膜所成的有機EL元件可撓性更高之顯示元件。Further, it is also possible to produce a display element which is more flexible than the organic EL element formed by the existing solid organic film.

[實施發明的最佳型態][Best form of implementing the invention]

以下為針對本發明進行更詳細之說明。The following is a more detailed description of the invention.

本發明相關之有機電致發光元件為具備有陽極與陰極，及介於此等各極之間於常溫下為液體之發光層者。The organic electroluminescence device according to the present invention is a light-emitting layer including an anode and a cathode, and a liquid layer which is liquid at normal temperature between the respective electrodes.

此處，所謂的常溫為依據JIS Z 8703所規定之20℃±15℃(5～35℃)範圍的意思。Here, the normal temperature is a range of 20 ° C ± 15 ° C (5 to 35 ° C) defined by JIS Z 8703.

作為液體發光層，只要是整體發光層為顯示液體狀性質者即可，可使用發光層構成材料之載體輸送材料及發光材料之至少一方為液體，同時構成發光層之整體組成物為液狀者。As the liquid light-emitting layer, as long as the entire light-emitting layer exhibits a liquid-like property, at least one of the carrier transport material and the light-emitting material using the light-emitting layer constituent material may be a liquid, and the entire composition of the light-emitting layer may be liquid. .

另外，依不同物質，有些無法明確地分辨載體輸送能及發光能之兩機能，例如在咔唑、三芳胺、碳縮合環系色素等之中，亦存在同時具有兩機能者。In addition, depending on the substance, some of the functions of the carrier transport energy and the luminescence energy cannot be clearly distinguished. For example, among carbazole, triarylamine, carbon condensed ring-based pigments, etc., there are also two functions.

本發明之整體發光層只要是顯示液體狀，可使用同時具有此兩機能之物質，或者只要是顯示液狀者，單獨使用其亦可。The entire light-emitting layer of the present invention may be used as long as it exhibits a liquid state, or may be used alone as long as it exhibits a liquid state.

在本發明中，作為液體之載體輸送材料，適合使用以式(1)所示之化合物。In the present invention, as the carrier transporting material for the liquid, a compound represented by the formula (1) is suitably used.

【化6】【化6】

X─Y　(1)X-Y (1)

此處，X為電荷輸送部，表示為咔唑、三唑、咪唑、二唑、2,5-二苯-1,3,4-二唑、芳基環烷烴、三芳胺、苯二胺、二苯乙烯、唑、三苯基甲烷、吡唑啉系化合物、蔥、茀酮、聚苯胺、矽烷、吡咯、茀、紫質、喹吖酮、氧化三苯膦、蔥衍生物，四并苯((tetracene)衍生物，芘衍生物，紅螢烯(rubrene)衍生物，十環烯(decacyclene)衍生物，苝衍生物等之碳縮合環系色素、金屬或無金屬之酞青素、金屬或無金屬之萘酞青、聯苯胺。Here, X is a charge transporting portion, which is represented by carbazole, triazole, imidazole, Diazole, 2,5-diphenyl-1,3,4- Diazole, arylcycloalkane, triarylamine, phenylenediamine, stilbene, Azole, triphenylmethane, pyrazoline compound, onion, fluorenone, polyaniline, decane, pyrrole, indole, purpurin, quinophthalone, triphenylphosphine oxide, onion derivative, tetracene Derivatives, anthracene derivatives, rubrene derivatives, decacyclene derivatives, anthracene derivatives, etc., carbon condensed ring-based pigments, metal or metal-free anthocyanins, metals or metals-free Naphthoquinone blue, benzidine.

此等之中又以具有優異之電洞輸送性能之觀點而言，以咔唑為佳。Among these, carbazole is preferred from the viewpoint of excellent hole transport performance.

另一方面，Y為連結於前述電荷輸送部X之至少1個的取代基，可示為含有醚鍵、硫醚鍵、酯鍵、碳酸酯鍵或醯胺鍵之碳數1～30之烷基。尚，此等醚鍵、硫醚鍵、酯鍵、碳酸酯鍵、醯胺鍵亦可存在於X與Y之連結部(此點，後述之Z亦為相同)。On the other hand, Y is a substituent which is bonded to at least one of the charge transporting units X, and can be represented by an alkyl group having 1 to 30 carbon atoms including an ether bond, a thioether bond, an ester bond, a carbonate bond or a guanamine bond. base. Further, these ether bonds, thioether bonds, ester bonds, carbonate bonds, and guanamine bonds may be present in the joint portion between X and Y (this point is also the same as Z described later).

此時，烷基可任意為直鏈、分支、環狀，但在使用直鏈狀烷基時，由於烷鏈彼此間之歛集等分子間相互之作用，因而可能提升結晶性及增加黏度，所以較佳為分支狀之烷基。In this case, the alkyl group may be linear, branched or cyclic. However, when a linear alkyl group is used, crystallinity and viscosity increase may be promoted due to interaction between molecules such as agglomerates. Therefore, it is preferably a branched alkyl group.

作為如此碳數1～30之烷基之具體例，可舉例如甲基、乙基、n-丙基、i-丙基、c-丙基、n-丁基、i-丁基、s-丁基、t-丁基、c-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、c-戊基、2-甲基-c-丁基、n-已基、1-甲基-n-戊基、2-甲基-n-戊基、1,1-二甲基-n-丁基、1-乙基-n-丁基、1,1,2-三甲基-n-丙基、c-已基、1-甲基-c-戊基、1-乙基-c-丁基、1,2-二甲基-c-丁基、n-庚基、n-辛基、2-乙基已基、n-壬基、n-癸基、n-十一基、n-十二基、n-十三基、n-十四基、n-十五基、n-十六基、n-十七基、n-十八基、n-十九基、n-二十基等。Specific examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, c-propyl group, n-butyl group, i-butyl group, and s-. Butyl, t-butyl, c-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1, 1-Dimethyl-n-propyl, c-pentyl, 2-methyl-c-butyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, c-hexyl, 1-methyl-c -pentyl, 1-ethyl-c-butyl, 1,2-dimethyl-c-butyl, n-heptyl, n-octyl, 2-ethylhexyl, n-fluorenyl, n -fluorenyl, n-undecyl, n-dodecyl, n-tridedecyl, n-tetradecyl, n-pentadecayl, n-hexadecanyl, n-heptadecyl, n-eighteen Base, n-nine group, n- twenty base, and the like.

所謂的含有醚鍵、硫醚鍵、酯鍵、碳酸酯鍵或醯胺鍵之碳數1～30之烷基，可舉例在如同上述的烷基之任意位置具有此等鍵者，具體可舉例如下述之取代基。The alkyl group having 1 to 30 carbon atoms which contains an ether bond, a thioether bond, an ester bond, a carbonate bond or a guanamine bond can be exemplified by having such a bond at any position as the above alkyl group, and specific examples thereof Substituents as described below.

作為含有醚鍵之上述烷基之具體例，可舉例有CH₂ OCH₃ 、CH₂ OCH₂ CH₃ 、CH₂ O(CH₂ )₂ CH₃ 、CH₂ OCH(CH₃ )₂ 、CH₂ O(CH₂ )₃ CH₃ 、CH₂ OCH₂ CH(CH₃ )₂ 、CH₂ OCH(CH₃ )₃ 、CH₂ O(CH₂ )₄ CH₃ 、CH₂ OCH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ OCH₂ CH(CH₃ )CH₃ 、CH₂ O(CH₂ )₂ CH(CH₃ )CH₃ 、CH₂ OC(CH₃ )₂ CH₃ 、CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ O(CH₂ )₅ CH₃ 、CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ OCH₂ CH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ O(CH₂ )₂ CH(CH₃ )CH₂ CH₃ 、CH₂ O(CH₂ )₃ CH(CH₃ )CH₃ 、CH₂ OC(CH₃ )₂ (CH₂ )₂ CH₃ 、CH₂ OCH(CH₂ CH₃ )(CH₂ )₂ CH₃ 、CH₂ OC(CH₃ )₂ CH(CH₃ )CH₃ 、CH₂ O(CH₂ )₆ CH₃ 、CH₂ O(CH₂ )₇ CH₃ 、CH₂ OCH₂ CH(CH₂ CH₃ )(CH₂ )₃ CH₃ 、CH₂ O(CH₂ )₈ CH₃ 、CH₂ O(CH₂ )₉ CH₃ 、CH₂ O(CH₂ )₁₀ CH₃ 、CH₂ O(CH₂ )₁₁ CH₃ 、CH₂ O(CH₂ )₁₂ CH₃ 、CH₂ O(CH₂ )₁₃ CH₃ 、CH₂ O(CH₂ )₁₄ CH₃ 、CH₂ O(CH₂ )₁₅ CH₃ 、CH₂ O(CH₂ )₁₆ CH₃ 、CH₂ O(CH₂ )₁₇ CH₃ 、CH₂ O(CH₂ )₁₈ CH₃ 、CH₂ O(CH₂ )₁₉ CH₃ 、CH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ O(CH₂ )₂ CH₃ 、CH₂ CH₂ OCH(CH₃ )₂ 、CH₂ CH₂ O(CH₂ )₃ CH₃ 、CH₂ CH₂ OCH₂ CH(CH₃ )₂ 、CH₂ CH₂ OCH(CH₃ )₃ 、CH₂ CH₂ O(CH₂ )₄ CH₃ 、CH₂ CH₂ OCH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ OCH₂ CH(CH₃ )CH₃ 、CH₂ CH₂ O(CH₂ )₂ CH(CH₃ )CH₃ 、CH₂ CH₂ OC(CH₃ )₂ CH₃ 、CH₂ CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ O(CH₂ )₅ CH₃ 、CH₂ CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ OCH₂ CH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ O(CH₂ )₂ CH(CH₃ )CH₂ CH₃ 、CH₂ CH₂ O(CH₂ )₃ CH(CH₃ )CH₃ 、CH₂ CH₂ OC(CH₃ )₂ (CH₂ )₂ CH₃ 、CH₂ CH₂ OCH(CH₂ CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ OC(CH₃ )₂ CH(CH₃ )CH₃ 、CH₂ CH₂ O(CH₂ )₆ CH₃ 、CH₂ CH₂ O(CH₂ )₇ CH₃ 、CH₂ CH₂ OCH₂ CH(CH₂ CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ O(CH₂ )₈ CH₃ 、CH₂ CH₂ O(CH₂ )₉ CH₃ 、CH₂ CH₂ O(CH₂ )₁₀ CH₃ 、CH₂ CH₂ O(CH₂ )₁₁ CH₃ 、CH₂ CH₂ O(CH₂ )₁₂ CH₃ 、CH₂ CH₂ O(CH₂ )₁₃ CH₃ 、CH₂ CH₂ O(CH₂ )₁₄ CH₃ 、CH₂ CH₂ O(CH₂ )₁₅ CH₃ 、CH₂ CH₂ O(CH₂ )₁₆ CH₃ 、CH₂ CH₂ O(CH₂ )₁₇ CH₃ 、CH₂ CH₂ O(CH₂ )₁₈ CH₃ 、CH₂ CH₂ O(CH₂ )₁₉ CH₃ 、CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₃ )₂ 、CH₂ CH₂ CH₂ O(CH₂ )₃ CH₃ 、CH₂ CH₂ CH₂ OCH₂ CH(CH₃ )₂ 、CH₂ CH₂ CH₂ OCH(CH₃ )₃ 、CH₂ CH₂ CH₂ O(CH₂ )₄ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ OCH₂ CH(CH₃ )CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₂ CH(CH₃ )CH₃ 、CH₂ CH₂ CH₂ OC(CH₃ )₂ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₅ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ CH₂ OCH₂ CH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₂ CH(CH₃ )CH₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₃ CH(CH₃ )CH₃ 、CH₂ CH₂ CH₂ OC(CH₃ )₂ (CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₂ CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ OC(CH₃ )₂ CH(CH₃ )CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₆ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₇ CH₃ 、CH₂ CH₂ CH₂ OCH₂ CH(CH₂ CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₈ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₉ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₀ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₁ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₃ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₄ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₅ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₆ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₇ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₈ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₉ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 基等，或以下述式所示之基等。Specific examples of the above alkyl group having an ether bond include CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , CH ₂ O(CH ₂ ) ₂ CH ₃ , CH ₂ OCH(CH ₃ ) ₂ , and CH ₂ O. (CH ₂ ) ₃ CH ₃ , CH ₂ OCH ₂ CH(CH ₃ ) ₂ , CH ₂ OCH(CH ₃ ) ₃ , CH ₂ O(CH ₂ ) ₄ CH ₃ , CH ₂ OCH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ OCH ₂ CH(CH ₃ )CH ₃ , CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₃ , CH ₂ OC(CH ₃ ) ₂ CH ₃ , CH ₂ OCH(CH ₃ ) (CH ₂ ) ₃ CH ₃ , CH ₂ O(CH ₂ ) ₅ CH ₃ , CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , CH ₂ O(CH ₂ ) ₃ CH(CH ₃ )CH ₃ , CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ )CH ₃ , CH ₂ O(CH ₂ ) ₆ CH ₃ , CH ₂ O(CH ₂ ) ₇ CH ₃ , CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ O(CH ₂ ) ₈ CH ₃ , CH ₂ O(CH ₂ ) ₉ CH ₃ , CH ₂ O (CH ₂ ) ₁₀ CH ₃ , CH ₂ O(CH ₂ ) ₁₁ CH ₃ , CH ₂ O(CH ₂ ) ₁₂ CH ₃ , CH ₂ O(CH ₂ ) ₁₃ CH ₃ , CH ₂ O(CH ₂ ) ₁₄ CH ₃ , CH ₂ O(CH ₂ ) ₁₅ CH ₃ , CH ₂ O(CH ₂ ) ₁₆ CH ₃ , CH ₂ O(CH ₂ ) ₁₇ CH ₃ , CH ₂ O(CH ₂ ) ₁₈ CH ₃ , CH ₂ O(CH ₂ ) ₁₉ CH ₃ , CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ OCH(CH ₃ ) ₂ , CH ₂ CH ₂ O(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ OCH ₂ CH(CH ₃ ) ₂ , CH ₂ CH ₂ OCH(CH ₃ ) ₃ , CH ₂ CH ₂ O(CH ₂ ) ₄ CH ₃ , CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ O(CH ₂ ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ OC(CH ₃ ) ₂ CH ₃ , CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₅ CH ₃ , CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₂ CH (CH ₃ )CH ₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₃ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ OCH (CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₆ CH ₃ , CH ₂ CH ₂ O (CH ₂ ) ₇ CH ₃ , CH ₂ CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₈ CH ₃ , CH ₂ CH ₂ O(CH ₂ ₉ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₀ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₁ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₃ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₄ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₅ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₆ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₇ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₈ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₉ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₃ ) ₂ , CH ₂ CH ₂ CH ₂ O (CH ₂ ₃ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ ) ₂ , CH ₂ CH ₂ CH ₂ OCH(CH ₃ ) ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₄ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₂ CH(CH ₃ ) CH ₃ , CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₅ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ O ( CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₃ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OC(CH ₃ ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₆ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₇ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ( CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₈ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₉ CH ₃ , CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₀ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₁ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₂ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₃ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₄ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₅ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₆ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₇ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₈ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₉ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ _{_{_{_{CH 2 CH 2 CH 2 OCH 2}}}} CH 2 CH 2 OCH 3, CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 3, CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ group or the like, or a group represented by the following formula.

