KR20110113297A - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Novel compounds for organic electronic material and organic electroluminescent device using the same Download PDF

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KR20110113297A
KR20110113297A KR1020100032608A KR20100032608A KR20110113297A KR 20110113297 A KR20110113297 A KR 20110113297A KR 1020100032608 A KR1020100032608 A KR 1020100032608A KR 20100032608 A KR20100032608 A KR 20100032608A KR 20110113297 A KR20110113297 A KR 20110113297A
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organic
compound
heteroaryl
aryl
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이수용
조영준
권혁주
김봉옥
김성민
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다우어드밴스드디스플레이머티리얼 유한회사
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Priority to KR1020100032608A priority Critical patent/KR20110113297A/en
Priority to PCT/KR2011/001920 priority patent/WO2011126225A1/en
Priority to TW100111966A priority patent/TW201204729A/en
Publication of KR20110113297A publication Critical patent/KR20110113297A/en

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Abstract

본 발명은 신규한 유기 전자재료용 화합물, 이를 포함하고 있는 유기 전계 발광 소자에 관한 것으로, 상세하게는 본 발명에 따른 유기 전자재료용 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다.
[화학식 1]

Figure pat00047

상기 화학식 1에서, X 및 Ar1 내지 Ar4는 각각 발명의 상세한 설명에서 정의한 바와 같다.
본 발명에 따른 유기 전자재료용 화합물은 전자전달 효율이 높아 소자 제작시 결정화를 방지할 뿐만 아니라 층 형성이 양호하여 소자의 전류특성을 개선시킴으로서 소자의 구동전압을 저하시키고 동시에 전력효율이 향상된 OLED 소자를 제조할 수 있는 장점이 있다.The present invention relates to a novel compound for an organic electronic material, and an organic electroluminescent device including the same. Specifically, the compound for an organic electronic material according to the present invention is represented by the following Chemical Formula 1.
[Formula 1]
Figure pat00047

In Formula 1, X and Ar 1 to Ar 4 are as defined in the detailed description of the invention, respectively.
The compound for an organic electronic material according to the present invention has a high electron transfer efficiency, which not only prevents crystallization during device fabrication but also has a good layer formation to improve the current characteristics of the device, thereby lowering the driving voltage of the device and at the same time improving the power efficiency. There is an advantage to manufacture.

Description

신규한 유기 전자재료용 화합물 및 이를 포함하는 유기 전계 발광 소자{Novel compounds for organic electronic material and organic electroluminescent device using the same}Novel compounds for organic electronic material and organic electroluminescent device using the same

본 발명은 신규한 유기 전자재료용 화합물, 이를 포함하는 유기 전계 발광 소자에 관한 것으로서, 더욱 상세하게는 본 발명에 따른 유기 전자재료용 화합물은 유기 전계 발광 소자의 전자전달재료로 사용될 수 있다.The present invention relates to a novel compound for an organic electronic material, an organic electroluminescent device comprising the same, and more particularly, the compound for an organic electronic material according to the present invention can be used as an electron transfer material of the organic electroluminescent device.

표시 소자 중, 전기 발광 소자(electroluminescence device: EL device)는 자체 발광형 표시 소자로서 시야각이 넓고 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있으며, 1987년 이스트만 코닥(Eastman Kodak)사에서는 발광층 형성용 재료로서 저분자인 방향족 디아민과 알루미늄 착물을 이용하고 있는 유기 EL 소자를 처음으로 개발하였다[Appl. Phys. Lett. 51, 913, 1987].Among the display elements, an electroluminescence device (EL device) is a self-luminous display element that has a wide viewing angle, excellent contrast, and high response speed.Eastman Kodak Co., Ltd. in 1987 An organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer formation material was first developed [Appl. Phys. Lett. 51, 913, 1987].

유기 EL 소자는 전자 주입 전극(음극) 과 정공 주입 전극(양극) 사이에 형성된 유기막에 전하를 주입하면 전자와 정공이 쌍을 이룬 후 소멸하면서 빛을 내는 소자이다. 플라스틱 같은 휠 수 있는(flexible) 투명 기판 위에도 소자를 형성할 수 있을 뿐 아니라, 플라즈마 디스플레이 패널(Plasma Display Panel)이나 무기 EL 디스플레이에 비해 낮은 전압에서 (10V이하) 구동이 가능하고, 또한 전력 소모가 비교적 적으며, 색감이 뛰어나다는 장점이 있다. An organic EL device is a device that emits light when an electron is injected into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) and then disappears after pairing electrons and holes. The device can be formed on a flexible transparent substrate such as plastic, and can be driven at a lower voltage (less than 10V) compared to a plasma display panel or an inorganic EL display, and also consumes power. It is relatively small and has the advantage of excellent color.

유기 EL 소자에서 발광 효율, 수명 등의 성능을 결정하는 가장 중요한 요인은 발광 재료로서, 이러한 발광 재료에 요구되는 몇 가지 특성으로는 고체상태에서 형광 양자 수율이 커야하고, 전자와 정공의 이동도가 높아야 하며, 진공 증착시 쉽게 분해되지 않아야 하고, 균일한 박막을 형성, 안정해야한다. In organic EL devices, the most important factor that determines the performance of light emission efficiency, lifetime, etc. is a light emitting material. Some characteristics required for such a light emitting material include high quantum fluorescence yield in solid state, and mobility of electrons and holes. It should be high, not easily decomposed during vacuum deposition, and form a stable thin film.

유기 발광 재료는 크게 고분자 재료와 저분자 재료로 나눌 수 있는데, 저분자 계열의 재료는 분자 구조 면에서 금속 착화합물과 금속을 포함하지 않는 순수 유기 발광 재료가 있다. 이러한 발광 재료로는 트리스(8-퀴놀리놀라토)알루미늄 착제 등의 킬레이트 착제, 쿠마린 유도체, 테트라페닐부타디엔 유도체, 비스스타이릴아릴렌 유도체, 옥사다이아졸 유도체 등의 발광 재료가 알려져 있고, 이들로부터는 청색에서 적색까지의 가시 영역 발광을 얻을 수 있다고 보고되었다.Organic light emitting materials can be classified into high molecular materials and low molecular materials. Low molecular materials include pure organic light emitting materials that do not contain metal complexes and metals in terms of molecular structure. As such light emitting materials, light emitting materials such as chelate complexes such as tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives and oxadiazole derivatives are known. Has been reported to obtain visible region luminescence from blue to red.

풀칼라 OLED 디스플레이의 구현을 위해서는 RGB 3가지의 발광재료를 사용하게 되는데 유기 EL 전체의 특성을 향상시키는데 고효율 장수명의 RGB 발광재료의 개발이 중요한 과제라고 할 수 있다. 발광재료는 기능적인 측면에서 호스트 재료와 도판트 재료로 구분될 수 있는데 일반적으로 EL 특성이 가장 우수한 소자 구조로는 호스트에 도판트를 도핑하여 발광층을 만드는 것으로 알려져 있다. 최근에 고효율, 장수명 유기 EL 소자의 개발이 시급한 과제로 대두되고 있으며, 특히 중대형 OLED 패널에서 요구하고 있는 EL 특성 수준을 고려해 볼 때 기존의 발광재료에 비해 매우 우수한 재료의 개발이 시급한 실정이다.In order to realize a full color OLED display, three kinds of RGB light emitting materials are used, and development of high efficiency long life RGB light emitting materials is an important task to improve the characteristics of the entire organic EL. The light emitting material can be classified into a host material and a dopant material in terms of its function. In general, a device structure having excellent EL characteristics is known to make a light emitting layer by doping a host with a dopant. Recently, the development of high efficiency and long life organic EL devices has emerged as an urgent task, and considering the level of EL characteristics required in medium and large OLED panels, it is urgent to develop materials that are much superior to existing light emitting materials.

또한, 기존 전자 전달 재료의 대표적인 예로는, 1987년 Kodak이 발표한 다층박막 OLED 이전부터 사용되어진 tris(8-hydroxyquinoline)aluminum(III) (Alq)과 같은 알루미늄 착체와 1990년대 중반 일본에서 발표되었던 bis(10-hydroxybenzo- [h]quinolinato)beryllium (Bebq)과 같은 베릴륨 착체(Bebq)[T. Sato et.al. J. Mater. Chem. 10 (2000) 1151] 등이 있다. 그러나, 이들 재료의 경우, 그 한계가 2002년 이후로 OLED가 상용화되면서 대두되기 시작하였고, 이후로 고성능의 전자 전달 재료가 다수 연구 발표되어, 상용화에 근접하게 되었다.In addition, representative examples of conventional electron transfer materials include aluminum complexes such as tris (8-hydroxyquinoline) aluminum (III) (Alq), which were used before the multilayer thin film OLED announced by Kodak in 1987, and bis, which was released in Japan in the mid-1990s. Beryllium complexes such as (10-hydroxybenzo- [h] quinolinato) beryllium (Bebq) [T. Sato et.al. J. Mater. Chem. 10 (2000) 1151]. However, for these materials, the limit began to emerge as the commercialization of OLED since 2002, and since then, a large number of high-performance electron transfer materials have been researched and announced, and are approaching commercialization.

Figure pat00001
Figure pat00001

한편, 비 금속착체 계열로, 현재까지 발표된 좋은 특성의 전자 전달재료로는 spiro-PBD[N. Johansson et.al. Adv. Mater. 10 (1998) 1136], PyPySPyPy[M. Uchida et.al. Chem. Mater. 13 (2001) 2680] 및 Kodak의 TPBI[Y.-T. Tao et.al. Appl. Phys. Lett. 77 (2000) 1575] 등이 있으나, 전기 발광 특성 및 수명 측면에서 아직 많은 개선의 여지가 남아 있다.On the other hand, as a non-metallic complex, spiro-PBD [N. Johansson et.al. Adv. Mater. 10 (1998) 1136, PyPy SPyPy [M. Uchida et.al. Chem. Mater. 13 (2001) 2680] and Kodak's TPBI [Y.-T. Tao et.al. Appl. Phys. Lett. 77 (2000) 1575], but there is still much room for improvement in terms of electroluminescent properties and lifetime.

