KR20120020818A - 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 PDFInfo
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Abstract
Description
본 발명은 신규한 유기 전자재료용 화합물 및 이를 포함하고 있는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel compound for organic electronic materials and an organic electroluminescent device comprising the same.
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 이루어 여기자를 생성한다. 여기자의 비활성시의 발광(인광 또는 형광)을 이용함으로써 빛이 방출된다. 유기 EL 소자는 약 10V의 전압과 약 100?10,000cd/㎡의 높은 휘도로 편광을 방출하며, 단순히 형광물질을 선택함으로써 파란색에서 빨간색까지의 스펙트럼으로 빛을 방출한다는 특징이 있다. 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, 전력 소모가 비교적 적으며, 색감이 뛰어나다는 장점이 있다. The organic EL element injects charge into an organic film formed between the electron injection electrode (cathode) and the hole injection electrode (anode) to generate excitons by pairing electrons and holes. Light is emitted by using light emission (phosphorescence or fluorescence) when the excitons are inactive. The organic EL device emits polarized light with a voltage of about 10V and a high luminance of about 100 to 10,000 cd / m 2, and emits light in a spectrum from blue to red by simply selecting a fluorescent material. 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 has a relatively low power consumption. It has a small and 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. 이러한 측면에서 호스트 재료의 개발이 해결해야 할 가장 중요한 요소 중의 하나이다. 이때 고체 상태의 용매 및 에너지 전달자 역할을 하는 호스트 물질의 바람직한 특성은 순도가 높아야하며, 진공증착이 가능하도록 적당한 분자량을 가져야 한다. 또한 유리 전이온도와 열분해온도가 높아 열적 안정성을 확보해야하며, 장수명화를 위해 높은 전기화학적 안정성이 요구되며, 무정형박막을 형성하기 용이해야 하며, 인접한 다른 층의 재료들과는 접착력이 좋은 반면 층간이동은 하지 않아야 한다.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. In this respect, the development of host materials is one of the most important factors to be solved. In this case, the desirable properties of the host material serving as a solvent and energy transporter in the solid state should be high in purity and have an appropriate molecular weight to enable vacuum deposition. In addition, high glass transition temperature and pyrolysis temperature should ensure thermal stability, high electrochemical stability is required for long life, easy to form amorphous thin film, good adhesion with other adjacent materials, Should not.
유기 EL 소자를 도핑기술을 사용하여 제조하는 경우 여기상태에서 호스트분자로부터 도판트로의 에너지전달은 100%가 되지 못하고, 도판트뿐만 아니라 호스트물질도 빛을 방출하게 된다. 특히 적색발광소자인 경우에는 호스트물질이 도판트보다 가시성이 큰 파장범위에서 빛을 방출하기 때문에 색순도가 호스트물질의 흐린 광방출에 의해 악화된다. 또 실제로 적용하는 경우 발광수명 및 지속성이 개선될 필요가 있다.When an organic EL device is manufactured using a doping technique, energy transfer from the host molecule to the dopant in the excited state is less than 100%, and not only the dopant but also the host material emits light. In particular, in the case of a red light emitting device, since the host material emits light in a wavelength range where visibility is greater than that of the dopant, color purity is deteriorated by light emission of the host material. In addition, the light emission life and the sustainability need to be improved in practical application.
한편, 인광 발광체의 호스트 재료로는 현재까지 CBP가 가장 널리 알려져 있으며, BCP 및 BAlq 등의 정공차단층을 적용한 고효율의 OLED가 공지되어 있으며, 일본의 파이오니어 등에서는 BAlq 유도체를 호스트로 이용한 고성능의 OLED가 공지되어 있다.On the other hand, CBP is the most widely known host material for phosphorescent emitters, and high-efficiency OLEDs using a hole blocking layer such as BCP and BAlq are known, and high-performance OLEDs using BAlq derivatives as a host are known in Pioneer, Japan. Is known.