【化7】【化7】

作為含有硫醚鍵之上述烷基之具體例，可舉例如以硫原子(S)取代含有上述醚鍵之烷基的氧原子(O)之基等。Specific examples of the alkyl group having a thioether bond include, for example, a group in which an oxygen atom (O) of an alkyl group containing the above ether bond is substituted by a sulfur atom (S).

作為含有酯鍵之上述烷基之具體例，可舉例如以C(O)O或OC(O)取代含有上述醚鍵之烷基的氧原子(O)之基等。Specific examples of the alkyl group having an ester bond include a group in which an oxygen atom (O) of an alkyl group containing the above ether bond is substituted by C(O)O or OC(O).

作為含有碳酸酯鍵之上述烷基之具體例，可舉例如以OC(O)O取代含有上述醚鍵之烷基的氧原子(O)之基等。Specific examples of the alkyl group having a carbonate bond include, for example, a group in which an oxygen atom (O) of an alkyl group containing the above ether bond is substituted by OC(O)O.

作為含有醯胺鍵之碳數1～30烷基，可舉例如以C(O)NH或NHC(O)取代含有上述醚鍵之烷基的氧原子(O)之基等。The alkyl group having 1 to 30 carbon atoms containing a guanamine bond may, for example, be a group in which an oxygen atom (O) of an alkyl group containing the above ether bond is substituted by C(O)NH or NHC(O).

在此等之中，又以容易成為液體之觀點而言，較佳為碳數6～30之取代基，具體為c-已基、1-甲基-c-戊基、1-乙基-c-丁基、1,2-二甲基-c-丁基、n-庚基、n-辛基、2-乙基已基、n-壬基、n-癸基、n-十一基、n-十二基、n-十三基、n-十四基、n-十五基、n-十六基、n-十七基、n-十八基、n-十九基、n-二十基基、CH₂ O(CH₂ )₅ CH₃ 、CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ OCH₂ CH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ O(CH₂ )₂ CH(CH₃ )CH₂ CH₃ 、CH₂ O(CH₂ )₃ CH(CH₃ )CH₃ 、CH₂ OC(CH₃ )₂ (CH₂ )₂ CH₃ 、CH₂ OCH(CH₂ CH₃ )(CH₂ )₂ CH₃ 、CH₂ OC(CH₃ )₂ CH(CH₃ )CH₃ 、CH₂ O(CH₂ )₆ CH₃ 、CH₂ O(CH₂ )₇ CH₃ 、CH₂ OCH₂ CH(CH₂ CH₃ )(CH₂ )₃ CH₃ 、CH₂ O(CH₂ )₈ CH₃ 、CH₂ O(CH₂ )₉ CH₃ 、CH₂ O(CH₂ )₁₀ CH₃ 、CH₂ O(CH₂ )₁₁ CH₃ 、CH₂ O(CH₂ )₁₂ CH₃ 、CH₂ O(CH₂ )₁₃ CH₃ 、CH₂ O(CH₂ )₁₄ CH₃ 、CH₂ O(CH₂ )₁₅ CH₃ 、CH₂ O(CH₂ )₁₆ CH₃ 、CH₂ O(CH₂ )₁₇ CH₃ 、CH₂ O(CH₂ )₁₈ CH₃ 、CH₂ O(CH₂ )₁₉ CH₃ 、CH₂ CH₂ O(CH₂ )₅ CH₃ 、CH₂ CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ OCH₂ CH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ O(CH₂ )₂ CH(CH₃ )CH₂ CH₃ 、CH₂ CH₂ O(CH₂ )₃ CH(CH₃ )CH₃ 、CH₂ CH₂ OC(CH₃ )₂ (CH₂ )₂ CH₃ 、CH₂ CH₂ OCH(CH₂ CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ OC(CH₃ )₂ CH(CH₃ )CH₃ 、CH₂ CH₂ O(CH₂ )₆ CH₃ 、CH₂ CH₂ O(CH₂ )₇ CH₃ 、CH₂ CH₂ OCH₂ CH(CH₂ CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ O(CH₂ )₈ CH₃ 、CH₂ CH₂ O(CH₂ )₉ CH₃ 、CH₂ CH₂ O(CH₂ )₁₀ CH₃ 、CH₂ CH₂ O(CH₂ )₁₁ CH₃ 、CH₂ CH₂ O(CH₂ )₁₂ CH₃ 、CH₂ CH₂ O(CH₂ )₁₃ CH₃ 、CH₂ CH₂ O(CH₂ )₁₄ CH₃ 、CH₂ CH₂ O(CH₂ )₁₅ CH₃ 、CH₂ CH₂ O(CH₂ )₁₆ CH₃ 、CH₂ CH₂ O(CH₂ )₁₇ CH₃ 、CH₂ CH₂ O(CH₂ )₁₈ CH₃ 、CH₂ CH₂ O(CH₂ )₁₉ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₅ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ CH₂ OCH₂ CH(CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₂ CH(CH₃ )CH₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₃ CH(CH₃ )CH₃ 、CH₂ CH₂ CH₂ OC(CH₃ )₂ (CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ OCH(CH₂ CH₃ )(CH₂ )₂ CH₃ 、CH₂ CH₂ CH₂ OC(CH₃ )₂ CH(CH₃ )CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₆ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₇ CH₃ 、CH₂ CH₂ CH₂ OCH₂ CH(CH₂ CH₃ )(CH₂ )₃ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₈ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₉ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₀ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₁ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₂ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₃ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₄ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₅ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₆ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₇ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₈ CH₃ 、CH₂ CH₂ CH₂ O(CH₂ )₁₉ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₃ 基等，以及此等基之氧原子(O)被硫原子(S)所取代之基，或被C(O)O或OC(O)所取代之基，或被OC(O)O所取代之基，或被C(O)NH或NHC(O)所取代之基等為合適。Among these, in view of being easy to be a liquid, a substituent having 6 to 30 carbon atoms is preferable, specifically c-hexyl group, 1-methyl-c-pentyl group, 1-ethyl- C-butyl, 1,2-dimethyl-c-butyl, n-heptyl, n-octyl, 2-ethylhexyl, n-fluorenyl, n-fluorenyl, n-undecyl , n-dodecyl, n-trideyl, n-tetradecyl, n-pentadepyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-n-19, n - icoyl, CH ₂ O(CH ₂ ) ₅ CH ₃ , CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ ,CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , CH ₂ O(CH ₂ ) ₃ CH(CH ₃ )CH ₃ , CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ ,CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ )CH ₃ , CH ₂ O(CH ₂ ) ₆ CH ₃ , CH ₂ O(CH ₂ ) ₇ CH ₃ , CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ O(CH ₂ ) ₈ CH ₃ , CH ₂ O(CH ₂ ) ₉ CH ₃ , CH ₂ O(CH ₂ ) ₁₀ CH ₃ , CH ₂ O(CH ₂ ) ₁₁ CH ₃ , CH ₂ O(CH ₂ ) ₁₂ CH ₃ , CH ₂ O(CH ₂ ) ₁₃ CH ₃ , CH ₂ O(CH ₂ ) ₁₄ CH ₃ , CH ₂ O(CH ₂ ) ₁₅ CH ₃ , CH ₂ O(CH ₂ ) ₁₆ CH ₃ , CH ₂ O(CH ₂ ) ₁₇ CH ₃ , CH ₂ O(CH ₂ ) ₁₈ CH ₃ , CH ₂ O(CH ₂ ) ₁₉ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₅ CH ₃ , CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₃ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ OC (CH ₃ ) ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₆ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₇ CH ₃ , CH ₂ CH ₂ OCH ₂ CH(CH ₂ CH ₃ ) (CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₈ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₉ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₀ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₁ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₂ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₃ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₄ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₅ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₆ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₇ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₈ CH ₃ , CH ₂ CH ₂ O(CH ₂ ) ₁₉ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₅ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ ,CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₃ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OCH(CH ₂ CH ₃ ) (CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ )CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₆ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₇ CH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₈ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₉ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₀ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₁ CH ₃ , CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₂ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₃ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₄ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₅ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₆ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₇ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₈ CH ₃ , CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₉ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ group, etc., and the oxygen atom of these groups (O) a group substituted by a sulfur atom (S), or a group substituted by C(O)O or OC(O), or a group substituted by OC(O)O, or C(O)NH Or the base substituted by NHC (O) is suitable.

更佳為CH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 、CH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₂ CH₂ CH₂ OCH₃ 基等。More preferably CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ ,CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ C H ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ group or the like.

作為合適的載體輸送材料，可舉例如下述之咔唑(X1)、N,N-二取代或N,N,N-三取代之芳基胺(X2)等。As a suitable carrier transport material, for example, the following carbazole (X1), N,N-disubstituted or N,N,N-trisubstituted arylamine (X2) and the like can be given.

【化9】【化9】

上述式中，Y¹ ～Y⁶ 分別獨立地示為為氫原子，或者是可具有醚鍵、硫醚、酯鍵、碳酸酯鍵或醯胺鍵等之碳數1～30之烷基(惟，Y¹ ～Y³ 中至少1個及Y⁴ ～Y⁶ 中至少1個為上述烷基)、A¹ 及A² 示為單鍵或者是取代或非取代之芳香族環。In the above formula, Y ¹ to Y ⁶ are each independently represented as a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms which may have an ether bond, a thioether, an ester bond, a carbonate bond or a guanamine bond. At least one of Y ¹ to Y ³ and at least one of Y ⁴ to Y ⁶ are the above alkyl group, and A ¹ and A ² are each a single bond or a substituted or unsubstituted aromatic ring.

此處，所謂‘烷基’之用語，為含有如甲基、乙基、異丙基、t-丁基、2-乙基已基、環已基之線狀、分支型、環狀烷，此與上述一般式(1)之使熔點下降之官能基(Y)為相當，此具體例及合適例如同上述。Here, the term "alkyl" is a linear, branched, or cyclic alkane containing, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, or a cyclohexyl group. This corresponds to the functional group (Y) which lowers the melting point of the above general formula (1), and this specific example and suitable are, for example, the same as described above.