Figure pat00002
Figure pat00002

종래의 전자 전달 재료에 있어서, 특히 주목할 만한 것은 발표하는 내용 대비 실제로 단순히 구동 전압만을 약간 개선한다거나, 소자 구동 수명의 현저한 저하 등의 문제점들을 보이고 있고, 컬러별 소자 수명의 편차 및 열적 안정성 저하 등의 부작용적 특성을 나타낸다는 것이다. 현재까지 OLED 패널의 대형화에 걸림돌로 작용하고 있는 소비 전력, 휘도의 증가 등 목표를 달성하기 위해서는 상기의 부작용적 특성들은 큰 장애가 되고 있는 게 현실이라고 하겠다.In the conventional electron transfer material, it is particularly noteworthy that compared to what is disclosed, there are problems such as a simple improvement in driving voltage only, a significant reduction in device driving life, and a variation in device life and thermal stability by color. Side effects. In order to achieve the goals such as power consumption and brightness, which have been obstacles to the large-sized OLED panel, the side effects mentioned above are becoming obstacles.

따라서 본 발명의 목적은 상술한 바와 같은 기존의 전자전달재료의 약점을 보완하고 전자전달 효율, 소비 전력 및 소자 수명을 보다 개선시킨 신규한 유기 전자재료용 화합물을 제공하는 것이며, 또 다른 목적으로서 상기 신규한 유기 전자재료용 화합물을 포함하는 유기 전계 발광 소자를 제공하는 것이다. Accordingly, an object of the present invention is to provide a novel compound for organic electronic materials which compensates for the weak points of the conventional electron transfer materials as described above and further improves the electron transfer efficiency, power consumption, and device life. It is an object to provide an organic electroluminescent device comprising a novel compound for organic electronic materials.

본 발명은 하기 화학식 1로 표시되는 유기 전자재료용 화합물, 이를 포함하고 있는 유기 전계 발광 소자에 관한 것으로, 본 발명에 따른 유기 전자재료용 화합물은 전자전달재료로서, 전자전달 효율이 높아 소자 제작시 결정화를 방지할 뿐만 아니라 층 형성이 양호하여 소자의 전류특성을 개선시킴으로서 소자의 구동전압을 저하시키고 동시에 전력효율이 향상된 OLED 소자를 제조할 수 있는 장점이 있다.The present invention relates to a compound for an organic electronic material represented by the following Chemical Formula 1, and an organic electroluminescent device comprising the same. The compound for an organic electronic material according to the present invention is an electron transfer material and has high electron transfer efficiency. In addition to preventing crystallization, the layer formation is good, thereby improving the current characteristics of the device, thereby lowering the driving voltage of the device, and at the same time, manufacturing an OLED device having improved power efficiency.

[화학식 1][Formula 1]

Figure pat00003
Figure pat00003

[상기 화학식 1에서, [In Formula 1,

X는 -C(R1)(R2)-, -Si(R3)(R4)-, -S- 또는 -O-이고;X is —C (R 1 ) (R 2 ) —, —Si (R 3 ) (R 4 ) —, —S— or —O—;

R1 내지 R4는 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴 또는 헤테로아릴(C3-C30)이거나, R1과 R2 또는 R3와 R4는 서로 독립적으로 융합고리를 포함하거나 포함하지 않는 (C3-C12)알킬렌 또는 (C3-C12)알케닐렌으로 연결되어 스피로고리 또는 융합고리를 형성할 수 있고;R 1 to R 4 are independently of each other (C1-C30) alkyl, (C6-C30) aryl or heteroaryl (C3-C30), or R 1 and R 2 or R 3 and R 4 are each independently a fused ring. Can be linked with (C3-C12) alkylene or (C3-C12) alkenylene to form a spirogory or fused ring;

Ar1 내지 Ar4는 서로 독립적으로 수소, (C1-C30)알킬, 할로겐, 디(C1-C30)알킬보라닐, 디(C6-C30)아릴보라닐, 시아노, (C3-C30)시클로알킬, 모폴리노, 티오모폴리노, 피페리디노, 5원 내지 7원의 헤테로시클로알킬, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, 카바졸릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴티오, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 또는 하이드록시이고;Ar 1 to Ar 4 are independently of each other hydrogen, (C1-C30) alkyl, halogen, di (C1-C30) alkylboranyl, di (C6-C30) arylboranyl, cyano, (C3-C30) cycloalkyl , Morpholino, thiomorpholino, piperidino, 5- to 7-membered heterocycloalkyl, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, ( C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, carbazolyl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) Arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy;

상기 R1 내지 R4의 알킬, 아릴 또는 헤테로아릴 및 Ar1 내지 Ar4의 알킬, 시클로알킬, 헤테로시클로알킬, 바이시클로알킬, 알킬보라닐, 아릴보라닐, 알케닐, 알키닐, 아릴, 알콕시, 아릴옥시, 헤테로아릴, 아르알킬, 아릴티오, 알킬아미노, 아릴아미노, 트리알킬실릴, 디알킬아릴실릴 또는 트리아릴실릴은 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴티오, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 또는 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;Alkyl, aryl or heteroaryl of R 1 to R 4 and alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, alkylboranyl, arylboranyl, alkenyl, alkynyl, aryl, alkoxy of Ar 1 to Ar 4 , Aryloxy, heteroaryl, aralkyl, arylthio, alkylamino, arylamino, trialkylsilyl, dialkylarylsilyl or triarylsilyl is deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen , Cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6- C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) heteroaryl, (C6-C30) aryl Substituted (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) Arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsil , Tri (C6-C30) arylsilyl, it may be further substituted with one or more selected from the group consisting of nitro, or hydroxy;

상기 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함한다.]
Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]

본 발명에 기재된 「알킬」은 탄소 원자 및 수소 원자만으로 구성된 직쇄 또는 분지쇄의 포화된 1가 탄화수소 라디칼 또는 그의 조합물을 포함하며, 또한, 「알콕시」 및 「알킬티오」는 각각 -O-알킬기 및 -S-알킬기로, 여기서 알킬은 상기 정의한 바와 같다."Alkyl" described in the present invention includes a straight or branched chain saturated monovalent hydrocarbon radical or a combination thereof composed of only carbon and hydrogen atoms, and "alkoxy" and "alkylthio" each represent an -O-alkyl group. And an -S-alkyl group, wherein alkyl is as defined above.

본 발명에 기재된 「아릴」은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로 페닐, 나프틸, 비페닐, 안트릴, 인데닐(indenyl), 플루오레닐, 페난트릴, 트리페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 플루오란텐일 등을 포함하지만, 이에 한정되지 않는다. 상기 나프틸은 1-나프틸 및 2-나프틸을 포함하며, 안트릴은 1-안트릴, 2-안트릴 및 9-안트릴을 포함하며, 플루오레닐은 1-플루오레닐, 2-플루오레닐, 3-플루오레닐, 4-플루오레닐 및 9-플루오레닐을 모두 포함한다. 본 발명에 기재된 「헤테로아릴」은 방향족 고리 골격 원자로서 B, N, O, S, P(=O), Si 및 P로부터 선택되는 1 내지 4개의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠 환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 또한, 본 발명에서의 헤테로아릴은 하나 이상의 헤테로아릴이 단일결합으로 연걸된 형태도 포함한다. 상기 헤테로아릴기는 고리내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다. 구체적인 예로 퓨릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아졸릴, 테트라졸릴, 퓨라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴, 벤조퓨란일, 벤조티오펜일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴녹살리닐, 카바졸릴, 페난트리딘일, 벤조디옥솔릴 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드(예를 들어, 피리딜 N-옥사이드, 퀴놀릴 N-옥사이드), 이들의 4차 염 등을 포함하지만, 이에 한정되지 않는다."Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthasenyl, fluoranthenyl, and the like. It is not limited to this. Said naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl is 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. The "heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si, and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. Meaning an aryl group which is 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, the heteroaryl in the present invention also includes a form in which one or more heteroaryls are linked by a single bond. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as zolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothia Zolyl, Benzoisoxazolyl, Benzoxazolyl, Isoindoleyl, Indolyl, Indazolyl, Benzothiadiazolyl, Quinolyl, Isoquinolyl, Cinolinyl, Quinazolinyl, Quinoxalinyl, Carbazolyl, Phenantridinyl , Polycyclic heteroaryls such as benzodioxolyl and the like, and their corresponding N-oxides (eg, pyridyl N-oxides, quinolyl N-oxides), quaternary salts thereof, and the like. .