作為芳香族環，可舉例如苯環、萘環等。The aromatic ring may, for example, be a benzene ring or a naphthalene ring.

本發明應防止因分子量增加之黏度增加，較佳以Y¹ 、Y² 、Y⁴ 及Y⁵ 為氫原子、Y³ 及Y⁶ 為烷者，更以A¹ ,A² 為苯環或單鍵者為佳。The present invention should prevent an increase in viscosity due to an increase in molecular weight, preferably Y ¹ , Y ² , Y ⁴ and Y ⁵ are hydrogen atoms, Y ³ and Y ⁶ are alkane, and A ¹ , A ² are benzene rings or single The key is better.

由此等之觀點，以下述化合物(X3)為佳、更佳為化合物(3)、又更佳為化合物(4)或化合物(5)，但不限定於此等。From the viewpoint of the above, the following compound (X3) is preferred, more preferably compound (3), still more preferably compound (4) or compound (5), but is not limited thereto.

【化10】【化10】

【化11】【化11】

(式中，Y³ 與上述為相同意思)。(wherein Y ³ has the same meaning as described above).

【化12】【化12】

又，以下述所示之化合物亦可適合使用。Further, a compound shown below can also be suitably used.

【化13】【化13】

(式中Y⁴ ～Y¹¹ 分別獨立示為氫原子，或者是可含有醚鍵、硫醚、酯鍵、碳酸酯鍵或醯胺鍵等之碳數1～30之烷基(惟，Y⁴ ～Y⁶ 中至少1個、Y⁷ 及Y⁸ 之至少1個、Y⁹ ～Y¹¹ 中至少1個為上述烷基)。(In the formula, Y ⁴ to Y ¹¹ are each independently represented by a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether, an ester bond, a carbonate bond or a guanamine bond (only, Y ^{4 )} At least one of -Y ⁶ , at least one of Y ⁷ and Y ⁸ , and at least one of Y ⁹ to Y ¹¹ is the above alkyl group).

【化14】【化14】

(式中，R¹ ～R⁴ 相互獨立示為碳數1～30之烷基)。(wherein R ¹ to R ⁴ are each independently shown to be an alkyl group having 1 to 30 carbon atoms).

【化15】【化15】

尚，作為後述發光材料若為使用液體材料時，只要構成發光層之整體材料為液體，亦可使用於常溫下為固體者來作為載體輸送材料。When a liquid material is used as the light-emitting material to be described later, the entire material constituting the light-emitting layer may be a liquid, and it may be used as a carrier transport material when it is solid at normal temperature.

作為如此的載體輸送材料，只要從向來公知之材料中適當選擇即可，可舉例如(三苯胺)二聚體衍生物(TPD)、(α-萘基二苯胺)二聚體(α-NPD)、[(三苯基胺)二聚體]螺旋二聚體(Spiro-TAD)等之三芳胺類、4,4’,4”-參[3-甲苯基(苯基)胺基]三苯基胺(m-MTDATA)、4,4’,4”-參[1-萘基(苯基)胺基]三苯基胺(1-TNATA)等之星狀胺(Starburst Amine)類；5,5”-雙-{4-[雙(4-甲苯基)胺基]苯基}-2,2’：5’,2”三聯噻吩(BMA-3T)等之寡聚噻吩(oligothiophene)類、聚乙烯基咔唑類等之電洞輸送材料；Alq₃ 、BAlq、DPVBi、(2-(4-聯苯基)-5-(4-t-丁基苯基)-1,3,4-二唑)(PBD)、三唑衍生物(TAZ)、Bathocuproin(BCP)、Silole衍生物等之電子輸送材料。As such a carrier transporting material, as long as it is appropriately selected from materials which are known in the art, for example, (triphenylamine) dimer derivative (TPD) or (α-naphthyldiphenylamine) dimer (α-NPD) may be mentioned. , [(triphenylamine) dimer] helical dimer (Spiro-TAD) and other triarylamines, 4,4',4"-gin[3-tolyl (phenyl)amino] a class of starburst Amines such as phenylamine (m-MTDATA), 4,4', 4"-para-[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA); Oligothiophene of 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2"tripithiophene (BMA-3T) a hole transporting material such as a polyvinyl carbazole; Alq ₃ , BAlq, DPVBi, (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3, 4- Electron transport materials such as oxadiazole) (PBD), triazole derivatives (TAZ), Bathocuproin (BCP), Silole derivatives, and the like.

作為構成本發明發光層之另外一側之材料之發光材料，由公知者中適當選擇即可，例如可使用蔥衍生物、四并苯((tetracene)衍生物、芘衍生物、紅螢烯(rubrene)衍生物、十環烯(decacyclene)衍生物等之碳縮合環系色素；苝二醯亞胺(Perylene Diimide)等之苝衍生物；玫瑰紅B等之系色素；花青系色素；香豆素6、C545T等之香豆素系色素；Qd4、DEQ等之喹吖酮系色素；方酸(squarylium)系色素；苯乙烯基系色素；吡唑哢衍生物；NileRed等之吩噁嗪酮(phenoxazon)系色素；咔唑；三芳胺；參(2-苯基吡啶)銥(III)(Ir(ppy)₃ )、參[2-苯基-4-(2-乙基環己氧基)吡啶]銥(III)(Ir(ehppy)₃ )等之銥錯合物；Alq3(alumiquinolinol)錯合物、Bebq2(benzoquinolinol beryllium)錯合物、苯并唑基鋅錯合物、苯并噻唑鋅錯合物、氮甲烷基鋅錯合物、紫質鋅錯合物、銪錯合物等之由Al、Zn、Be或Tb、Eu、Dy等稀土金屬所成的中心金屬，及由二唑、噻二唑、苯基吡啶、苯基苯并咪唑、喹啉構造等配位基所構造之金屬錯合物等。The luminescent material constituting the material of the other side of the light-emitting layer of the present invention may be appropriately selected from known ones, and for example, an onion derivative, a tetracene derivative, an anthracene derivative, or a red fluorene (for example) may be used. a carbon condensed ring-based dye such as a derivative or a decacyclene derivative; an anthracene derivative such as Perylene Diimide; rose red B or the like a pigment; a cyanine pigment; a coumarin pigment such as coumarin 6, C545T; a quinophthalone dye such as Qd4 or DEQ; a squarylium dye; a styrene-based pigment; a derivative; a phenoxazon-based dye of NileRed; a carbazole; a triarylamine; a ginseng (2-phenylpyridine) ruthenium (III) (Ir(ppy) ₃ ), a gin [2-phenyl-4 -(2-ethylcyclohexyloxy)pyridine] ruthenium (III) (Ir(ehppy) ₃ ) and other ruthenium complex; Alq3 (alumiquinolinol) complex, Bebq2 (benzoquinolinol beryllium) complex, benzo Rare earths such as Al, Zn, Be or Tb, Eu, Dy, etc., such as azolyl zinc complex, benzothiazole zinc complex, nitrogen alkyl zinc complex, purple zinc complex, ruthenium complex, etc. The central metal formed by the metal, and A metal complex or the like constructed by a ligand such as an oxadiazole, a thiadiazole, a phenylpyridine, a phenylbenzimidazole or a quinoline structure.

此等之中又以所謂在發光效率優異之觀點，較佳為紅螢烯衍生物。Among these, a red fluorene derivative is preferable from the viewpoint of excellent luminous efficiency.

另外，在本發明中，作為發光材料亦可使用以式(2)所示之液狀化合物。Further, in the present invention, a liquid compound represented by the formula (2) can also be used as the luminescent material.

【化16】【化16】

Z─W　(2)Z-W (2)

此處，Z為色素部，示為碳縮合環系色素、苝衍生物、系色素、花青系色素、香豆素系色素、喹吖酮系色素、方酸(squarylium)系色素、苯乙烯基系色素、吡唑衍生物、吩噁嗪酮(phenoxazon)系色素、咔唑、三芳胺、銥錯合物、由Al、Zn、Be或稀土金屬所成的中心金屬及配位基所構成的金屬錯合物；W為連結於上述色素部Z之至少1個的取代基，示為可含有醚鍵、硫醚鍵、酯鍵、碳酸酯鍵或醯胺鍵之碳數1～30之烷基。Here, Z is a dye moiety, and is shown as a carbon condensed ring-based dye, an anthracene derivative, Pigment, cyanine pigment, coumarin pigment, quinophthalone dye, squarylium dye, styryl dye, pyrazole a derivative, a phenoxazon-based dye, a carbazole, a triarylamine, a ruthenium complex, a metal complex composed of a central metal and a ligand composed of Al, Zn, Be or a rare earth metal; W is a substituent which is bonded to at least one of the dye portions Z, and is represented by an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether bond, an ester bond, a carbonate bond or a guanamine bond.

作為上述色素部及烷基之具體例，可舉例如上述同樣者。Specific examples of the dye portion and the alkyl group include the same as described above.

作為合適之Z，可舉例如碳縮環系色素，特別是紅螢烯衍生物、芘衍生物；作為合適之W，可舉例如碳數1～30之烷基，特別是碳數6～30之烷基。As a suitable Z, for example, a carbon condensed ring-based dye, particularly a fluorene oxide derivative or an anthracene derivative, and a suitable alkyl group, for example, an alkyl group having 1 to 30 carbon atoms, particularly a carbon number of 6 to 30, may be mentioned. Alkyl group.

作為具體的發光材料，例如發光特性優異之碳縮合環系色素，可舉例如下述芘衍生物(Z1)。As a specific luminescent material, for example, a carbon condensed ring-based dye which is excellent in luminescent properties, for example, the following hydrazine derivative (Z1) can be mentioned.

【化17】【化17】

上述式中，W¹ ～W⁴ 分別獨立示為氫原子，或者是可含有醚鍵、硫醚、酯鍵、碳酸酯鍵或醯胺鍵等之碳數1～30之烷基(惟，W¹ ～W⁴ 中至少1個為上述烷基)；A¹ ～A⁴ 示為單鍵，或者是取代或非取代之芳香族環。此處，作為烷基之具體例，可舉例與上述Y為同樣者；作為芳香族環之具體例，可舉例與上述為同樣者。In the above formula, W ¹ to W ⁴ are each independently represented by a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether, an ester bond, a carbonate bond or a guanamine bond (only, W At least one of ¹ to W ⁴ is the above alkyl group; and A ¹ to A ⁴ are each a single bond or a substituted or unsubstituted aromatic ring. Here, as a specific example of the alkyl group, the same as the above-mentioned Y may be mentioned, and as a specific example of the aromatic ring, the same as the above may be mentioned.

此情形時亦應防止隨分子量之增加所造成黏度之上昇，以A¹ ～A⁴ 為單鍵者，即W¹ ～W⁴ 為直接鍵結於碳縮合環之化合物(Z2)為佳、更佳為W¹ ～W⁴ 之至少1個為氫原子，特別是3個為氫原子者。In this case as well, the increase in viscosity due to the increase in molecular weight should be prevented. It is preferred that the compounds A ¹ to A ⁴ are single bonds, that is, W ¹ to W ⁴ are directly bonded to the carbon condensation ring (Z2). Preferably, at least one of W ¹ to W ⁴ is a hydrogen atom, and particularly three of them are hydrogen atoms.

由此等之觀點，以下述化合物(Z3)為佳，但不限定於此等。From the viewpoint of the above, the following compound (Z3) is preferred, but is not limited thereto.

【化18】【化18】

【化19】【化19】

將以上述(Z1)～(Z3)所示之化合物作為液體發光體，亦可做成具備非主客系統(Host-Guest System)之發光層之有機EL元件。The compound represented by the above (Z1) to (Z3) is used as a liquid illuminator, and an organic EL device having a luminescent layer of a host-guest system can also be used.

又，若載體輸送材料為液體時，只要構成發光層之整體材料為液體，亦可使用於常溫下為固體者來作為發光材料。Further, when the carrier transport material is a liquid, the entire material constituting the light-emitting layer may be a liquid, and it may be used as a light-emitting material when it is solid at normal temperature.

作為如此之發光材料，從向來公知之材料中適當選擇即可，可舉例如參(8-羥基喹啉)鋁(III)(Alq₃ )、雙(8-羥基喹啉)鋅(II)(Znq₂ )、雙(2-甲基-8-羥基喹啉)(p-苯基苯酚)鋁(III)(BAlq)、4,4’-雙(2,2-二乙烯基聯本基)聯苯基(DPVBi)等。As such a light-emitting material, a material which is known in the art may be appropriately selected, and examples thereof include argon (8-hydroxyquinoline) aluminum (III) (Alq ₃ ) and bis(8-hydroxyquinoline) zinc (II) ( Znq ₂ ), bis(2-methyl-8-hydroxyquinoline) (p-phenylphenol) aluminum (III) (BAlq), 4,4'-bis(2,2-divinylcarbyl) Biphenyl (DPVBi) and the like.

上述載體輸送材料及發光材料之調合比率，只要是整體組成物成為液體之範圍即可，並無特別限定，以質量比時，可使載體輸送材料：發光材料=99.99：0.01～50：50左右，但較佳為99：1。The blending ratio of the carrier transporting material and the luminescent material is not particularly limited as long as the total composition is in the range of the liquid, and the carrier transporting material: luminescent material = 99.99: 0.01 to 50: 50 at a mass ratio , but preferably 99:1.

本發明之有機電致發光元件因為是具有上述液體發光層之特徵，所以其他元件之構成構件並無特別之限制，可適當採用向來公知者。Since the organic electroluminescence device of the present invention is characterized by having the liquid luminescent layer described above, the constituent members of the other elements are not particularly limited, and those conventionally known can be suitably employed.

例如，作為陽極材料，可使用以銦錫氧化物(ITO)、銦鋅氧化物(IZO)為代表之透明電極或具有高電荷輸送性之聚噻吩衍生物、聚苯胺衍生物等。For example, as the anode material, a transparent electrode typified by indium tin oxide (ITO), indium zinc oxide (IZO), a polythiophene derivative having high charge transportability, a polyaniline derivative, or the like can be used.

作為陰極材料，可使用鋁、鎂-銀合金、鋁-鋰合金、鋰、鈉、鉀、銫、銫添加ITO等。As the cathode material, ITO or the like can be added using aluminum, a magnesium-silver alloy, an aluminum-lithium alloy, lithium, sodium, potassium, rubidium or cesium.

又，本發明之有機電致發光元件除了陽極、陰極及發光層之外，亦可具備有機電致發光元件一般所使用之各種機能層。Further, the organic electroluminescence device of the present invention may include various functional layers generally used in organic electroluminescence devices in addition to the anode, the cathode, and the light-emitting layer.

作為如此之機能層，可舉例如電洞輸送層、電洞注入層、電子輸送層、電子注入層、載體塊層等。As such a functional layer, for example, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a carrier block layer, and the like can be given.

電洞輸送層為設置於陽極與發光層之間，為具有將由陽極所注入之電洞輸送至發光層機能之層，作為其材料，可舉例與上述載體輸送材料所示例之電洞輸送材料為同樣者。The hole transport layer is disposed between the anode and the light-emitting layer, and has a layer for transporting the hole injected from the anode to the function of the light-emitting layer. As a material thereof, the hole transport material exemplified by the carrier transport material is exemplified as The same.

又，電洞注入層為設置於電洞輸送層與陽極之間，為具有提高由陽極之電洞注入效率機能之層。Further, the hole injection layer is provided between the hole transport layer and the anode, and has a function of improving the efficiency of injection of the hole from the anode.

作為形成電洞注入層之材料，可舉例如銅酞青素、4,4’,4”-參[3-甲苯基(苯基)胺基]三苯基胺(m-MTDATA)等。The material for forming the hole injection layer may, for example, becopeptin, 4,4',4"-gin[3-tolyl(phenyl)amino]triphenylamine (m-MTDATA).

電子輸送層為設置於陰極與發光層之間，為具有將由陰極所注入之電子輸送至發光層機能之層，作為其材料，可舉例與上述載體輸送材料所示例之電子輸送材料為同樣者。The electron transport layer is provided between the cathode and the light-emitting layer, and has a layer for transporting electrons injected from the cathode to the function of the light-emitting layer. The material thereof may be the same as the electron transport material exemplified as the carrier transport material.

電子注入層為設置於電子輸送層與陰極之間，為具有提高由陰極之電子注入效率機能之層。The electron injecting layer is disposed between the electron transporting layer and the cathode, and has a function of improving the electron injection efficiency of the cathode.

作為形成如此的電子注入層材料，可舉例如氧化鋰(Li₂ O)、氧化鎂(MgO)、氧化鋁(Al₂ O₃ )、氟化鋰(LiF)、氟化鎂(MgF₂ )、氟化鍶(SrF₂ )、Li(acac)、醋酸鋰、安息香酸鋰等。Examples of the material for forming such an electron injecting layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), lithium fluoride (LiF), and magnesium fluoride (MgF ₂ ). Barium fluoride (SrF ₂ ), Li (acac), lithium acetate, lithium benzoate, and the like.

載體塊層為控制發光領域之層，可形成於上述任意之層間之層。The carrier block layer is a layer that controls the field of light emission and can be formed in a layer between any of the above layers.

作為形成如此的載體塊層材料，可舉例如PBD、TAZ、BCP等。Examples of the material for forming such a carrier block layer include PBD, TAZ, BCP, and the like.

接著，一邊參考圖面一邊說明本發明之電致發光元件之一實施型態。Next, an embodiment of the electroluminescent device of the present invention will be described with reference to the drawings.

圖1為關於本發明之一實施型態之電致發光元件，以有機EL元件1表示。Fig. 1 shows an electroluminescent device according to an embodiment of the present invention, which is represented by an organic EL device 1.

此有機EL元件1，為具備陽極10與陰極20，及介於此等各極10，20之間於常溫下為液體之發光層50(以下稱為液體發光層50)。The organic EL element 1 is provided with an anode 10 and a cathode 20, and a light-emitting layer 50 (hereinafter referred to as a liquid-emitting layer 50) which is liquid at normal temperature between the respective electrodes 10 and 20.

更具體為在具備陽極10，及在此上所層合之電洞注入層30與陰極20之同時，具備由電洞注入層30與陰極20，與在此等之間設置有以Ag製間隔器40所形成之空間中所填充的液體發光層50。More specifically, the anode injection layer 30 and the cathode 20 which are laminated thereon are provided, and the hole injection layer 30 and the cathode 20 are provided, and an interval of Ag is provided therebetween. The liquid luminescent layer 50 filled in the space formed by the device 40.

在本實施型態中，陽極10為由玻璃基板11，與在此上所成膜之ITO基板12所構成。In the present embodiment, the anode 10 is composed of a glass substrate 11 and an ITO substrate 12 formed thereon.

另一方面，陰極20為由玻璃基板13，與在此上所成膜之ITO基板14，以及更在此上所成膜之Cs₂ CO₃ 層15所構成。On the other hand, the cathode 20 is composed of a glass substrate 13, an ITO substrate 14 formed thereon, and a Cs ₂ CO ₃ layer 15 formed thereon.

又，電洞注入層30為由PEDOT：PSS膜所構成。Further, the hole injection layer 30 is composed of a PEDOT:PSS film.

液體發光層50為含有載體輸送材料及發光材料所構成，在本實施型態，則以含有液體載體輸送材料之9-(2-乙基已基)咔唑(EHCz)，與於常溫下為固體發光材料之紅螢烯所構成。The liquid light-emitting layer 50 is composed of a carrier transport material and a light-emitting material. In the present embodiment, 9-(2-ethylhexyl)carbazole (EHCz) containing a liquid carrier transport material is used at room temperature. The solid luminescent material is composed of red fluorene.

作為構成如以上之有機EL元件之製作方法，並無特別的限制，例如可使用如下述之手法。The method for producing the organic EL element as described above is not particularly limited, and for example, the following method can be used.

首先，在陽極10上使用旋轉塗佈法將PEDOT：PSS塗佈，並將其加熱成膜成電洞注入層30。First, PEDOT:PSS is applied on the anode 10 by spin coating, and heated to form a hole injection layer 30.

於此電洞注入層30上，將Ag蒸鍍成條紋狀形成間隔器(spacer)40。On the hole injection layer 30, Ag is vapor-deposited into stripes to form a spacer 40.

另一方面，在玻璃基板13及ITO基板14之層合體上，將Cs₂ CO₃ 之甲醇溶液以旋轉塗佈法塗佈，並成膜成Cs₂ CO₃ 層。On the other hand, on a laminate of the glass substrate 13 and the ITO substrate 14, a methanol solution of Cs ₂ CO ₃ was applied by a spin coating method to form a Cs ₂ CO ₃ layer.

接著，在陽極10(電洞注入層30)上所形成之間隔器40之間，滴下含有指定量紅螢烯之9-(2-乙基已基)咔唑(EHCz)液體，形成液體發光層50，再以適當之壓力將陰極20壓著於其上，得到有機EL元件1。Next, a 9-(2-ethylhexyl)carbazole (EHCz) liquid containing a specified amount of erythritol is dropped between the spacers 40 formed on the anode 10 (hole injection layer 30) to form a liquid luminescence. The layer 50 is pressed against the cathode 20 at an appropriate pressure to obtain an organic EL element 1.

尚，構成各層之材料，並不限定於在上述實施型態所使用之材料，只要能發揮各層之機能，可由上述示例之各種材料中適當選擇使用。In addition, the material constituting each layer is not limited to the material used in the above-described embodiment, and any of the above-described various materials can be appropriately selected and used as long as the function of each layer can be exhibited.

例如，亦可將液體發光層50以不使用間隔器，僅以陽極10及陰極20挾持住，製作成如圖2、3所示般的有機EL元件2、3。For example, the liquid-emitting layer 50 can be formed by using only the anode 10 and the cathode 20 without using a spacer, and the organic EL elements 2 and 3 as shown in Figs. 2 and 3 can be produced.

又，各層之成膜方法也不限定於上述實施型態之手法，對應所使用之材料，可適當採用蒸鍍法、噴霧法、噴墨法、濺鍍法等公知之手法。Further, the film formation method of each layer is not limited to the above-described embodiment, and a known method such as a vapor deposition method, a spray method, an inkjet method, or a sputtering method can be suitably used depending on the material to be used.

[實施例][Examples]

以下舉例合成例及實施例，更具體說明本發明，惟，本發明不限定於下述之實施例。The present invention will be more specifically described by way of the following examples and examples, but the invention is not limited to the examples described below.

另外，在實施例所使用的測定裝置如同以下。Further, the measuring device used in the examples is as follows.

(1)電流-電壓-輝度特性(1) Current-voltage-luminance characteristics

以附光電偵測器之半導體參數分析儀(Agilent公司製、B1500A)與光功率計(NEWPORT、1930C)予以計測。It was measured with a semiconductor parameter analyzer (manufactured by Agilent, B1500A) and an optical power meter (NEWPORT, 1930C) with a photodetector.

(2)EL發光光譜(2) EL luminescence spectrum

以多頻分光器(PMA-11，濱松Photonics(股)製)予以計測。It was measured by a multi-frequency spectroscope (PMA-11, manufactured by Hamamatsu Photonics Co., Ltd.).

(3)¹ H-NMR(3) ¹ H-NMR

裝置：AVANCE 500、Bruker公司製Device: AVANCE 500, made by Bruker

裝置：JNM-LA400、日本電子DATUM(股)製Device: JNM-LA400, Japan Electronics DATUM (share) system

(4)基質輔助雷射脫附游離飛行時間質量分析(4) Quality analysis of matrix-assisted laser desorption free flight time

基質輔助雷射脫附游離飛行時間質譜儀裝置(MALDI-TOF-MS)、Autoflex-III.Bruker Daltonics公司製Matrix-assisted laser desorption free time-of-flight mass spectrometer (MALDI-TOF-MS), manufactured by Autoflex-III. Bruker Daltonics

[合成例1]EHPy之合成[Synthesis Example 1] Synthesis of EHPy

【化20】【化20】

將4-(1-芘基)酪酸(5.8g，20.0mmol)、1-溴-2-乙基己烷(7.7g，40.0mmol)及碳酸鉀(8.3g，60.0mmol)加入DMF(7.1mL)中，以90℃攪拌4小時。將溶劑減壓餾去後，加入氯仿(50mL)予以水洗(50mL×3)。加入硫酸鎂乾燥，並以柱層析法(n-己烷/氯仿=8/2(v/v))予以純化，得到為無色透明之液體EHPy(7.41g)。鑑定為以¹ H-NMR光譜來進行。NMR光譜如圖29所示。4-(1-indolyl)butyric acid (5.8 g, 20.0 mmol), 1-bromo-2-ethylhexane (7.7 g, 40.0 mmol) and potassium carbonate (8.3 g, 60.0 mmol) were added to DMF (7.1 mL) In the mixture, the mixture was stirred at 90 ° C for 4 hours. After the solvent was distilled off under reduced pressure, chloroform (50 mL) was added and washed with water (50mL×3). It was dried over magnesium sulfate, and purified by column chromatography (n-hexane / chloroform = 8/2 (v/v)) to give a colorless transparent liquid EHPy (7.41 g). It was identified as being carried out by ¹ H-NMR spectrum. The NMR spectrum is shown in Figure 29.