또한, 본 발명에 기재되어 있는 “(C1-C30)알킬, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬옥시, (C1-C30)알킬티오, (C1-C30)알킬옥시카보닐, (C1-C30)알킬카보닐, (C1-C30)알킬옥시카보닐옥시, (C1-C30)알킬카보닐옥시” 등의 알킬은 탄소수 1 내지 20개로 제한될 수 있고, 탄소수 1 내지 10개로 제한될 수 있다. “(C6-C30)아릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴옥시, (C6-C30)아릴티오, (C6-C30)아릴카보닐, (C6-C30)아릴옥시카보닐, (C6-C30)아릴카보닐옥시, (C6-C30)아릴옥시카보닐옥시”등의 아릴은 탄소수 6 내지 20개로 제한될 수 있고, 탄소수 6 내지 12개로 제한될 수 있다. “(C3-C30)헤테로아릴”의 헤테로아릴은 탄소수 4 내지 20개로 제한될 수 있고, 탄소수 4 내지 12개로 제한될 수 있다. “(C3-C30)시클로알킬”의 헤테로아릴은 탄소수 3 내지 20개로 제한될 수 있고, 탄소수 3 내지 7개로 제한될 수 있다. “(C2-C30)알케닐 또는 알키닐””의 알케닐 또는 알키닐은 탄소수 2 내지 20개로 제한될 수 있고, 탄소수 2 내지 10개로 제한될 수 있다.
Also described herein are “(C1-C30) alkyl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C6-C30) ar (C1-C30) ) Alkyl, (C1-C30) alkyloxy, (C1-C30) alkylthio, (C1-C30) alkyloxycarbonyl, (C1-C30) alkylcarbonyl, (C1-C30) alkyloxycarbonyloxy, ( Alkyl, such as "C1-C30) alkylcarbonyloxy", may be limited to 1 to 20 carbon atoms, and may be limited to 1 to 10 carbon atoms. “(C6-C30) aryl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) Aryloxy, (C6-C30) arylthio, (C6-C30) arylcarbonyl, (C6-C30) aryloxycarbonyl, (C6-C30) arylcarbonyloxy, (C6-C30) aryloxycarbonyloxy Aryl such as ”may be limited to 6 to 20 carbon atoms, and may be limited to 6 to 12 carbon atoms. Heteroaryl of "(C3-C30) heteroaryl" may be limited to 4 to 20 carbon atoms, it may be limited to 4 to 12 carbon atoms. Heteroaryl of "(C3-C30) cycloalkyl" may be limited to 3 to 20 carbon atoms, it may be limited to 3 to 7 carbon atoms. Alkenyl or alkynyl of "(C2-C30) alkenyl or alkynyl""may be limited to 2 to 20 carbon atoms, and may be limited to 2 to 10 carbon atoms.

상기 화학식 1에서 X는 -C(R1)(R2)-, -Si(R3)(R4)-, -S- 또는 -O-이고, R1 내지 R4는 서로 독립적으로 (C1-C30)알킬 또는 (C6-C30)아릴이거나, R1과 R2 또는 R3와 R4는 서로 독립적으로 융합고리를 포함하거나 포함하지 않는 (C3-C12)알킬렌 또는 (C3-C12)알케닐렌으로 연결되어 스피로고리 또는 융합고리를 형성할 수 있다.In Formula 1, X is -C (R 1 ) (R 2 )-, -Si (R 3 ) (R 4 )-, -S- or -O-, and R 1 to R 4 are independently of each other (C1 (C 3 -C 12) alkylene or (C 3 -C 12) alke, or C 1 -C 30) aryl, or R 1 and R 2 or R 3 and R 4 independently or without fused ring It may be linked with niylene to form a spirogory or fused ring.

즉, 상기 R1과 R2가 융합고리를 포함하거나 포함하지 않는 알킬렌 또는 알케닐렌으로 연결되어 하기구조에서 선택되는 스피로고리 또는 융합고리를 형성할 수 있으며, 이에 한정되지는 않는다.That is, the R 1 and R 2 may be connected to an alkylene or alkenylene containing or without a fused ring to form a spirogory or a fused ring selected from the following structures, but is not limited thereto.

Figure pat00004
Figure pat00004

또한, 상기 R3와 R4 역시 융합고리를 포함하거나 포함하지 않는 알킬렌 또는 알케닐렌으로 연결되어 하기구조에서 선택되는 스피로고리 또는 융합고리를 형성할 수 있으며, 이에 한정되지는 않는다.In addition, the R 3 and R 4 may also be connected to alkylene or alkenylene, which may or may not include a fused ring, to form a spirogory or fused ring selected from the following structures, but is not limited thereto.

Figure pat00005
Figure pat00005

상기 Ar1 내지 Ar4는 서로 독립적으로 (C3-C30)시클로알킬, 모폴리노, 티오모폴리노, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, 카바졸릴, (C6-C30)아릴티오, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴 또는 트리(C6-C30)아릴실릴에서 선택된다.Ar 1 to Ar 4 are independently of each other (C3-C30) cycloalkyl, morpholino, thiomorpholino, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alky Neyl, (C6-C30) aryl, (C6-C30) aryloxy, (C3-C30) heteroaryl, carbazolyl, (C6-C30) arylthio, tri (C1-C30) alkylsilyl, di (C1-C30 ) Alkyl (C6-C30) arylsilyl or tri (C6-C30) arylsilyl.

또한, 상기 R1 내지 R4의 알킬 또는 아릴 및 Ar1 내지 Ar4의 시클로알킬, 바이시클로알킬, 알케닐, 알키닐, 아릴, 아릴옥시, 헤테로아릴, 아릴티오, 트리알킬실릴, 디알킬아릴실릴 또는 트리아릴실릴은 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴티오, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 또는 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.
In addition, alkyl or aryl of R 1 to R 4 and cycloalkyl, bicycloalkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl, arylthio, trialkylsilyl, dialkylaryl of Ar 1 to Ar 4 Silyl or triarylsilyl is deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30 ) Bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl , (C3-C30) heteroaryl substituted with (C1-C30) alkyl, (C3-C30) heteroaryl substituted with (C6-C30) aryl, (C6-C30) ar (C1-C30) alkyl, (C6 -C30) arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) aryl One or more selected from the group consisting of silyl, tri (C6-C30) arylsilyl, nitro or hydroxy Can be substituted.

본 발명에 따른 유기 전자재료용 화합물은 보다 구체적으로 하기의 화합물로서 예시될 수 있으나, 하기 화합물이 본 발명을 한정하는 것은 아니다.The compound for an organic electronic material according to the present invention may be more specifically exemplified as the following compound, but the following compound is not intended to limit the present invention.

Figure pat00006
Figure pat00006

Figure pat00007
Figure pat00007

Figure pat00008
Figure pat00008

Figure pat00009
Figure pat00009

Figure pat00010
Figure pat00010

Figure pat00011
Figure pat00011

Figure pat00012
Figure pat00012

Figure pat00013
Figure pat00013

Figure pat00014
Figure pat00014

Figure pat00015
Figure pat00015

Figure pat00016
Figure pat00016

Figure pat00017
Figure pat00017

Figure pat00018
Figure pat00018

Figure pat00019
Figure pat00019

Figure pat00020
Figure pat00020

Figure pat00021
Figure pat00021

Figure pat00022
Figure pat00022

Figure pat00023
Figure pat00023

Figure pat00024
Figure pat00024

Figure pat00025
Figure pat00025

Figure pat00026
Figure pat00026

Figure pat00027
Figure pat00027

본 발명에 따른 유기 전자재료용 화합물은 하기 반응식 1에 나타난 바와 같이, 제조될 수 있다.The compound for an organic electronic material according to the present invention can be prepared, as shown in Scheme 1 below.

[반응식 1]Scheme 1

Figure pat00028
Figure pat00028

[상기 반응식 1에서, X 및 Ar1 내지 Ar4는 상기 화학식 1에서의 정의와 동일하다.][In Reaction Scheme 1, X and Ar 1 to Ar 4 are the same as the definition in Formula 1.]

본 발명은 유기 전계 발광 소자를 제공하며, 본 발명에 따른 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어져 있으며, 상기 유기물층은 상기 화학식 1의 유기 전자재료용 화합물을 하나 이상 포함하는 것을 특징으로 한다. 상기 유기 전자재료용 화합물은 전자전달층의 재료로 사용되어진다.The present invention provides an organic electroluminescent device, the organic electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one compound for an organic electronic material of Chemical Formula 1. The compound for an organic electronic material is used as a material for the electron transport layer.

본 발명에 따른 상기 화학식 1의 유기 전자재료용 화합물을 전자전달층에 사용하는 경우 구동 전압 저하로 OLED 소비 전력을 현저히 감소시키며 우수한 발광 효율을 가진다.When the compound for the organic electronic material of Formula 1 according to the present invention is used in the electron transport layer, OLED power consumption is significantly reduced due to a decrease in driving voltage, and has excellent light emission efficiency.

또한, 상기 유기물층은 상기 화학식 1의 유기 전자재료용 화합물이 포함된 층 하나 이상과 형광호스트-형광도판트 또는 인광호스트-인광도판트로 이루어진 발광층 하나 이상을 포함하는 것을 특징으로 하며, 본 발명의 유기 전계 발광 소자에 적용되는 형광호스트, 형광도판트, 인광호스트 또는 인광도판트는 특별히 제한되지는 않는다.In addition, the organic material layer is characterized in that it comprises at least one layer containing the compound for the organic electronic material of Formula 1 and at least one light emitting layer consisting of a fluorescent host-fluorescent dopant or a phosphorescent host-phosphorescent dopant, the organic of the present invention The fluorescent host, fluorescent dopant, phosphorescent host or phosphorescent dopant applied to the electroluminescent device is not particularly limited.

본 발명의 유기 전계 발광 소자에 있어서, 화학식 1의 유기 전자재료용 화합물을 포함하고, 동시에 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 화합물을 포함할 수 있다. 상기 아릴아민계 화합물 또는 스티릴아릴아민계 화합물은 출원번호 제10-2008-0123276호, 제10-2008-0107606호 또는 제10-2008-0118428호에 예시되어 있으나, 이에 한정되지는 않는다. In the organic electroluminescent device of the present invention, it may include at least one compound selected from the group consisting of a compound for an organic electronic material of formula (1) and at the same time an arylamine compound or styrylarylamine compound. The arylamine-based compound or styrylarylamine-based compound is exemplified in Patent Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but is not limited thereto.

또한, 본 발명의 유기 전계 발광 소자에 있어서, 유기물층에 상기 화학식 1의 유기 전자재료용 화합물 이외에 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 착체화합물을 더 포함할 수도 있고, 상기 유기물층은 전자전달층과 발광층 이외에 전하생성층을 포함할 수 있다.In addition, in the organic electroluminescent device of the present invention, in the organic material layer, in addition to the compound for the organic electronic material of Formula 1, Group 1, Group 2, 4 cycle, 5 cycle transition metals, lanthanum series metals and organic metal of d-transition element It may further comprise one or more metals or complex compounds selected from the group consisting of, the organic material layer may include a charge generating layer in addition to the electron transport layer and the light emitting layer.

또한, 상기 유기물층에 상기 유기 전자재료용 화합물 이외에 적색, 녹색 또는 청색 발광을 하는 유기발광층 하나 이상을 동시에 포함하여 백색 발광을 하는 백색 유기 전계 발광 소자를 형성할 수 있다. 상기 청색, 녹색 또는 적색 발광을 하는 화합물은 출원번호 제10-2008-0123276호, 제10-2008-0107606호 또는 제10-2008-0118428호에 예시되어 있으나, 이에 한정되지는 않는다. In addition, a white organic electroluminescent device for emitting white light may be formed on the organic material layer by simultaneously including one or more organic light emitting layers emitting red, green, or blue light in addition to the compound for organic electronic materials. The compound emitting blue, green, or red light is exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606, or 10-2008-0118428, but is not limited thereto.

본 발명의 유기 전계 발광 소자에 있어서, 한 쌍의 전극의 적어도 한쪽의 내측표면에, 칼코제나이드(chalcogenide)층, 할로겐화 금속층 및 금속 산화물층으로부터 선택되는 일층(이하, 이들을 "표면층"이라고 지칭함) 이상을 배치하는 것이 바람직하다. 구체적으로는, 발광 매체층 측의 양극 표면에 규소 및 알루미늄의 금속의 칼코제나이드(산화물을 포함한다)층을, 또한 발광매체층 측의 음극 표면에 할로겐화 금속층 또는 금속 산화물층을 배치하는 것이 바람직하다. 이것에 의해, 구동의 안정화를 얻을 수 있다. 상기 칼코제나이드로서는 예컨대 SiOx(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON 등을 바람직하게 들 수 있으며, 할로겐화 금속으로서는 예컨대 LiF, MgF2, CaF2, 불화 희토류 금속 등을 바람직하게 들 수 있으며, 금속 산화물로서는 예컨대 Cs2O, Li2O, MgO, SrO, BaO, CaO 등을 바람직하게 들 수 있다.In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Examples of the chalcogenide include SiO x (1 ≦ X ≦ 2 ), AlO X (1 ≦ X ≦ 1.5), SiON, SiAlON, and the like, and examples of the metal halide include LiF, MgF 2 , CaF 2 , and fluoride. Rare earth metals and the like are preferable. Examples of the metal oxides include Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO and the like.

또한, 본 발명의 유기 전계 발광 소자에 있어서, 이렇게 제작된 한 쌍의 전극의 적어도 한쪽의 표면에 전자 전달 화합물과 환원성 도판트의 혼합 영역 또는 정공 전달 화합물과 산화성 도판트의 혼합 영역을 배치하는 것도 바람직하다. 이러한 방식으로, 전자 전달 화합물이 음이온으로 환원되므로 혼합 영역으로부터 발광 매체에 전자를 주입 및 전달하기 용이해진다. 또한, 정공 전달 화합물은 산화되어 양이온으로 되므로 혼합 영역으로부터 발광 매체에 정공을 주입 및 전달하기 용이해진다. 바람직한 산화성 도판트로서는 각종 루이스산 및 억셉터(acceptor) 화합물을 들 수 있다. 바람직한 환원성 도판트로서는 알칼리 금속, 알칼리 금속 화합물, 알칼리 토류 금속, 희토류 금속 및 이들의 혼합물을 들 수 있다. 또한 환원성 도판트층을 전하생성층으로 사용하여 두 개 이상의 발광층을 가진 백색 유기 전계 발광 소자를 제작할 수 있다.Further, in the organic electroluminescent device of the present invention, disposing a mixed region of an electron transfer compound and a reducing dopant or a mixed region of a hole transfer compound and an oxidative dopant on at least one surface of the pair of electrodes thus produced desirable. In this way, the electron transfer compound is reduced to an anion, thereby facilitating injection and transfer of electrons from the mixed region into the light emitting medium. In addition, since the hole transport compound is oxidized to become a cation, it is easy to inject and transfer holes from the mixed region to the light emitting medium. Preferred oxidative dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and mixtures thereof. In addition, a white organic electroluminescent device having two or more light emitting layers may be manufactured using a reducing dopant layer as a charge generation layer.

본 발명에 따른 유기 전자재료용 화합물은 전자전달 효율이 높아 전자전달층에 포함되어 소자 제작시 결정화를 방지할 뿐만 아니라 층 형성이 양호하여 소자의 전류특성을 개선시킴으로서 소자의 구동전압을 저하시키고 소비전력을 현저히 감소시킬 뿐만 아니라 동등 이상의 발광 효율을 나타내는 OLED 소자를 제조할 수 있는 장점이 있다.The compound for an organic electronic material according to the present invention is included in the electron transporting layer having high electron transfer efficiency to prevent crystallization during device fabrication, and to improve layer current by improving layer current, thereby lowering driving voltage and consuming a device. In addition to significantly reducing the power, there is an advantage in that an OLED device can be produced that exhibits luminous efficiency equal to or more than that.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 들어 본 발명에 따른 유기 전자재료용 화합물, 이의 제조방법 및 소자의 발광특성을 설명하나, 이는 단지 그 실시 양태를 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, for the detailed understanding of the present invention, a compound for an organic electronic material according to the present invention, a method for preparing the same, and a light emitting property of the device will be described with reference to a representative compound of the present invention, but only for the purpose of illustrating the embodiments thereof. It does not limit the scope of the present invention.

[제조예 1]화합물 2의 제조Preparation Example 1 Preparation of Compound 2

Figure pat00029
Figure pat00029

화합물 A의 제조Preparation of Compound A

질소 분위기 하에서 2,7-디브로모플루오렌 (10 g, 0.037 mol)을 THF 200mL에 가하고, -78℃로 냉각한 후 n-BuLi (2.5M in Hexane) (1.2 당량)을 천천히 첨가하였다. 2시간 후 1M HCl을 가하고 30분 동안 교반시킨 다음, EA와 증류수로 3번 씻어주었다. 얻어진 유기층을 실리카겔 필터로 여과시켜 얻어진 여액을 회전 증발기로 용매를 제거한 후 흰색 고체로 화합물 A (7 g, 97 %)를 얻었다. 2,7-dibromofluorene (10 g, 0.037 mol) was added to 200 mL of THF under nitrogen atmosphere, cooled to -78 ° C, and n-BuLi (2.5 M in Hexane) (1.2 equiv) was added slowly. After 2 hours, 1M HCl was added, stirred for 30 minutes, and washed three times with EA and distilled water. The obtained organic layer was filtered through a silica gel filter, and the obtained filtrate was removed with a rotary evaporator to obtain Compound A (7 g, 97%) as a white solid.

화합물 B의 제조Preparation of Compound B

화합물 A (10 g, 0.05 mol)을 아세트산 100mL에 용해시키고, 0℃에서 발연질산(fuming nitric acid) (50 당량)과 황산 (30 mL)을 첨가한 후 서서히 실온으로 온도를 올린 후 30분 동안 교반시켰다. 생성된 고체를 감압 여과한 후 아세트산으로 2번 씻어주었다. 얻어진 유기층을 감압증류하여 용매를 제거시킨 후 컬럼크로마토그래피로 정제하여 순수한 노란색 고체로 화합물 B (4.2 g, 30 %)를 얻었다. Compound A (10 g, 0.05 mol) was dissolved in 100 mL of acetic acid, fuming nitric acid (50 equiv) and sulfuric acid (30 mL) were added at 0 ° C., and then slowly raised to room temperature for 30 minutes. Stirred. The resulting solid was filtered under reduced pressure and washed twice with acetic acid. The obtained organic layer was distilled under reduced pressure to remove the solvent, and then purified by column chromatography to give the compound B (4.2 g, 30%) as a pure yellow solid.

화합물 C의 제조Preparation of Compound C

염산 (30 mL)과 에탄올 (12 mL), SnCl2 (4 g)와 화합물 B (4.2 g, 0.014 mol)을 질소 분위기 하에서 4시간 동안 환류 교반시킨 후 생성된 흰색 고체를 여과하여 염산으로 씻어주었다. 아세트산 (20 mL)와 무수아세트산 (20 mL)의 혼합시킨 후 상기 얻어진 흰색 고체 (3 g)를 0℃에서 천천히 첨가하였다. 20분후 천천히 실온으로 온도를 올린 후 24시간 동안 교반시켰다. 반응 종결 후 증류수를 천천히 가하고 회전 증발기를 이용하여 용매를 제거한 후 디클로메탄으로 추출한 후 증류수로 3번 씻어주었다. 얻어진 유기층을 감압증류하여 용매를 제거시킨 후 컬럼크로마토그래피로 정제하여 순수한 흰색 고체로 화합물 C (3.5 g, 75 %)를 얻었다. Hydrochloric acid (30 mL), ethanol (12 mL), SnCl 2 (4 g), and Compound B (4.2 g, 0.014 mol) were stirred under reflux for 4 hours under a nitrogen atmosphere, and the resulting white solid was filtered and washed with hydrochloric acid. . After mixing acetic acid (20 mL) and acetic anhydride (20 mL), the white solid (3 g) obtained above was added slowly at 0 ° C. After 20 minutes, the temperature was slowly raised to room temperature and stirred for 24 hours. After completion of the reaction, distilled water was slowly added, the solvent was removed using a rotary evaporator, extracted with dichloromethane, and washed three times with distilled water. The obtained organic layer was distilled under reduced pressure to remove the solvent, and then purified by column chromatography to give the compound C (3.5 g, 75%) as a pure white solid.