[合成例2]EHTPA之合成[Synthesis Example 2] Synthesis of EHTPA

【化21】【化21】

於氮氣流下，將3-胺苯酚(11g，100mmol)、溴苯(31g，200mmol)、叔丁醇鈉(38g，400mmol)、三叔丁基膦(0.40g，2.00mmol)及乙酸鈀(0.45g，2.00mmol)加入到二甲苯(250g)中，以120℃攪拌8小時。於反應溶液中加入氯仿(1.0L)，以10質量%氯化銨水溶液(500mL×2)予以洗淨後，進行水洗(500mL×2)。以硫酸鎂乾燥後，以柱層析法(矽膠，n-己烷/氯仿=1/1(v/v))予以純化，得到灰色粉末狀之化合物1(15.5g，收率59%)。3-Amine phenol (11 g, 100 mmol), bromobenzene (31 g, 200 mmol), sodium t-butoxide (38 g, 400 mmol), tri-tert-butylphosphine (0.40 g, 2.00 mmol) and palladium acetate (0.45) g, 2.00 mmol) was added to xylene (250 g), and stirred at 120 ° C for 8 hours. Chloroform (1.0 L) was added to the reaction solution, and the mixture was washed with a 10% by mass aqueous ammonium chloride solution (500 mL × 2), and then washed with water (500 mL × 2). After drying over magnesium sulfate, it was purified by column chromatography (yield: hexane, chloroform = 1/1 (v/v)) to give Compound 1 (15.5 g, yield 59%) as a white powder.

【化22】【化22】

將上述所得到的化合物1(2.6g，10.0mmol)、氯甲酸2-乙基己酯(2.1g，11.0mmol)及三乙胺(2.1g，22.0mmol)溶解於氯仿(50g)中，並以室溫攪拌1小時。將反應溶液以過濾除去不溶物後減壓餾去。柱層析法(以矽膠，n-己烷/氯仿=1/1(v/v))予以純化，得到無色透明之液體的EHTPA(3.0g，收率72%)。鑑定為以¹ H-NMR光譜來進行。NMR光譜如圖30所示。The above-obtained compound 1 (2.6 g, 10.0 mmol), 2-ethylhexyl chloroformate (2.1 g, 11.0 mmol) and triethylamine (2.1 g, 22.0 mmol) were dissolved in chloroform (50 g). Stir at room temperature for 1 hour. The reaction solution was filtered to remove insoluble matter, and then evaporated under reduced pressure. Column chromatography (purified by hydrazine, n-hexane / chloroform = 1 / 1 (v/v)) afforded EHTPA (3.0 g, yield 72%) as a colorless transparent liquid. It was identified as being carried out by ¹ H-NMR spectrum. The NMR spectrum is shown in Figure 30.

[合成例3]EHOXD之合成[Synthesis Example 3] Synthesis of EHOXD

【化23】【化23】

將3-羥基安息香酸甲酯(7.6g，50mmol)、1-溴-2-乙基己烷(19g，100mmol)及碳酸鉀(35g，250mmol)加入DMF(30mL)中，以80℃攪拌7小時。將溶劑減壓餾去後，加入氯仿(100mL)進行水洗(50mL×3)。使用硫酸鎂乾燥後，以柱層析法(n-己烷/乙酸乙酯=95/5(v/v))予以純化，得到白色粉末狀之化合物2(12.3g，收率93%)。Methyl 3-hydroxybenzoate (7.6 g, 50 mmol), 1-bromo-2-ethylhexane (19 g, 100 mmol) and potassium carbonate (35 g, 250 mmol) were added to DMF (30 mL) and stirred at 80 ° C. hour. After the solvent was distilled off under reduced pressure, chloroform (100 mL) was added and washed with water (50mL×3). After drying over magnesium sulfate, it was purified by column chromatography (n-hexane/ethyl acetate=95/5 (v/v)) to afford Compound 2 (12.3 g, yield 93%).

【化24】【化24】

將上述所得到的化合物2(12g，50mmol)溶解於THF中，並加入氫氧化鈉(2.0g，50mmol)、水(10g)及甲醇(10g)。將此反應溶液以80℃攪拌3小時後，加入氯仿(300mL)，進行水洗(150mL×3)。使用硫酸鎂乾燥後，藉由將溶劑減壓餾去得到化合物3(12.5g，收率99%)。The compound 2 (12 g, 50 mmol) obtained above was dissolved in THF, and sodium hydroxide (2.0 g, 50 mmol), water (10 g) and methanol (10 g) were added. After the reaction solution was stirred at 80 ° C for 3 hours, chloroform (300 mL) was added and washed with water (150 mL × 3). After drying with magnesium sulfate, the solvent was evaporated under reduced pressure to give Compound 3 (12.5 g, yield: 99%).

【化25】【化25】

將上述所得到的化合物3(13g，50mmol)懸濁於亞硫醯氯(18mL)中，以90℃加熱迴流4小時。以減壓餾去將亞硫醯氯餾去後，再將所得到之液體溶解於氯仿(50mL)中。在其反應溶液中緩慢加入三乙胺(5.1g，50mmol)及苯甲醯聯胺(benzohydrazide)(6.8g，50mmol)氯仿溶液(50mL)，於室溫下攪拌19小時。於反應溶液中加入氯仿(300mL)，進行水洗(150mL×3)。使用硫酸鎂乾燥，藉由將溶劑減壓餾去得到半成品之褐色的化合物4(18g)。The compound 3 (13 g, 50 mmol) obtained above was suspended in sulfinium chloride (18 mL), and heated to reflux at 90 ° C for 4 hours. After the thiousine chloride was distilled off under reduced pressure, the obtained liquid was dissolved in chloroform (50 mL). Triethylamine (5.1 g, 50 mmol) and benzohydrazide (6.8 g, 50 mmol) in chloroform (50 mL) were slowly added to the reaction solution, and stirred at room temperature for 19 hours. Chloroform (300 mL) was added to the reaction solution, and the mixture was washed with water (150 mL × 3). Drying with magnesium sulfate and distilling off the solvent under reduced pressure gave a semi-finished brown compound 4 (18 g).

【化26】【化26】

將化合物4(18g，50mmol)加入於亞硫醯氯(100mL)中，並迴流2小時。將亞硫醯氯減壓餾去後，使溶解於氯仿(300mL)中，以5質量%碳酸氫鈉水溶液予以洗淨(150mL×1)，更進行水洗(150mL×1)。使用硫酸鎂乾燥後，以柱層析法(矽膠，己烷/乙酸乙酯=95/5(v/v))予以純化，得到淡黃色之液體的EHOXD(9.0g，收率50%)。鑑定為以¹ H-NMR光譜來進行。NMR光譜如圖31所示。Compound 4 (18 g, 50 mmol) was added to sulphuryl chloride (100 mL) and refluxed for 2 h. After sulfhydryl chloride was distilled off under reduced pressure, the mixture was dissolved in chloroform (300 mL), washed with 5% aqueous sodium hydrogen carbonate solution (150 mL×1), and washed with water (150 mL×1). After drying over magnesium sulfate, it was purified by column chromatography (yield: hexane/ethyl acetate=95/5 (v/v)) to give EHOXD (9.0 g, yield 50%) as a pale yellow liquid. It was identified as being carried out by ¹ H-NMR spectrum. The NMR spectrum is shown in Figure 31.

[合成例4]EH₂ TPPO之合成[Synthesis Example 4] Synthesis of EH ₂ TPPO

【化27】【化27】

將3-溴酚(8.7g，50.0mmol)、1-溴-2-乙基己烷(19g，100mmol)及碳酸鉀(35g，250mmol)加入到DMF(50g)中，以80℃攪拌8小時。以過濾將不溶物除去後，將溶劑減壓餾去。於殘渣中加入氯仿(100mL)，進行水洗(100mL×2)、純化，得到黃色液體狀之化合物5(14g，收率98%)。3-Bromophenol (8.7 g, 50.0 mmol), 1-bromo-2-ethylhexane (19 g, 100 mmol) and potassium carbonate (35 g, 250 mmol) were added to DMF (50 g) and stirred at 80 ° C for 8 hours. . After the insoluble matter was removed by filtration, the solvent was distilled off under reduced pressure. Chloroform (100 mL) was added to the residue, and the mixture was washed with water (100 mL×2) and purified to give Compound 5 (14 g, yield 98%).

【化28】【化28】

將上述所得到的化合物5(3.6g，13.0mmol)冷卻到-60℃後使溶解於THF(100mL)中，花10分鐘將1.6Mn-丁基鋰己烷溶液滴下。以-60℃攪拌1小時後，緩慢加入二氯苯基膦(1.1g，6.00mmol)，將反應溶液徐徐回溫至室溫並攪拌3小時。將溶劑減壓餾去後，將殘渣溶解於氯仿(100mL)中，以飽和食鹽水(100mL)予以洗淨，接著以水(100mL×2)進行洗淨。將溶劑減壓餾去，以柱層析法(矽膠，己烷/乙酸乙酯=3/97(v/v))得到無色透明液體。於所得到的液體中加入THF(50mL)，花5分鐘將30%過氧化氫水(4.0mL)滴下。將反應溶液於室溫下攪拌20分鐘後，加入硫代硫酸鈉(5.5g)，更於室溫下攪拌5分鐘。將不溶物除去後，將溶劑減壓餾去。以柱層析法(矽膠，n-己烷/乙酸乙酯=8/2～1/1(v/v))予以純化，得到無色透明液體狀之EH₂ TPPO(1.1g)。鑑定為以1H-NMR光譜來進行。NMR光譜如圖32所示。The compound 5 (3.6 g, 13.0 mmol) obtained above was cooled to -60 ° C, dissolved in THF (100 mL), and the 1.6 Mn-butyl lithium hexane solution was dropped over 10 minutes. After stirring at -60 ° C for 1 hour, dichlorophenylphosphine (1.1 g, 6.00 mmol) was slowly added, and the reaction solution was gradually warmed to room temperature and stirred for 3 hours. The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform (100 mL), washed with saturated brine (100 mL), and washed with water (100 mL×2). The solvent was distilled off under reduced pressure, and purified by column chromatography (yield, hexane/ethyl acetate=3/97 (v/v)). THF (50 mL) was added to the obtained liquid, and 30% hydrogen peroxide water (4.0 mL) was dropped over 5 minutes. After the reaction solution was stirred at room temperature for 20 minutes, sodium thiosulfate (5.5 g) was added, and the mixture was stirred at room temperature for 5 minutes. After the insoluble matter was removed, the solvent was distilled off under reduced pressure. By column chromatography (silica gel, N- hexane / ethyl acetate = 8/2 ~ 1/1 (v / v)) were purified to obtain a colorless transparent liquid of EH ₂ TPPO (1.1g). It was identified as carried out by 1H-NMR spectrum. The NMR spectrum is shown in Figure 32.

[合成例5]EH₄ DPA之合成[Synthesis Example 5] Synthesis of EH ₄ DPA

【化29】【化29】

將9,10-雙(3,5-二羥基苯基)蔥(1.0g，2.54mmol)、1-溴-2-乙基己烷(3.9g，20.3mmol)及碳酸鉀(7.0g，50.7mmol)加入到DMF(30mL)中，以80℃攪拌5小時。將溶劑減壓餾去後，加入氯仿(300mL)進行水洗(150mL×3)。加入硫酸鎂乾燥後，以柱層析法(矽膠，n-己烷/乙酸乙酯=95/5(v/v))予以純化，並得到白色粉末狀之EH₄ DPA(2.03g)。鑑定為以¹ H-NMR光譜來進行。NMR光譜如圖33所示。9,10-bis(3,5-dihydroxyphenyl) onion (1.0 g, 2.54 mmol), 1-bromo-2-ethylhexane (3.9 g, 20.3 mmol) and potassium carbonate (7.0 g, 50.7) Methyl) was added to DMF (30 mL) and stirred at 80 ° C for 5 hours. After the solvent was distilled off under reduced pressure, chloroform (300 mL) was added and washed with water (150 mL×3). After drying over magnesium sulfate were added to column chromatography (silica gel, N- hexane / ethyl acetate = 95/5 (v / v )) were purified, and the white powder EH ₄ DPA (2.03g). It was identified as being carried out by ¹ H-NMR spectrum. The NMR spectrum is shown in Figure 33.

另外，將所得到的白色粉末照射UV燈之照片如圖36所示，將EH₄ DPA以相對於全質量為30質量%溶解於EHCz中，並進行UV照射之照片如圖37所示。目視上，EH₄ DPA為均勻溶解在EHCz中，不受到濃度消光影響，在EHCz中之PL發光已是明確的。Further, a photograph of the obtained white powder irradiated with a UV lamp is shown in Fig. 36, and a photograph of EH ₄ DPA dissolved in EHCz at 30 mass% with respect to the total mass and subjected to UV irradiation is shown in Fig. 37 . Visually, EH ₄ DPA is uniformly dissolved in EHCz and is not affected by concentration extinction. The PL luminescence in EHCz is already clear.

[合成例6]Ir(ehppy)₃ 之合成[Synthesis Example 6] Synthesis of Ir(ehppy) ₃

【化30】【化30】

將2-碘吡啶(3.1g，15.0mmol)、3-(4,4,5,5-四甲基-1,3,2-二噁硼烷-2-基)酚(5.0g，23.0mmol)、[1,1’-雙(二苯基膦基)二茂鐵]二氯化鈀(II)二氯(1.8g，2.00mmol)及碳酸鉀(9.3g，68.0mmol)懸濁於DMF(110mL)/水(60mL)混合溶劑中，以90℃攪拌3小時。之後，反應溶液經由減壓過濾將不溶物去除，將溶劑減壓餾去。於殘渣中加入氯仿(100mL)，進行水洗(100mL×3)。以硫酸鎂乾燥後，以柱層析法(矽膠，氯仿/甲醇=99/1(v/v))得到化合物6(2.1g，收率82%)。2-iodopyridine (3.1 g, 15.0 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenol (5.0 g, 23.0 mmol) ), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (1.8 g, 2.00 mmol) and potassium carbonate (9.3 g, 68.0 mmol) suspended in DMF The mixture was stirred at 90 ° C for 3 hours in a mixed solvent of (110 mL) / water (60 mL). Thereafter, the reaction solution was removed by filtration under reduced pressure, and the solvent was evaporated under reduced pressure. Chloroform (100 mL) was added to the residue, and the mixture was washed with water (100 mL × 3). After drying over magnesium sulfate, the compound 6 (2.1 g, yield 82%) was obtained by column chromatography (yield, chloroform/methanol=99/1 (v/v)).

【化31】【化31】

將上述所得到的化合物6(860mg，5.00mmol)、1-溴-2-乙基己烷(1.1g，6.00mmol)及碳酸鉀(3.5g，25.0mmol)加入到DMF(17mL)中，以90℃加熱攪拌3小時。反應溶液放冷後，將溶劑減壓餾去。以柱層析法(矽膠，氯仿)予以純化，得到無色透明液狀之化合物7(1.4g，收率71%)。Compound 6 (860 mg, 5.00 mmol), 1-bromo-2-ethylhexane (1.1 g, 6.00 mmol) and potassium carbonate (3.5 g, 25.0 mmol) obtained above were added to DMF (17 mL) The mixture was heated and stirred at 90 ° C for 3 hours. After the reaction solution was allowed to cool, the solvent was evaporated under reduced pressure. Purification by column chromatography (yield: chloroform) gave Compound 7 (yield: 71%).

【化32】【化32】

於氮氣流下，將上述所得到的化合物7(850mg，3.00mmol)及參(2,4-戊二酮)銥(III)(240mmg，0.50mmol)加入到乙二醇(5.0mL)中，以190℃加熱攪拌80小時。於反應溶液中加入氯仿(100mL)，以1N鹽酸進行2次洗淨後，進行2次水洗。使用硫酸鎂乾燥有機相後，將溶劑減壓餾去。以柱層析法(矽膠，氯仿/n-己烷=1：9～3：7(v/v))予以純化，並以甲醇固液洗淨後得到褐色固體狀之Ir(ehppy)₃ (40mg，收率7.8%)。鑑定為以¹ H-NMR光譜及MALDI-TOF-MS光譜來進行。NMR光譜如圖34、MALDI-TOF-MS光譜如圖35所示。The above obtained compound 7 (850 mg, 3.00 mmol) and ginseng (2, 4-pentanedione) ruthenium (III) (240 mmg, 0.50 mmol) were added to ethylene glycol (5.0 mL) under a nitrogen stream. The mixture was stirred under heating at 190 ° C for 80 hours. Chloroform (100 mL) was added to the reaction solution, and the mixture was washed twice with 1N hydrochloric acid, and then washed twice with water. After drying the organic phase with magnesium sulfate, the solvent was evaporated under reduced pressure. Purification by column chromatography (cluorochrome, chloroform/n-hexane = 1:9 to 3:7 (v/v)), and eluting with methanol solid to give Ir(ehppy) ₃ as a brown solid. 40 mg, yield 7.8%). It was identified as ¹ H-NMR spectrum and MALDI-TOF-MS spectrum. The NMR spectrum is shown in Fig. 34, and the MALDI-TOF-MS spectrum is shown in Fig. 35.

又，將Ir(ehppy)₃ 以相對於全質量為6.8質量%溶解於EHCz中，並進行UV照射之照片如圖38所示。目視上，Ir(ehppy)₃ 為均勻溶解於EHCz中，不受到濃度消光之影響，在EHCz中之PL發光已是明確的。Further, a photograph in which Ir(ehppy) ₃ was dissolved in EHCz at 6.8% by mass based on the total mass and subjected to UV irradiation is shown in Fig. 38 . Visually, Ir(ehppy) ₃ is uniformly dissolved in EHCz and is not affected by concentration extinction. The PL luminescence in EHCz is already clear.

[實施例1][Example 1]

使用在玻璃基板11上成膜有ITO基板12(膜厚100nm、薄片電阻25Ω/sq)作為陽極10。為形成交叉型電極，將ITO蝕刻成寬2mm。陽極10以中性洗劑(Cica clean LX-II、關東化學(股)製)進行10分鐘之超音波洗淨，更以離子交換水進行10分中洗淨後，以丙酮、異丙醇分別進行10分鐘之洗淨。之後，在沸騰的異丙醇中進行煮沸洗淨，最後進行UV臭氧處理15分鐘。As the anode 10, an ITO substrate 12 (film thickness: 100 nm, sheet resistance: 25 Ω/sq) was formed on the glass substrate 11. To form a cross-type electrode, ITO was etched to a width of 2 mm. The anode 10 was ultrasonically washed for 10 minutes with a neutral detergent (Cica clean LX-II, manufactured by Kanto Chemical Co., Ltd.), and further washed with ion-exchanged water for 10 minutes, and then acetone and isopropyl alcohol, respectively. Wash for 10 minutes. Thereafter, it was boiled and washed in boiling isopropanol, and finally subjected to UV ozone treatment for 15 minutes.

以旋轉塗佈法將PEDOT：PSS(Bayer公司製、PI4083)塗佈於其上。此時PEDOT：PSS的膜厚約為40nm。然後，於空氣中以120℃，進行30分鐘之加熱處理，將不要之水分除去成膜成電洞注入層30。更將Ag蒸鍍成條紋狀作為間隔器40。此時之膜厚為約80nm。PEDOT:PSS (manufactured by Bayer Co., Ltd., PI4083) was applied thereon by spin coating. At this time, the film thickness of PEDOT:PSS is about 40 nm. Then, heat treatment was performed at 120 ° C for 30 minutes in the air, and unnecessary water was removed to form a hole injection layer 30. Further, Ag is vapor-deposited into a stripe shape as the spacer 40. The film thickness at this time was about 80 nm.

作為陰極20，使用ITO/Cs₂ CO₃ 。首先，與陽極10使用同樣的玻璃基板13及ITO基板14之層合體，進行與陽極10同樣的蝕刻及洗淨處理。然後，以旋轉塗佈法由Cs₂ CO₃ 之甲醇溶液(1mg/1ml)成膜成Cs₂ CO₃ 層15。此時之膜厚為10～30nm左右。As the cathode 20, ITO/Cs ₂ CO _{3 was used} . First, the same laminate of the glass substrate 13 and the ITO substrate 14 is used for the anode 10, and the same etching and cleaning treatment as that of the anode 10 is performed. Then, a Cs ₂ CO ₃ layer 15 was formed by a spin coating method from a methanol solution of Cs ₂ CO ₃ (1 mg / 1 ml). The film thickness at this time is about 10 to 30 nm.

在如以上所成膜成的陽極10上，且在間隔器40之間，滴下含有紅螢烯1質量%之9-(2-乙基已基)咔唑(EHCz)液體之發光中心，形成液體發光層50。然後，以適當之壓力將陰極20壓著於其上，製作出有機EL元件1。元件1之膜厚為約200～400nm左右。On the anode 10 formed as described above, and between the spacers 40, an illuminating center containing a 9-% by mass of 9-% 2-ethylhexyl carbazole (EHCz) liquid of red fluorene is dropped. Liquid luminescent layer 50. Then, the cathode 20 is pressed thereon with an appropriate pressure to fabricate the organic EL element 1. The film thickness of the element 1 is about 200 to 400 nm.

對於以上所製作的有機EL元件1，進行電流-電壓-輝度特性、外部量子效率(EQE)-電流密度特性及EL發光光譜之測定。結果如圖4～6所示。The organic EL element 1 produced above was subjected to measurement of current-voltage-luminance characteristics, external quantum efficiency (EQE)-current density characteristics, and EL emission spectrum. The results are shown in Figures 4-6.

如圖4之元件之電流-電壓-輝度特性圖表所示，從約2V以上開始即可観測到注入電流，到50V為止電流為以電壓之一次方比例上昇。EL發光為從15V以上開始即可観測到，在50V之外加電壓，觀測到約0.35cd/m² 之發光輝度。此時之電流密度約為0.26mA/cm² 。As shown in the graph of the current-voltage-luminance characteristic of the element of Fig. 4, the injection current can be detected from about 2 V or more, and the current rises to a ratio of one voltage to 50 V. The EL luminescence was measured from 15 V or more, and a voltage was applied in addition to 50 V, and an illuminance of about 0.35 cd/m ^{2 was} observed. The current density at this time was about 0.26 mA/cm ² .

又，由圖5之外部量子效率(EQE)-電流密度特性圖表，可估算EL外部量子效率約為0.03%。Further, from the external quantum efficiency (EQE)-current density characteristic chart of Fig. 5, the external quantum efficiency of EL can be estimated to be about 0.03%.

更，如圖6之EL發光光譜之觀測結果所示般，可了解在3種的外加電壓下均可觀測到由基於紅螢烯之EL發光。Further, as shown by the observation result of the EL luminescence spectrum of Fig. 6, it can be understood that EL luminescence based on red fluorene is observed under three kinds of applied voltages.

[實施例2][Embodiment 2]

在主化合物(host compound)EHCz99.0質量份中加入客化合物(guest compound)紅螢烯1.0質量份，使紅螢烯完全溶解於EHCz中製成液體發光體。1.0 part by mass of a guest compound red fluorene was added to 99.0 parts by mass of a host compound EHCz, and red fluorene was completely dissolved in EHCz to prepare a liquid illuminant.

EL元件之製作如以下般進行。The EL element was produced as follows.

準備已施予以界面活性劑、純水、異丙醇之順序之超音波洗淨，並以UV/臭氧處理(Filgen公司製、UV253S)12分鐘後之附有ITO玻璃基板2片。Ultrasonic cleaning in which the surfactant, pure water, and isopropyl alcohol were applied was prepared, and two sheets of ITO glass substrate were attached by UV/ozone treatment (UV253S, manufactured by Filgen) for 12 minutes.

如圖2所示，在一側之附有ITO12之玻璃基板11上，以3000rpm回轉數、30秒之旋轉塗佈法將PEDOT：PSS(Bayer公司製、PI4083)塗佈，並以200℃，10分鐘之大氣中之加熱，將不溶性的電洞注入層30成膜於陽極側基板10之ITO12上。As shown in Fig. 2, PEDOT:PSS (manufactured by Bayer Co., Ltd., PI4083) was applied to a glass substrate 11 having ITO 12 on one side thereof at a number of revolutions of 3000 rpm and 30 seconds, and at 200 ° C, The insoluble hole injection layer 30 was formed on the ITO 12 of the anode side substrate 10 by heating in the atmosphere for 10 minutes.

接下來，將另一側之附有ITO14之玻璃基板13置入於手套箱(glove box)中，並於ITO14上以旋轉塗佈法使用Cs₂ CO₃ 1質量%之甲醇溶液將Cs₂ CO₃ 塗佈上去，以150℃加熱1小時，得到電子注入層15之Cs₂ CO₃ 成膜於ITO14上之陰極側基板20。Next, with the other side of the glass substrate 13 placed in the glove box ITO14 (glove box) in and on the coating method used ITO14 rotation Cs ₂ CO ₃ 1% by mass methanol solution of Cs ₂ CO _{3 was} applied and heated at 150 ° C for 1 hour to obtain Cs ₂ CO _{3 of the} electron injecting layer 15 to be formed on the cathode side substrate 20 on the ITO 14.