화합물 D의 제조Preparation of Compound D

-10℃에서 아세트산 (10 mL)와 발연질산(fuming nitric acid) (10 mL)를 혼합시킨 후 동온도에서 화합물 C (3.5 g, 0.0145 mol)를 천천히 첨가하였다. 10분 후 반응물을 차가운 증류수에 붓고 감압 여과하여 얻어진 유기물을 컬럼크로마토그래피로 정제하여 순수한 노란색 고체로 화합물 D (3.4 g, 59 %)를 얻었다. Acetic acid (10 mL) and fuming nitric acid (10 mL) were mixed at -10 ° C, and Compound C (3.5 g, 0.0145 mol) was slowly added at the same temperature. After 10 minutes, the reaction mixture was poured into cold distilled water and filtered under reduced pressure. The organic substance was purified by column chromatography to obtain Compound D (3.4 g, 59%) as a pure yellow solid.

화합물 E의 제조Preparation of Compound E

화합물 D (3.4 g, 0.009 mol)에 황산 (24 mL) 및 증류수 (20 mL)를 차례로 천천히 첨가하였다. 그런 다음 상기 반응물을 2시간 동안 90℃에서 환류교반시켰다. 반응 종결 후 반응물을 차가운 증류수에 붓고 감압여과하였다. 얻어진 유기물을 컬럼크로마토그래피로 정제하여 노란색 고체로 화합물 E (2 g, 70 %)를 얻었다.To compound D (3.4 g, 0.009 mol) was added slowly sulfuric acid (24 mL) and distilled water (20 mL). The reaction was then stirred at reflux at 90 ° C. for 2 hours. After completion of the reaction, the reaction was poured into cold distilled water and filtered under reduced pressure. The obtained organic material was purified by column chromatography to obtain compound E (2 g, 70%) as a yellow solid.

화합물 F의 제조Preparation of Compound F

화합물 E (2 g, 0.006 mol)에 브로모벤젠 (1.1 g), Pd(OAc)2 (0.04 g) 및 Cs2CO3 (4.1 g)를 첨가한 후 질소 분위기 하에서 톨루엔 (25 mL)과 P(t-Bu)3 (0.4 mL)을 첨가한 후 80℃에서 12시간 동안 환류 교반시켰다. 반응 종결 후 EA와 증류수를 이용하여 추출한 후 회전 증발기로 용매를 제거한 후 얻어진 유기물을 컬럼크로마토그래피로 정제하여 노란색 고체로 화합물 F (2 g, 71 %)를 얻었다.To compound E (2 g, 0.006 mol) was added bromobenzene (1.1 g), Pd (OAc) 2 (0.04 g) and Cs 2 CO 3 (4.1 g), followed by toluene (25 mL) and P under nitrogen atmosphere. (t-Bu) 3 (0.4 mL) was added followed by stirring under reflux at 80 ° C. for 12 h. After completion of the reaction, the mixture was extracted using EA and distilled water, and then the solvent was removed using a rotary evaporator, and the obtained organic material was purified by column chromatography to obtain Compound F (2 g, 71%) as a yellow solid.

화합물 G의 제조Preparation of Compound G

화합물 F (2 g, 0.0043 mol)에 에탄올 (20 mL)을 첨가하고 10분 동안 교반시킨 후 Pd/C (0.3 g)을 수소(5 psi)분위기 하, 90℃에서 4시간 동안 환류 교반시켰다. 반응 종결 후 반응물을 감압 여과한 후 얻어진 유기물을 컬럼크로마토그래피로 정제하여 노란색 고체로 화합물 G (1.8 g, 74 %)를 얻었다.Ethanol (20 mL) was added to Compound F (2 g, 0.0043 mol) and stirred for 10 minutes, followed by stirring at Pd / C (0.3 g) at reflux for 4 hours at 90 ° C. under a hydrogen (5 psi) atmosphere. After completion of the reaction, the reaction product was filtered under reduced pressure and the organic substance was purified by column chromatography to give the compound G (1.8 g, 74%) as a yellow solid.

화합물 2의 제조Preparation of Compound 2

화합물 G (1.3 g, 0.003 mol)에 2-나프토산(2-naphthoic acid) (1.4 g)과 아세트산 (50 mL)를 첨가한 후 12시간 동안 환류 교반시켰다. 반응 종결 후 EA와 증류수를 이용하여 추출한 후 회전 증발기로 용매를 제거하고 얻어진 유기물을 컬럼크로마토그래피로 정제하여 아이보리색 고체로 화합물 2 (1.2 g, 55 %)를 얻었다.
2-naphthoic acid (1.4 g) and acetic acid (50 mL) were added to compound G (1.3 g, 0.003 mol), followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted using EA and distilled water, and then the solvent was removed by a rotary evaporator, and the organic substance was purified by column chromatography to obtain a compound 2 (1.2 g, 55%) as an ivory solid.

[[ 제조예Manufacturing example 2] 화합물 49의 제조 2] Preparation of Compound 49

Figure pat00030
Figure pat00030

화합물 H의 제조Preparation of Compound H

디벤조[b,d]티오펜 (9.2g, 0.05 mol)과 과산화수소 (21.6 mL)와 메탄올 (300 mL)을 넣고 5분 동안 실온에서 교반한다. 그런 다음 ZrCl4 (46.5 g)을 넣고 실온에서 3분 동안 교반한다. 그럼다음 CHCl3 와 증류수를 이용하여 추출 후 컬럼분리하여 화합물 H를 97 % 수율로 얻었다.Dibenzo [b, d] thiophene (9.2 g, 0.05 mol), hydrogen peroxide (21.6 mL) and methanol (300 mL) were added and stirred at room temperature for 5 minutes. Then ZrCl 4 (46.5 g) was added and stirred at room temperature for 3 minutes. Then, extracted with CHCl 3 and distilled water and then separated by column to obtain a compound H in 97% yield.

화합물 I의 제조Preparation of Compound I

화합물 H (8.5g, 0.042 mol) 와 H2SO4 (36.7 mL), AcOH (36.7 mL) 및 HNO3 (40 mL)를 모두 넣고 실온에서 2시간 동안 교반한다. 반응 종결 후 증류수를 첨가하면 고체가 생성된다. 고체를 필터하여 화합물 I를 89 % 수율로 얻었다.Add compound H (8.5 g, 0.042 mol), H 2 SO 4 (36.7 mL), AcOH (36.7 mL) and HNO 3 (40 mL) and stir at room temperature for 2 hours. After completion of the reaction, distilled water is added to form a solid. The solid was filtered to give compound I in 89% yield.

화합물 J의 제조Preparation of Compound J

화합물 I (9.2 g, 0.03 mol) 과 HCl (60 mL), SnCl2 (47 mL) 및 AcOH (100 mL)를 모두 넣고 12시간 동안 교반한다. 반응 종결 후 HCl 을 이용하여 필터 후 MeOH 로 씻어 주어 화합물 J를 74 % 수율로 얻었다.Add compound I (9.2 g, 0.03 mol), HCl (60 mL), SnCl 2 (47 mL), and AcOH (100 mL) and stir for 12 hours. After completion of the reaction, the mixture was washed with MeOH and filtered using HCl to obtain Compound J in 74% yield.

화합물 K의 제조Preparation of Compound K

화합물 J (11g, 0.05 mol) 과 CuBr2 (22.8 g), t-BuNO2 (9.2 mL) 및 ACN (255 mL)을 모두 넣고 12시간 동안 환류교반한다. 반응종결 후 EA와 증류수를 이용하여 추출 후 컬럼크로마토그래피를 이용하여 화합물 K 를 70 % 수율로 얻었다.Add compound J (11 g, 0.05 mol), CuBr 2 (22.8 g), t-BuNO 2 (9.2 mL), and ACN (255 mL) to reflux for 12 hours. After completion of the reaction, the mixture K was extracted using EA and distilled water, and then purified by column chromatography to obtain a compound K in 70% yield.

화합물 L의 제조Preparation of Compound L

화합물 K (9.7 g, 0.03 mol), LiAlH4 (1.3 g)과 THF (174 mL)을 넣고 3시간 동안 환류교반한다. 반응 종결 후 EA 와 증류수를 이용하여 추출 후 컬럼크로마토그래피를 이용하여 화합물 L을 47 % 수율로 얻었다.Compound K (9.7 g, 0.03 mol), LiAlH 4 (1.3 g) and THF (174 mL) were added and stirred under reflux for 3 hours. After completion of the reaction, the compound L was obtained in 47% yield by column chromatography after extraction with EA and distilled water.

화합물 49의 제조Preparation of Compound 49

화합물 L을 중간물질로 해서 실시예 1과 동일한 방법으로 C-1 내지 G-1의 단계를 거쳐 화합물 49를 42 % 수율로 얻었다.
Compound 49 was obtained in 42% yield via the steps of C-1 to G-1 in the same manner as in Example 1 using compound L as an intermediate.

[[ 제조예Manufacturing example 3] 화합물 8의 제조 3] Preparation of Compound 8

Figure pat00031
Figure pat00031

화합물 A-1의 제조Preparation of Compound A-1

질소 분위기 하에서 2,7-디브로모플루오렌 (30g 0.109mol) 을 THF 500 mL에 가하고, -78℃로 냉각한 후 n-BuLi (2.5M in Hexane) (52.7 mL , 0.131mol) 을 천천히 첨가하였다. 1시간 후 물을 넣고 반응을 종료한 후, EA로 추출 후, 실리카겔 필터로 여과시켜 얻어진 여액을 회전 증발기로 제거한 후 흰색 고체로 화합물 A-1 (16g, 75.6%)을 얻었다.2,7-dibromofluorene (30g 0.109mol) was added to 500 mL of THF under nitrogen atmosphere, cooled to -78 ° C, and n-BuLi (2.5M in Hexane) (52.7 mL, 0.131mol) was added slowly. It was. After 1 hour, water was added and the reaction was completed, followed by extraction with EA, followed by filtration through a silica gel filter to remove the filtrate using a rotary evaporator, thereby obtaining Compound A-1 (16 g, 75.6%) as a white solid.