在手套箱中，將已事先調製好的液體發光體50少量滴下於陰極側基板20上，並以電洞注入層30之PEDOT：PSS所成膜的ITO陽極側基板10挾住，將所得到層合體之外側以夾子(clip)(圖示省略)挾住固定，製造出由玻璃基板/ITO(陽極)/PEDOT：PSS40nm/液體發光體層/Cs₂ CO₃ /ITO(陰極)/玻璃基板所成的EL元件2。元件面積為2mm×2mm。In the glove box, the liquid illuminant 50 which has been prepared in advance is dropped on the cathode side substrate 20 in a small amount, and is immersed in the ITO anode side substrate 10 formed by the PEDOT:PSS of the hole injection layer 30, and the obtained The outer side of the laminate was clamped and fixed by a clip (not shown) to produce a glass substrate/ITO (anode)/PEDOT:PSS 40 nm/liquid illuminant layer/Cs ₂ CO ₃ /ITO (cathode)/glass substrate. The EL element 2 is formed. The component area is 2 mm x 2 mm.

測定所製作EL元件之電流密度-電壓-輝度及發光光譜。結果如圖7～9所示。此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為560nm。The current density-voltage-luminance and luminescence spectrum of the produced EL element were measured. The results are shown in Figures 7-9. The film thickness of the liquid light-emitting layer of this device was 560 nm as a result of measurement of the dielectric constant.

如圖7所示般，在69.9V之外加電壓時，可得到11.0mA/cm² 之電流密度及2.6cd/m² 之最大輝度；如圖8所示般，在20V之外加電壓時，可得到0.005%之最大EL外部量子效率。又，如圖9所示的可得到由波峰為557nm所構成之橙色的電致發光。As shown in FIG. 7, when a voltage is applied outside 69.9 V, a current density of 11.0 mA/cm ² and a maximum luminance of 2.6 cd/m ² can be obtained; as shown in FIG. 8, when a voltage is applied outside 20 V, A maximum EL external quantum efficiency of 0.005% was obtained. Further, as shown in Fig. 9, an orange electroluminescence composed of a peak of 557 nm was obtained.

[實施例3][Example 3]

除了以下述式所示的TEGCz作為液體發光體之主化合物外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖10及圖11所示。The same EL element was produced and evaluated in the same manner as in Example 2 except that TEGCz represented by the following formula was used as the main compound of the liquid illuminant. The evaluation results are shown in FIGS. 10 and 11.

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為560nm。The film thickness of the liquid light-emitting layer of this device was 560 nm as a result of measurement of the dielectric constant.

如圖10所示般，在49.9V之外加電壓時，可得到1.0mA/cm² 之電流密度與21cd/m² 之最大輝度；如圖11所示般，在10V之外加電壓時，可得到0.72%之EL外部量子效率，與圖9同樣得到具有在555nm之發光波峰之橙色發光。As shown in FIG. 10, when a voltage is applied outside of 49.9 V, a current density of 1.0 mA/cm ² and a maximum luminance of 21 cd/m ² can be obtained; as shown in FIG. 11, when a voltage is applied in addition to 10 V, a voltage is obtained. The EL external quantum efficiency of 0.72% gave an orange luminescence having an emission peak at 555 nm as in Fig. 9 .

另外，TEGCz為參考Synthetic Metals，89(3)，171(1997)所記載之方法予以合成。In addition, TEGCz was synthesized by the method described in Synthetic Metals, 89 (3), 171 (1997).

【化33】【化33】

[實施例4][Example 4]

除了以下述式所示之EHTPA作為液體發光體之主化合物外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖12及圖13所示。The same EL element was produced and evaluated in the same manner as in Example 2 except that EHTPA represented by the following formula was used as the main compound of the liquid illuminant. The evaluation results are shown in FIGS. 12 and 13.

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為1090nm。The film thickness of the liquid light-emitting layer of this device was 1090 nm as a result of the measurement of the dielectric constant.

如圖12所示般，在57.6V之外加電壓時，可得到0.052mA/cm² 之電流密度；如圖13所示般，得到0.0041cd/m² 之最大輝度、0.0016%之EL外部量子效率，與圖9同樣得到具有在555nm之發光波峰之橙色發光。As shown in FIG. 12, when a voltage is applied at 57.6 V, a current density of 0.052 mA/cm ² can be obtained; as shown in FIG. 13, a maximum luminance of 0.0041 cd/m ² and an EL external quantum efficiency of 0.0016% are obtained. In the same manner as in Fig. 9, orange light having a luminescence peak at 555 nm was obtained.

【化34】【化34】

[實施例5][Example 5]

除了以下述式所示之EHOXD作為液體發光體之主化合物外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖14及圖15所示。The same EL element was produced and evaluated in the same manner as in Example 2 except that EHOXD represented by the following formula was used as the main compound of the liquid illuminant. The evaluation results are shown in Figs. 14 and 15 .

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為700nm。The film thickness of the liquid light-emitting layer of this device was 700 nm as a result of the measurement of the dielectric constant.

如圖14所示般，在36.8V之外加電壓時，可得到0.020mA/cm² 之電流密度與0.0018cd/m² 之最大輝度；如圖15所示般，30.7V之外加電壓時，可得到0.0033%之EL外部量子效率，與圖9同樣得到具有在556nm之發光波峰之橙色發光。As shown in FIG. 14, when a voltage is applied outside of 36.8 V, a current density of 0.020 mA/cm ² and a maximum luminance of 0.0018 cd/m ² can be obtained; as shown in FIG. 15, when a voltage is applied at 30.7 V, An EL external quantum efficiency of 0.0033% was obtained, and an orange luminescence having a luminescence peak at 556 nm was obtained in the same manner as in Fig. 9 .

【化35】【化35】

[實施例6][Embodiment 6]

除了以下述式所示的EH₂ TPPO作為液體發光體之主化合物外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖16及圖17所示。The same EL element was produced and evaluated in the same manner as in Example 2 except that EH ₂ TPPO represented by the following formula was used as the main compound of the liquid illuminant. The evaluation results are shown in Figs. 16 and 17 .

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為380nm。The film thickness of the liquid light-emitting layer of this device was 380 nm as a result of the measurement of the dielectric constant.

如圖16所示般，在44.0V之外加電壓時，可得到0.068mA/cm² 之電流密度與0.30cd/m² 之最大輝度；如圖17所示般，在40.5V之外加電壓時，可得到0.10%之EL外部量子效率，與圖9同樣得到具有在555nm之發光波峰之橙色發光。As shown in FIG. 16, when a voltage is applied in addition to 44.0 V, a current density of 0.068 mA/cm ² and a maximum luminance of 0.30 cd/m ² can be obtained; as shown in FIG. 17, when a voltage is applied outside of 40.5 V, An EL external quantum efficiency of 0.10% was obtained, and an orange luminescence having an emission peak at 555 nm was obtained in the same manner as in Fig. 9 .

【化36】【化36】

[實施例7][Embodiment 7]

除了以EHCz70.0質量份作為液體發光體之主化合物，以及以下述式所示m-4EHPA30.0質量份作為客化合物以外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖18～20所示。The same EL element was produced and evaluated in the same manner as in Example 2, except that 70.0 parts by mass of EHCz was used as the main compound of the liquid illuminant, and 30.0 parts by mass of m-4EHPA represented by the following formula was used as the guest compound. The evaluation results are shown in Figures 18-20.

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為910nm。The film thickness of the liquid light-emitting layer of this device was 910 nm as a result of the measurement of the dielectric constant.

如圖18所示般，在100V之外加電壓時，可得到0.16mA/cm² 之電流密度與0.013cd/m² 之最大輝度；如圖19所示般，在88.3V之外加電壓時，可得到0.014%之最大EL外部量子效率。又，如圖20所示的可得到具有波峰為424nm之純藍色的電致發光。As shown in FIG. 18, when a voltage is applied outside 100V, a current density of 0.16 mA/cm ² and a maximum luminance of 0.013 cd/m ² can be obtained; as shown in FIG. 19, when a voltage is applied outside of 88.3 V, A maximum EL external quantum efficiency of 0.014% was obtained. Further, as shown in Fig. 20, electroluminescence having a pure blue color having a peak of 424 nm was obtained.

【化37】【化37】

[實施例8]由非主客系統液體發光體之電致發光[Example 8] Electroluminescence of a liquid illuminant by a non-host system

除了以下述式所示EHPy作為液體發光體外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖21～23所示。The same EL element was produced and evaluated in the same manner as in Example 2 except that EHPy was used as a liquid light-emitting body as shown in the following formula. The evaluation results are shown in Figures 21-23.

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為1900nm。The film thickness of the liquid light-emitting layer of this device was 1900 nm as a result of the measurement of the dielectric constant.

如圖21，22所示般，在100V之外加電壓時，可得到0.98mA/cm² 之電流密度、0.84cd/m² 之最大輝度、0.023%之最大EL外部量子效率。又，如圖23所示般，得到在486nm具有波峰之純藍色之電致發光。As shown in Figs. 21 and 22, when a voltage was applied in addition to 100 V, a current density of 0.98 mA/cm ² , a maximum luminance of 0.84 cd/m ² , and a maximum EL external quantum efficiency of 0.023% were obtained. Further, as shown in Fig. 23, electroluminescence of pure blue having a peak at 486 nm was obtained.

【化38】【化38】

[實施例9]磷光發光性之主化合物之情形[Example 9] Case of main compound of phosphorescence

除了以EHCz92.8質量份作為液體發光體之主化合物，及以下述式所示Ir(ehppy)₃ 7.2質量份作為客化合物以外，與實施例2製作同樣的EL元件，並進行評價。評價結果如圖24～26所示。The same EL element was produced and evaluated in the same manner as in Example 2, except that the main compound of the liquid illuminant was 92.8 parts by mass of EHCz and the 7.2 parts by mass of Ir(ehppy) ₃ represented by the following formula was used as the guest compound. The evaluation results are shown in Figures 24 to 26.

此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為2200nm。The film thickness of the liquid light-emitting layer of this device was 2200 nm as a result of the measurement of the dielectric constant.

如圖24，25所示般，在100V之外加電壓時，可得到0.35mA/cm² 之電流密度、0.0024cd/m² 之最大輝度、0.00015%之最大EL外部量子效率。又，如圖26所示般，得到在559nm具有波峰之純藍色之電致發光。As shown in Figs. 24 and 25, when a voltage is applied in addition to 100 V, a current density of 0.35 mA/cm ² , a maximum luminance of 0.0024 cd/m ² , and a maximum EL external quantum efficiency of 0.00015% can be obtained. Further, as shown in Fig. 26, electroluminescence having a pure blue color having a peak at 559 nm was obtained.

【化39】【化39】

[實施例10]發光層之交換[Example 10] Exchange of light-emitting layers

EL元件的製作如以下般進行。準備已施予以界面活性劑、純水、異丙醇之順序之超音波洗淨，並以UV/臭氧處理(Filgen公司製、UV253S)12分鐘後之附有ITO玻璃基板2片。The EL element was fabricated as follows. Ultrasonic cleaning in which the surfactant, pure water, and isopropyl alcohol were applied was prepared, and two sheets of ITO glass substrate were attached by UV/ozone treatment (UV253S, manufactured by Filgen) for 12 minutes.

如圖3所示般，將少量作為液體發光體50之EHPy滴下於單側附有ITO12之玻璃基板11上，與另一側之附有ITO14之玻璃基板13挾持，將所得到的層合體之外側以夾子(圖示省略)挾住固定，製作由ITO(陽極)/EHPy/ITO(陰極)所構成的EL元件3。此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為500nm。元件面積為2mm×2mm。As shown in Fig. 3, a small amount of EHPy as the liquid illuminant 50 was dropped on the ITO12-attached glass substrate 11 on one side, and held on the other side with the ITO14-attached glass substrate 13, and the obtained laminate was The outer side was clamped and fixed by a clip (not shown), and an EL element 3 made of ITO (anode) / EHPy / ITO (cathode) was produced. The film thickness of the liquid light-emitting layer of this device was 500 nm as a result of the measurement of the dielectric constant. The component area is 2 mm x 2 mm.