화합물 B-1의 제조Preparation of Compound B-1

화합물 A-1 (16g, 0.082mol)을 아세트산 400mL에 용해시키고, 0℃에서 dropping funnel을 사용하여 발연질산(fuming nitric acid) (172mL, 4.1mol)과 황산 (43mL)을 첨가하고 24시간 교반시켰다. 생성된 고체를 감압 여과한 후 아세트산과 증류수로 씻어주었다. 얻어진 유기층을 감압증류하여 용매를 제거시킨 후 컬럼크로마토그래피로 정제하여 화합물 B-1 (16g, 81.5%)을 얻었다.Compound A-1 (16 g, 0.082 mol) was dissolved in 400 mL of acetic acid, fuming nitric acid (172 mL, 4.1 mol) and sulfuric acid (43 mL) were added using a dropping funnel at 0 ° C., and stirred for 24 hours. . The resulting solid was filtered under reduced pressure and washed with acetic acid and distilled water. The obtained organic layer was distilled under reduced pressure to remove the solvent, and then purified by column chromatography to obtain a compound B-1 (16g, 81.5%).

화합물 C-1의 제조Preparation of Compound C-1

화합물 B-1 (19g , 0.067mol)과 SnCl2 (120g, 0.536mol), HCl 152mL, 에탄올 80mL를 질소 분위기 하에서 4시간 동안 환류 교반시킨 후 생성된 고체를 여과하였다. 아세트산 (250 mL)와 무수아세트산 (100 mL)을 혼합시킨 후 상기 얻어진 고체를 천천히 가하고 상온에서 24시간 동안 환류 교반시켰다. 반응 종결 후 여과하여 흰색의 고체 C-1 (10g, 48.4%)을 얻었다.Compound B-1 (19 g, 0.067 mol), SnCl 2 (120 g, 0.536 mol), HCl 152 mL, and ethanol 80 mL were stirred under reflux for 4 hours under nitrogen atmosphere, and then the resulting solid was filtered. After acetic acid (250 mL) and acetic anhydride (100 mL) were mixed, the solid obtained was slowly added and stirred under reflux at room temperature for 24 hours. Filtration after completion of the reaction gave a white solid C-1 (10 g, 48.4%).

화합물 D-1의 제조Preparation of Compound D-1

-10℃에서 화합물 C-1 (10g, 0.0324mol)을 아세트산에 녹인 후, 동 온도에서 발연질산(fuming nitric acid) (75 mL)를 천천히 첨가하였다. 10분후 반응물을 차가운 증류수에 넣고 여과하여 고체를 얻었다. 얻어진 고체를 증류수와 헥산으로 세척 후 건조하여 노란색 고체 D-1 (5g, 38.7%)를 얻었다.Compound C-1 (10 g, 0.0324 mol) was dissolved in acetic acid at −10 ° C., and fuming nitric acid (75 mL) was slowly added at the same temperature. After 10 minutes, the reaction was poured into cold distilled water and filtered to obtain a solid. The obtained solid was washed with distilled water and hexane and dried to give a yellow solid D-1 (5 g, 38.7%).

화합물 E-1의 제조Preparation of Compound E-1

화합물 D-1 (5g, 0.0126mol)에 황산 (30 mL) 및 증류수 (8 mL)를 차례로 천천히 첨가하고, 반응물을 2시간 동안 150℃에서 환류교반시켰다. 반응 종결 후 반응물을 차가운 증류수에 붓고 감압여과 한 다음, 얻어진 유기물을 컬럼크로마토그래피로 정제하여 진한 붉은색 고체로 화합물 E-1 (3.5g, 88.4%)을 얻었다.To compound D-1 (5 g, 0.0126 mol) was added slowly sulfuric acid (30 mL) and distilled water (8 mL), and the reaction was stirred at reflux for 2 hours at 150 ° C. After completion of the reaction, the reaction mixture was poured into cold distilled water and filtered under reduced pressure, and then the obtained organic substance was purified by column chromatography to give the compound E-1 (3.5 g, 88.4%) as a dark red solid.

화합물 H의 제조Preparation of Compound H

화합물 E-1 (0.4 g, 0.078 mol)을 에탄올 (10 mL)에 녹인 후 Pd/C (70mg)을 넣고 90℃에서 4시간 동안 환류교반시켰다. 반응 종결 후 반응물을 여과한 다음, 염산을 넣은 후 용매를 제거하고 재결정 (Ethanol: THF = 1 :1)하여 화합물 H (0.43g, 91%)를 얻었다.Compound E-1 (0.4 g, 0.078 mol) was dissolved in ethanol (10 mL), Pd / C (70 mg) was added, and the mixture was stirred under reflux for 4 hours at 90 ° C. After completion of the reaction, the reaction mixture was filtered, and then added with hydrochloric acid, the solvent was removed and recrystallized (Ethanol: THF = 1: 1) to give a compound H (0.43g, 91%).

화합물 I-3의 제조Preparation of Compound I-3

화합물 I-1 (13g), 화합물 I-2 (4g)과 K2CO3 (4g), Cu powder (0.15g)을 모두 넣고 220℃에서 6시간 동안 교반시켰다. 그런 다음 과량 사용한 I-1을 증류하여 제거 후, 메탄올로 재결정 하여 흰색 고체로 화합물 I-3 (6g, 80%)을 얻었다.Compound I-1 (13g), compound I-2 (4g), K 2 CO 3 (4g), and Cu powder (0.15g) were added thereto and stirred at 220 ° C. for 6 hours. Then, the excess of I-1 was distilled off, and then recrystallized with methanol to obtain compound I-3 (6 g, 80%) as a white solid.

화합물 I-4의 제조Preparation of Compound I-4

화합물 I-3 (1g)을 에탄올에 녹인 후 과량의 KOH solution (10M in H2O)을 넣고 교반시켰다. 반응 종결 후 염산을 이용하여 추출한 후 여과하여 흰색고체로 화합물 I-4 (0.5g, 70%)을 얻었다.Compound I-3 (1 g) was dissolved in ethanol and excess KOH solution (10M in H 2 O) was added and stirred. After completion of the reaction, the mixture was extracted with hydrochloric acid and filtered to obtain the compound I-4 (0.5g, 70%) as a white solid.

화합물 J의 제조Preparation of Compound J

화합물 H (0.5 mmol)와 화합물 I-4 (1 mmol)을 glacial acetic acid 에 넣고 2시간 동안 교반한 다음, 생성된 고체를 여과 후 컬럼크로마토그래피로 정제하여 화합물 J (1g, 33.5%)을 얻었다.Compound H (0.5 mmol) and compound I-4 (1 mmol) were added to glacial acetic acid, followed by stirring for 2 hours. The resulting solid was filtered and purified by column chromatography to obtain compound J (1g, 33.5%). .

화합물 8의 제조Preparation of Compound 8

화합물 J (1g, 1.32 mmol)과 아이오도벤젠 (5.3 mmol), CuI (0.07 mmol), 18-크라운-6 (0.1 mmol) 및 1,2-다이클로로벤젠 (50 mL)를 모두 넣고 180℃에서 환류 교반시켰다. 반응 종결 후, EA로 추출하고 컬럼크로마토그래피로 정제하여 순수한 고체로 화합물 8 (1g, 83%)을 얻었다.
Add compound J (1 g, 1.32 mmol), iodobenzene (5.3 mmol), CuI (0.07 mmol), 18-crown-6 (0.1 mmol) and 1,2-dichlorobenzene (50 mL) at 180 ° C. It was stirred at reflux. After completion of the reaction, the mixture was extracted with EA and purified by column chromatography to obtain Compound 8 (1 g, 83%) as a pure solid.

상기 제조예 1 내지 3의 방법을 이용하여 유기 발광 화합물 1 내지 화합물 66을 제조하였으며, 표 1에 제조된 유기 발광 화합물들의 1H NMR 및 MS/FAB를 나타내었다.The organic light emitting compounds 1 to compound 66 were manufactured using the methods of Preparation Examples 1 to 3, and 1 H NMR and MS / FAB of the organic light emitting compounds prepared in Table 1 are shown.

[표 1]TABLE 1

Figure pat00032
Figure pat00032

Figure pat00033
Figure pat00033

Figure pat00034
Figure pat00034

[실시예 1-5] 본 발명에 따른 유기 전자재료용 화합물을 이용한 OLED 소자 제작Example 1-5 Fabrication of OLED Device Using Compound for Organic Electronic Materials According to the Present Invention

본 발명의 유기 전자재료용 화합물을 이용한 구조의 OLED 소자를 제작하였다.An OLED device having a structure using the compound for organic electronic materials of the present invention was produced.

우선, OLED용 글래스로부터 얻어진 투명전극 ITO 박막(15 Ω/□)을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다.First, the transparent electrode ITO thin film (15 Ω / □) obtained from the glass for OLED was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water in sequence, and then stored in isopropanol and used.

다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 하기 구조의 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐아민(2-TNATA)을 넣고, 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 60 nm 두께의 정공주입층을 증착하였다. 이어서, 진공 증착 장비 내의 다른 셀에 하기구조 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(NPB)을 넣고, 셀에 전류를 인가하여 NPB를 증발시켜 정공주입층 위에 20 nm 두께의 정공전달층을 증착하였다.Next, the ITO substrate is placed in the substrate folder of the vacuum deposition equipment, and the 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) tree having the following structure is installed in the cell in the vacuum deposition equipment. Phenylamine (2-TNATA) was added and evacuated until the vacuum in the chamber reached 10 -6 torr. Then, a current was applied to the cell to evaporate 2-TNATA to inject a 60 nm thick hole injection layer onto the ITO substrate. Subsequently, the following structure N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine (NPB) was added to another cell in the vacuum deposition equipment, NPB was evaporated by applying a current to deposit a 20 nm thick hole transport layer on the hole injection layer.

Figure pat00035
Figure pat00035

정공주입층, 정공전달층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 발광 재료로 발광호스트인 트리스(8-하이드록시퀴놀린)알루미늄(III) (Alq3)을 넣고, 또 다른 셀에는 발광도판트로 쿠마린 545T를 각각 넣은 후, 두 셀을 다른 속도로 증발시켜 도핑함으로써 상기 정공 전달층 위에 30 nm 두께의 발광층을 증착하였다. 이때의 도핑 농도는 Alq3 기준으로 2 내지 5 mol%가 바람직하다.After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. In one cell of the vacuum deposition equipment, tris (8-hydroxyquinoline) aluminum (III) (Alq3), which is a light emitting host, is put as a light emitting material, and in another cell, coumarin 545T is respectively used as a light emitting dopant, and then the two cells have different speeds. A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by evaporation and doping. The doping concentration at this time is preferably 2 to 5 mol% based on Alq3.

Figure pat00036
Figure pat00036

이어서 상기 발광층 위에 전자전달층으로써 본 발명에 따른 유기 전자재료용 화합물(예 : 화합물 2)을 20 nm 두께로 증착한 다음, 전자주입층으로 하기 구조의 화합물 리튬 퀴놀레이트 (Liq)를 1 내지 2 nm 두께로 증착한 후, 다른 진공 증착 장비를 이용하여 Al 음극을 150 nm의 두께로 증착하여 OLED를 제작하였다. Subsequently, a compound for an organic electronic material (for example, Compound 2) according to the present invention was deposited to a thickness of 20 nm as an electron transport layer on the light emitting layer, and then a compound lithium quinolate (Liq) having the following structure was used as an electron injection layer. After depositing at a thickness of nm, the OLED was manufactured by depositing an Al cathode at a thickness of 150 nm using another vacuum deposition equipment.

Figure pat00037
Figure pat00037

OLED 소자에 사용된 각 재료들은, 각각 10-6 torr 하에서 진공 승화 정제하여 OLED 발광재료로 사용하였다.
Each material used in the OLED device was vacuum sublimated and purified under 10 -6 torr, respectively, to be used as an OLED light emitting material.

[비교예 1] 종래의 전자전달재료를 이용한 OLED 소자의 발광 특성Comparative Example 1 Luminescence Characteristics of OLED Device Using Conventional Electron Transfer Material

실시예 1과 동일한 방법으로 정공주입층, 정공전달층 및 발광층을 형성시킨 후, 전자전달층으로써 하기 구조의 트리스(8-하이드록시퀴놀린)알루미늄(III) (Alq3)를 20 nm 두께로 증착한 다음, 전자주입층으로 Liq를 1 내지 2 nm 두께로 증착한 후, 다른 진공 증착 장비를 이용하여 Al 음극을 150 nm의 두께로 증착하여 OLED를 제작하였다. After the hole injection layer, the hole transport layer and the light emitting layer were formed in the same manner as in Example 1, tris (8-hydroxyquinoline) aluminum (III) (Alq3) having the following structure was deposited to a thickness of 20 nm as an electron transport layer. Next, Liq was deposited to a thickness of 1 to 2 nm with an electron injection layer, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED.

Figure pat00038
Figure pat00038

상기 실시예 1-5 및 비교예 1에서 제조된 본 발명에 따른 유기 전자재료용 화합물과 종래의 전자전달재료를 함유하는 OLED 소자의 전류효율 및 전력 효율을 각각 1,000 cd/m2에서 측정하여 하기 표 2에 나타내었다. The current efficiency and power efficiency of the OLED device containing the compound for an organic electronic material according to the present invention prepared in Example 1-5 and Comparative Example 1 and a conventional electron transfer material were measured at 1,000 cd / m 2 , respectively. Table 2 shows.

[표 2]TABLE 2

Figure pat00039
Figure pat00039

상기 표 2에서 알 수 있는 바와 같이, 화합물 52를 전자전달재료로 사용하는 경우(실시예 4), 가장 높은 전력 효율을 보였다. 특히, 화합물 52(실시예 4)는 종래의 Alq3를 전자전달층으로 사용했을 때(비교예 1) 대비 전력효율이 15 % 정도 향상되었으며, 화합물 16(실시예 3)은 종래 유기 전계발광 소자(비교예 1)와 비교할 때, 구동전압 면에서 1.4 V 정도 낮추었다.As can be seen in Table 2, when the compound 52 is used as the electron transport material (Example 4), the highest power efficiency was shown. In particular, Compound 52 (Example 4) has improved the power efficiency by about 15% compared to when using the conventional Alq3 as the electron transport layer (Comparative Example 1), Compound 16 (Example 3) is a conventional organic electroluminescent device ( As compared with Comparative Example 1), the voltage was lowered by 1.4 V in terms of driving voltage.

본 발명에서 개발한 화합물들을 전자전달층으로 사용하였을 때의 특성들이 나타난 표 2로부터, 본 발명에서 개발한 화합물들이 성능 측면에서 종래의 재료 대비 우수함을 알 수 있다.
Table 2 shows the properties of the compounds developed in the present invention when used as the electron transport layer, it can be seen that the compounds developed in the present invention are superior to the conventional materials in terms of performance.

[실시예 6 - 8] 본 발명에 따른 유기 발광 화합물을 이용한 OLED 소자 제작Example 6-8 Fabrication of OLED Device Using Organic Light-Emitting Compound According to the Present Invention

본 발명의 발광 재료를 이용한 구조의 OLED 소자를 제작하였다. 우선, OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막(15 Ω/□) 을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. 다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 하기 구조의 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA)을 넣고, 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 60 nm 두께의 정공주입층을 증착하였다.An OLED device having a structure using the light emitting material of the present invention was produced. First, a transparent electrode ITO thin film (15 Ω / □) obtained from an OLED glass (manufactured by Samsung Corning Corporation) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then stored in isopropanol. It was used after. Next, an ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (2) having the structure -TNATA), evacuated until the vacuum in the chamber reached 10 -6 torr, and then applied a current to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate.

이어서, 진공 증착 장비 내의 다른 셀에 하기구조 N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB)을 넣고, 셀에 전류를 인가하여 NPB를 증발시켜 정공주입층 위에 20 nm 두께의 정공전달층을 증착하였다.Subsequently, the following structure N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine (NPB) was added to another cell in the vacuum deposition apparatus, and NPB was applied by applying a current to the cell. A 20 nm thick hole transport layer was deposited on the hole injection layer by evaporation.

Figure pat00040
Figure pat00040

진공 증착 장비 내의 한쪽 셀에 호스트 재료로 10-6torr하에서 진공 승화 정제된 본 발명에 따른 화합물(예 :화합물 7)을 넣고, 다른쪽 셀에는 발광 도판트(예 :화합물 (piq)2Ir(acac))를 각각 넣은 후, 두 물질을 다른 속도로 증발시켜 4 내지 10 중량%로 도핑함으로써 상기 정공 전달층 위에 30 nm 두께의 발광층을 증착하였다.In one cell of a vacuum deposition apparatus, a compound according to the present invention (e.g. Compound 7), which is vacuum sublimated and purified at 10 -6 torr as a host material, is placed, and in another cell, a light emitting dopant (e.g., compound (piq) 2 Ir ( After each of acac)), 30 nm thick light emitting layer was deposited on the hole transport layer by evaporating the two materials at different rates and doping at 4 to 10% by weight.

Figure pat00041
Figure pat00041

이어서 상기 발광층 위에 정공차단층으로 하기 구조의 비스(2-메틸-8-퀴놀리네이토)(p-페닐페놀레이토)알루미늄(III) (Balq)을 5 nm의 두께로 증착시키고, 전자전달층으로써 하기 구조의 tris(8-hydroxyquinoline)-aluminum(III) (Alq3)를 20 nm 두께로 증착한 다음, 전자주입층으로 하기 구조의 화합물 lithium quinolate (Liq)를 1 내지 2 nm 두께로 증착한 후, 다른 진공 증착 장비를 이용하여 Al 음극을 150 nm의 두께로 증착하여 OLED를 제작하였다. Subsequently, bis (2-methyl-8-quinolinate) (p-phenylphenolrato) aluminum (III) (Balq) having the following structure is deposited as a hole blocking layer on the light emitting layer to a thickness of 5 nm, and an electron transport layer As a result of depositing tris (8-hydroxyquinoline) -aluminum (III) (Alq3) having a thickness of 20 nm and then depositing compound lithium quinolate (Liq) having a structure of 1 to 2 nm with an electron injection layer. Using another vacuum deposition equipment, an Al cathode was deposited to a thickness of 150 nm to manufacture an OLED.

Figure pat00042
Figure pat00042

[실시예 9-10] 본 발명에 따른 전기 발광 화합물을 이용한 OLED 소자의 제조Example 9-10 Fabrication of OLED Devices Using Electroluminescent Compounds According to the Present Invention

정공차단층을 제외한 나머지는 실시예 8과 동일한 방법으로 OLED 소자를 제작하였다.Except for the hole blocking layer, an OLED device was manufactured in the same manner as in Example 8.

[비교예 2] 종래의 발광 재료를 이용한 OLED 소자의 발광 특성Comparative Example 2 Light Emitting Characteristics of OLED Devices Using Conventional Light-Emitting Materials

진공 증착 장비 내의 한쪽 셀에 호스트 재료로서 본 발명의 화합물 대신 CBP를 사용한 것 외에는 실시예 6과 동일한 방법으로 OLED 소자를 제작하였다. An OLED device was manufactured in the same manner as in Example 6, except that CBP was used instead of the compound of the present invention as a host material in one cell in the vacuum deposition equipment.

Figure pat00043
Figure pat00043

본 발명에 따른 유기 발광 화합물을 함유하는 실시예 6 내지 실시예 8 및 실시예 9 내지 실시예 10의 OLED 소자와 비교예 2에서 제조된 종래의 발광 화합물을 함유하는 OLED 소자의 구동전압 및 발광효율을 1,000 cd/㎡ 에서 측정하여 하기 표 3에 나타내었다.Driving voltage and luminous efficiency of OLED devices of Examples 6 to 8 and 9 to 10 containing organic light emitting compounds according to the present invention and OLED devices containing conventional light emitting compounds prepared in Comparative Example 2 Was measured in 1,000 cd / ㎡ is shown in Table 3 below.