將所製作的EL元件之電流密度-電壓-輝度或發光光譜，以與實施例2同樣之手法測定。結果如圖27，28之圓點曲線所示。如圖27，28之圓點曲線所表示的，在95.4V之外加電壓時，可得到0.25mA/cm² 之電流密度、3.8cd/m² 之最大輝度、0.40%之最大EL外部量子效率。又，可得到與圖23同樣地在486nm具有波峰之藍綠色之電致發光。The current density-voltage-luminance or luminescence spectrum of the produced EL element was measured in the same manner as in Example 2. The results are shown in the dot curves of Figs. As shown by the dot curve of Figs. 27 and 28, when a voltage is applied in addition to 95.4 V, a current density of 0.25 mA/cm ² , a maximum luminance of 3.8 cd/m ² , and a maximum EL external quantum efficiency of 0.40% can be obtained. Further, in the same manner as in Fig. 23, electroluminescence of cyan with a crest at 486 nm was obtained.

接著將EL元件之夾子取下，以丙酮將液體發光體之EHPy所附著的ITO基板清洗，除去EHPy，並使丙酮自然乾燥。於此洗淨後的ITO基板上少量滴下EHPy，與另一側已洗淨之ITO基板挾持，並以夾子固定，再次製作由ITO(陽極)/EHPy/ITO(陰極)所構成的EL元件。此裝置之液體發光層之膜厚，以介電率測定之結果所算出之值為690nm。與上述同樣地，評價電流密度、輝度、電壓、EL之外部量子效率、發光光譜。結果如圖27，28之方點曲線所示。如圖27，28之方點曲線所示般，在100V之外加電壓時，可得到0.066mA/cm² 之電流密度、0.58cd/m² 之最大輝度、0.23%之最大EL外部量子效率。又，可得到與圖23同樣地在486nm具有波峰之藍綠色之電致發光。Next, the clip of the EL element was removed, and the ITO substrate adhered to the EHPy of the liquid illuminator was washed with acetone to remove EHPy, and the acetone was naturally dried. On the ITO substrate after the cleaning, a small amount of EHPy was dropped, and the ITO substrate was washed with the other side, and fixed by a clip, and an EL element composed of ITO (anode) / EHPy / ITO (cathode) was again produced. The film thickness of the liquid light-emitting layer of this device was 690 nm as a result of measurement of dielectric constant. The current density, luminance, voltage, external quantum efficiency of EL, and luminescence spectrum were evaluated in the same manner as above. The results are shown in the square curve of Figures 27 and 28. As shown by the square point curve of Figs. 27 and 28, when a voltage is applied in addition to 100 V, a current density of 0.066 mA/cm ² , a maximum luminance of 0.58 cd/m ² , and a maximum EL external quantum efficiency of 0.23% can be obtained. Further, in the same manner as in Fig. 23, electroluminescence of cyan with a crest at 486 nm was obtained.

1．．．有機EL元件(電致發光元件)1. . . Organic EL element (electroluminescence element)

10．．．陽極10. . . anode

20．．．陰極20. . . cathode

30．．．電洞注入層30. . . Hole injection layer

40．．．間隔器40. . . Spacer

50．．．液體發光層50. . . Liquid luminescent layer

[圖1]表示以實施例1製作的有機EL元件之概略剖面圖。Fig. 1 is a schematic cross-sectional view showing an organic EL device produced in Example 1.

[圖2]表示以實施例2製作的有機EL元件之概略剖面圖。Fig. 2 is a schematic cross-sectional view showing an organic EL device produced in Example 2.

[圖3]表示以實施例10製作的有機EL元件之概略剖面圖。Fig. 3 is a schematic cross-sectional view showing an organic EL device produced in Example 10.

[圖4]表示以實施例1所得到有機EL元件之電流-電壓-輝度特性之圖。Fig. 4 is a graph showing the current-voltage-luminance characteristics of the organic EL device obtained in Example 1.

[圖5]表示以實施例1所得到有機EL元件之外部量子效率(EQE)-電流密度特性之圖。Fig. 5 is a graph showing the external quantum efficiency (EQE)-current density characteristics of the organic EL device obtained in Example 1.

[圖6]以實施例1所得到有機EL元件之電致發光光譜圖。Fig. 6 is a chart showing the electroluminescence spectrum of the organic EL device obtained in Example 1.

[圖7]表示以實施例2所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 7 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 2.

[圖8]表示以實施例2所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 8 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 2.

[圖9]以實施例2所得到有機EL元件之電致發光光譜圖。Fig. 9 is a chart showing the electroluminescence spectrum of the organic EL device obtained in Example 2.

[圖10]表示以實施例3所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 10 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 3.

[圖11]表示以實施例3所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 11 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 3.

[圖12]表示以實施例4所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 12 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 4.

[圖13]表示以實施例4所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 13 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 4.

[圖14]表示以實施例5所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 14 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 5.

[圖15]表示以實施例5所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 15 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 5.

[圖16]表示以實施例6所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 16 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 6.

[圖17]表示以實施例6所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 17 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 6.

[圖18]表示以實施例7所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 18 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 7.

[圖19]表示以實施例7所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 19 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 7.

[圖20]以實施例7所得到有機EL元件之電致發光光譜圖。Fig. 20 is a chart showing the electroluminescence spectrum of the organic EL device obtained in Example 7.

[圖21]表示以實施例8所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 21 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 8.

[圖22]表示以實施例8所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 22 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 8.

[圖23]以實施例8所得到有機EL元件之電致發光光譜圖。Fig. 23 is a chart showing the electroluminescence spectrum of the organic EL device obtained in Example 8.

[圖24]表示以實施例9所得到有機EL元件之電流密度-電壓-輝度特性之圖。Fig. 24 is a graph showing current density-voltage-luminance characteristics of the organic EL device obtained in Example 9.

[圖25]表示以實施例9所得到有機EL元件之EL外部量子收率-電壓特性之圖。Fig. 25 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 9.

[圖26]以實施例9所得到有機EL元件之電致發光光譜圖。Fig. 26 is a chart showing the electroluminescence spectrum of the organic EL device obtained in Example 9.

[圖27]表示以實施例10所得到有機EL元件之電流密度-電壓-輝度特性之圖，圓點曲線為表示第1次元件製作時之資料，方點曲線為表示一度將裝置剝離，再度製作裝置時之資料。Fig. 27 is a graph showing the current density-voltage-luminance characteristic of the organic EL device obtained in Example 10. The dot curve indicates the data at the time of the first element fabrication, and the square curve indicates that the device was once peeled off again. Information when making the device.

[圖28]表示以實施例10所得到有機EL元件之EL外部量子收率-電壓特性之圖，圓點曲線為表示第1次元件製作時之資料，方點曲線為表示一度將裝置剝離，再度製作裝置時之資料。28 is a graph showing the EL external quantum yield-voltage characteristics of the organic EL device obtained in Example 10. The dot curve indicates the data at the time of the first element fabrication, and the square dot curve indicates that the device was once peeled off. Information on the time when the device was re-made.

[圖29]合成例1所得到的EHPy之¹ H-NMR光譜圖。Fig. 29 is a ¹ H-NMR spectrum chart of EHPy obtained in Synthesis Example 1.

[圖30]合成例2所得到的EHTPA之¹ H-NMR光譜圖。Fig. 30 is a ¹ H-NMR spectrum chart of EHTPA obtained in Synthesis Example 2.

[圖31]合成例3所得到的EHOXD之¹ H-NMR光譜圖。Fig. 31 is a ¹ H-NMR spectrum chart of EHOXD obtained in Synthesis Example 3.

[圖32]合成例4所得到的EH₂ TPPO之¹ H-NMR光譜圖。Fig. 32 is a ¹ H-NMR spectrum chart of EH ₂ TPPO obtained in Synthesis Example 4.

[圖33]合成例5所得到的EH₄ DPA之¹ H-NMR光譜圖。Fig. 33 is a ¹ H-NMR spectrum chart of EH ₄ DPA obtained in Synthesis Example 5.

[圖34]合成例6所得到的Ir(ehppy)₃ 之¹ H-NMR光譜圖。Fig. 34 is a ¹ H-NMR spectrum chart of Ir(ehppy) ₃ obtained in Synthesis Example 6.

[圖35]合成例6所得到Ir(ehppy)₃ 之MALDI-TOF-MS光譜圖。Fig. 35 is a MALDI-TOF-MS spectrum chart of Ir(ehppy) ₃ obtained in Synthesis Example 6.

[圖36]表示以UV燈照射由合成例5所得到EH₄ DPA之白色粉之照片圖。Fig. 36 is a photographic view showing the white powder of EH ₄ DPA obtained in Synthesis Example 5 irradiated with a UV lamp.

[圖37]表示將合成例5所得到的EH₄ DPA以相對於全質量為30質量%溶解於EHCz中，並進行UV照射之照片圖。FIG. 37 is a photographic diagram showing that EH ₄ DPA obtained in Synthesis Example 5 is dissolved in EHCz at 30% by mass based on the total mass, and UV irradiation is performed.

[圖38]表示將合成例6所得到的Ir(ehppy)₃ 以相對於全質量為6.8質量%溶解於EHCz中，並進行UV照射之照片圖。FIG. 38 is a photographic diagram showing that Ir(ehppy) ₃ obtained in Synthesis Example 6 is dissolved in EHCz at 6.8% by mass based on the total mass, and UV irradiation is performed.

11．．．玻璃基板11. . . glass substrate

12．．．ITO基板12. . . ITO substrate

13．．．玻璃基板13. . . glass substrate

14．．．ITO基板14. . . ITO substrate

15．．．電子注入層15. . . Electron injection layer

10．．．陽極10. . . anode

20．．．陰極20. . . cathode

30．．．電洞注入層30. . . Hole injection layer

40．．．間隔器40. . . Spacer

50．．．液體發光層50. . . Liquid luminescent layer

Claims

An organic electroluminescence device characterized by comprising an anode and a cathode, and a light-emitting layer interposed between the electrodes at a normal temperature; wherein the light-emitting layer is provided with a carrier having a liquid at a normal temperature and a light-emitting energy. The material or the light-emitting layer is a carrier transport material and a light-emitting material which are liquid at normal temperature; the material having the carrier transport energy and the light-emitting energy of the liquid at normal temperature is selected from the group consisting of carbazole, triarylamine, and carbon condensation ring-based pigment. The carrier transporting material which is a liquid at normal temperature is a compound represented by the formula (1), and in the formula XY (1), X is a charge transporting portion, and is represented by carbazole. Diazole, 2,5-diphenyl-1,3,4- An oxadiazole, a triarylamine, a phenylenediamine, an onion, a triphenylphosphine oxide, or a benzidine; and Y is a substituent which is bonded to at least one of the charge transporting units X, and is represented by an ether bond or a thioether bond. An alkyl group having 1 to 30 carbon atoms of an ester bond, a carbonate bond or a guanamine bond.

The organic electroluminescence device according to claim 1, wherein the luminescent material is a carbon condensed ring-based dye, an anthracene derivative, a pigment, a cyanine dye, a coumarin dye, a quinophthalone dye, a squarylium dye, a styrene dye, a pyrazole derivative, a phenoxazon dye, A carbazole, a triarylamine, a ruthenium complex, or a metal complex dye composed of a central metal and a ligand composed of Al, Zn, Be or a rare earth metal.

The organic electroluminescence device according to claim 2, wherein the luminescent material is a compound represented by the formula (2), and in the formula ZW (2), Z is a dye moiety and is represented by a carbon condensed ring-based pigment. , hydrazine derivatives, a pigment, a cyanine dye, a coumarin dye, a quinophthalone dye, a squarylium dye, a styrene dye, a pyrazole derivative, a phenoxazon dye, a carbazole, a triarylamine, a ruthenium complex, or a metal complex composed of a central metal and a ligand composed of Al, Zn, Be or a rare earth metal; and W is at least 1 bonded to the dye portion Y. The substituents are represented by an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether bond, an ester bond, a carbonate bond or a guanamine bond.

The organic electroluminescence device according to claim 1, wherein the charge transporting portion X is carbazole.

The organic electroluminescence device according to claim 1, wherein the substituent Y is an alkyl group having 1 to 30 carbon atoms.

The organic electroluminescence device according to claim 1, wherein the charge transporting portion X is carbazole, and the substituent Y is an alkyl group having 1 to 30 carbon atoms.

The organic electroluminescence device according to claim 1, wherein the carrier transport material is represented by the formula (3). (wherein Y has the same meaning as described above).

The organic electroluminescence device according to claim 7, wherein the carrier transport material is represented by the formula (4).

The organic electroluminescence device of claim 7, wherein the carrier transport material is represented by the formula (5).

The organic electroluminescence device according to claim 2, wherein the luminescent material is rubrene.