하기의 표 3으부터 본 발명에서 개발한 유기발광 화합물들이 성능 측면에서 종래의 재료 대비 우수한 특성을 보이는 것을 확인할 수 있다.From Table 3, it can be seen that the organic light emitting compounds developed in the present invention exhibit superior characteristics compared to conventional materials in terms of performance.

[표 3][Table 3]

Figure pat00044
Figure pat00044

상기 표 3으로부터 본 발명에서 개발한 화합물들의 발광 특성이 종래의 재료 대비 우수한 특성을 보이는 것을 확인할 수 있었다. 종래의 재료인 비교예 2의 소자에 비해 우수한 전류특성을 가져 0.2 V 이상 낮아진 구동전압을 나타냈으며, 우수한 발광특성으로 인해 비교예 2의 소자에 비해 1.1배 이상의 높은 전력효율 특성을 나타냈다. It can be seen from Table 3 that the luminescent properties of the compounds developed in the present invention show superior properties compared to conventional materials. Compared with the device of Comparative Example 2, which is a conventional material, the drive voltage was lowered by 0.2 V or more, and the power efficiency was 1.1 times higher than that of Comparative Example 2 due to the excellent light emission characteristics.

Claims (9)

하기 화학식 1로 표시되는 유기 전자재료용 화합물.
[화학식 1]
Figure pat00045

[상기 화학식 1에서,
X는 -C(R1)(R2)-, -Si(R3)(R4)-, -S- 또는 -O-이고;
R1 내지 R4는 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴 또는 헤테로아릴(C3-C30)이거나, R1과 R2 또는 R3와 R4는 서로 독립적으로 융합고리를 포함하거나 포함하지 않는 (C3-C12)알킬렌 또는 (C3-C12)알케닐렌으로 연결되어 스피로고리 또는 융합고리를 형성할 수 있고;
Ar1 내지 Ar4는 서로 독립적으로 수소, (C1-C30)알킬, 할로겐, 디(C1-C30)알킬보라닐, 디(C6-C30)아릴보라닐, 시아노, (C3-C30)시클로알킬, 모폴리노, 티오모폴리노, 피페리디노, 5원 내지 7원의 헤테로시클로알킬, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, 카바졸릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴티오, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 또는 하이드록시이고;
상기 R1 내지 R4의 알킬, 아릴 또는 헤테로아릴 및 Ar1 내지 Ar4의 알킬, 시클로알킬, 헤테로시클로알킬, 바이시클로알킬, 알킬보라닐, 아릴보라닐, 알케닐, 알키닐, 아릴, 알콕시, 아릴옥시, 헤테로아릴, 아르알킬, 아릴티오, 알킬아미노, 아릴아미노, 트리알킬실릴, 디알킬아릴실릴 또는 트리아릴실릴은 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴티오, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 또는 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고;
상기 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함한다.]Compound for an organic electronic material represented by the formula (1).
[Formula 1]
Figure pat00045

[In the above formula (1)
X is —C (R 1 ) (R 2 ) —, —Si (R 3 ) (R 4 ) —, —S— or —O—;
R 1 to R 4 are independently of each other (C1-C30) alkyl, (C6-C30) aryl or heteroaryl (C3-C30), or R 1 and R 2 or R 3 and R 4 are each independently a fused ring. Can be linked with (C3-C12) alkylene or (C3-C12) alkenylene to form a spirogory or fused ring;
Ar 1 to Ar 4 are independently of each other hydrogen, (C1-C30) alkyl, halogen, di (C1-C30) alkylboranyl, di (C6-C30) arylboranyl, cyano, (C3-C30) cycloalkyl , Morpholino, thiomorpholino, piperidino, 5- to 7-membered heterocycloalkyl, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, ( C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, carbazolyl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) Arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy;
Alkyl, aryl or heteroaryl of R 1 to R 4 and alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, alkylboranyl, arylboranyl, alkenyl, alkynyl, aryl, alkoxy of Ar 1 to Ar 4 , Aryloxy, heteroaryl, aralkyl, arylthio, alkylamino, arylamino, trialkylsilyl, dialkylarylsilyl or triarylsilyl is deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen , Cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6- C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) heteroaryl, (C6-C30) aryl Substituted (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) Arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsil , Tri (C6-C30) arylsilyl, it may be further substituted with one or more selected from the group consisting of nitro, or hydroxy;
Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.] 제 1항에 있어서,
X는 X는 -C(R1)(R2)-, -Si(R3)(R4)-, -S- 또는 -O-이거나, 하기 구조에서 선택되는 2가기이고;
Figure pat00046

R1 내지 R4는 서로 독립적으로 (C1-C30)알킬 또는 (C6-C30)아릴이고;
Ar1 내지 Ar4는 서로 독립적으로 (C3-C30)시클로알킬, 모폴리노, 티오모폴리노, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, 카바졸릴, (C6-C30)아릴티오, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴 또는 트리(C6-C30)아릴실릴이고;
상기 R1 내지 R4의 알킬 또는 아릴 및 Ar1 내지 Ar4의 시클로알킬, 바이시클로알킬, 알케닐, 알키닐, 아릴, 아릴옥시, 헤테로아릴, 아릴티오, 트리알킬실릴, 디알킬아릴실릴 또는 트리아릴실릴은 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C7-C30)바이시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (C3-C30)헤테로아릴, (C1-C30)알킬이 치환된 (C3-C30)헤테로아릴, (C6-C30)아릴이 치환된 (C3-C30)헤테로아릴, (C6-C30)아르(C1-C30)알킬, (C6-C30)아릴티오, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, 트리(C1-C30)알킬실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, 트리(C6-C30)아릴실릴, 나이트로 또는 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있는 것을 특징으로 하는 유기 전자재료용 화합물.The method of claim 1,
X is X is -C (R 1 ) (R 2 )-, -Si (R 3 ) (R 4 )-, -S- or -O-, or a divalent group selected from the following structures;
Figure pat00046

R 1 to R 4 are independently of each other (C1-C30) alkyl or (C6-C30) aryl;
Ar 1 to Ar 4 are independently of each other (C3-C30) cycloalkyl, morpholino, thiomorpholino, (C7-C30) bicycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl , (C6-C30) aryl, (C6-C30) aryloxy, (C3-C30) heteroaryl, carbazolyl, (C6-C30) arylthio, tri (C1-C30) alkylsilyl, di (C1-C30) Alkyl (C6-C30) arylsilyl or tri (C6-C30) arylsilyl;
To the R 1 to R 4 alkyl or aryl, and cycloalkyl, bicycloalkyl of Ar 1 to Ar 4 of the alkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl, arylthio, trialkylsilyl, dialkyl aryl silyl or Triarylsilyl is deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30) bike Roalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, ( (C3-C30) heteroaryl substituted with C1-C30) alkyl, (C3-C30) heteroaryl substituted with (C6-C30) aryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) ) Arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, Further substituted with one or more selected from the group consisting of tri (C6-C30) arylsilyl, nitro or hydroxy Number of compounds for organic electronic material, characterized in that. 제 1항 내지 제 2항에서 선택되는 어느 한 항에 따른 유기 전자재료용 화합물을 전자전달재료로 포함하는 것을 특징으로 하는 유기 전계 발광 소자.An organic electroluminescent device comprising the compound for organic electronic material according to any one of claims 1 to 2 as an electron transfer material. 제 3항에 있어서,
상기 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어져 있으며, 상기 유기물층은 상기 화학식 1의 유기 발광 화합물이 포함된 층 하나 이상과 형광호스트-형광도판트 또는 인광호스트-인광도판트로 이루어진 발광층 하나 이상을 포함하는 것을 특징으로 하는 유기 전계 발광 소자. The method of claim 3, wherein
The organic electroluminescent device includes a first electrode; A second electrode; And one or more organic material layers interposed between the first electrode and the second electrode, wherein the organic material layer comprises at least one layer containing the organic light emitting compound of Formula 1 and a fluorescent host-fluorescent plate or phosphorescent host-phosphorescent plate. An organic electroluminescent device comprising at least one light emitting layer consisting of. 제 4항에 있어서,
상기 유기물층에 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 아민계 화합물을 더 포함하는 것을 특징으로 하는 유기 전계 발광 소자. The method of claim 4, wherein
An organic electroluminescent device further comprising at least one amine compound selected from the group consisting of an arylamine compound or a styrylarylamine compound in the organic layer. 제 4항에 있어서,
상기 유기물층에 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 착체화합물을 더 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 4, wherein
An organic electric field further comprising at least one metal or a complex compound selected from the group consisting of Group 1, Group 2, 4, 5 cycle transition metals, lanthanum series metals and organic metals of d-transition elements in the organic layer. Light emitting element. 제 4항에 있어서,
상기 유기물층은 발광층 및 전하생성층을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 4, wherein
The organic material layer is an organic electroluminescent device comprising a light emitting layer and a charge generating layer. 제 4항에 있어서,
상기 유기물층에 청색, 적색 또는 녹색 발광을 하는 유기발광층 하나 이상을 동시에 포함하여 백색 발광을 하는 유기 전계 발광 소자.The method of claim 4, wherein
An organic electroluminescent device which emits white light by simultaneously including at least one organic light emitting layer emitting blue, red or green light in the organic material layer. 제 4항에 있어서,
한 쌍의 전극중 하나 이상의 내측표면에 환원성 도판트(dopant)와 유기물의 혼합 영역, 또는 산화성 도판트와 유기물의 혼합 영역이 배치되는 것을 특징으로 하는 유기 발광 소자.The method of claim 4, wherein
An organic light emitting device according to claim 1, wherein a mixed region of a reducing dopant and an organic material or a mixed region of an oxidative dopant and an organic material is disposed on at least one inner surface of the pair of electrodes.
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