그러나 기존의 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮고 열적 안정성이 매우 좋지 않아서, 진공 하에서 고온 증착 공정을 거칠 때, 물질이 변하는 등 단점을 갖고 있다. OLED에서 전력효율 = (π/전압) × 전류효율 이므로, 전력효율은 전압에 반비례하는데, OLED의 소비 전력이 낮으려면 전력 효율이 높아야한다. 실제 인광 발광 재료를 사용한 OLED는 형광 발광 재료를 사용한 OLED에 비해 전류 효율(cd/A)이 상당히 높으나, 인광 발광 재료의 호스트로 BAlq 나 CBP 등 종래의 재료를 사용할 경우, 형광재료를 사용한 OLED에 비해 구동 전압이 높아서 전력 효율(lm/w)면에서 큰 이점이 없었다. 또한, OLED 소자에서의 수명 측면에서도 결코 만족할만한 수준이 되질 못하여 더욱 안정되고, 더욱 성능이 뛰어난 호스트 재료의 개발이 요구되고 있다.However, existing materials have advantages in terms of luminescence properties, but the glass transition temperature is low and the thermal stability is not very good, and thus has a disadvantage such that the material changes when undergoing a high temperature deposition process under vacuum. Since power efficiency = (π / voltage) × current efficiency in OLEDs, power efficiency is inversely proportional to voltage. However, low power consumption of OLEDs requires high power efficiency. Actually, OLEDs using phosphorescent materials have significantly higher current efficiency (cd / A) than OLEDs using fluorescent materials.However, when a conventional material such as BAlq or CBP is used as a host of phosphorescent materials, OLEDs using fluorescent materials Compared with the higher driving voltage, there was no significant advantage in terms of power efficiency (lm / w). In addition, in terms of lifespan in OLED devices, they are never satisfactory, and development of a more stable and more excellent host material is required.
따라서 본 발명의 목적은 첫째로, 상기한 문제점들을 해결하기 위하여 기존의 재료보다 발광 효율 및 소자 수명이 좋으며, 적절한 색좌표를 갖는 우수한 골격의 유기 전자재료용 화합물을 제공하는 것이며 둘째로, 상기 유기 전자재료용 화합물을 발광 재료로서 채용하는 고효율 및 장수명의 유기 전계 발광 소자를 제공하는 것이다. Accordingly, an object of the present invention is to firstly provide a compound for organic electronic material having a good skeleton having an excellent luminous efficiency and device life, and having an appropriate color coordinate, in order to solve the above problems. It is to provide a high efficiency and long life organic electroluminescent element employing a compound for a material as a light emitting material.
본 발명은 하기 화학식 1로 표시되는 유기 전자재료용 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것으로서, 본 발명에 따른 유기 전자재료용 화합물은 기존 재료에 비해 발광 효율이 좋고 재료의 수명특성이 뛰어나 소자의 구동수명이 매우 우수할 뿐만 아니라 전력효율의 상승을 유도하여 소비전력이 개선된 OLED 소자를 제조할 수 있는 장점이 있다.The present invention relates to a compound for an organic electronic material represented by the following formula (1) and an organic electroluminescent device comprising the same, the compound for an organic electronic material according to the present invention has better luminous efficiency and excellent life characteristics of the material than the conventional material The driving life of the device is very excellent and there is an advantage of manufacturing an OLED device with improved power consumption by inducing an increase in power efficiency.
[화학식 1][Formula 1]
[상기 화학식 1에서, [In Formula 1,
L1 및 L2는 서로 독립적으로 화학결합, (C3-C30)시클로알킬렌, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L 1 and L 2 are independently of each other a chemical bond, (C3-C30) cycloalkylene, (C6-C30) arylene or (C3-C30) heteroarylene;
X1 및 X2는 서로 독립적으로 CR6 또는 N이고, 단, X1와 X2가 동시에 CR6는 아니고;X 1 and X 2 are independently of each other CR 6 or N, provided that X 1 and X 2 are not CR 6 simultaneously;
R1 내지 R6는 서로 독립적으로 수소, 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 하이드록시이며;R 1 to R 6 are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (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) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy;
상기 L1 및 L2의 시클로알킬렌, 아릴렌, 헤테로아릴렌 및 상기 R1 내지 R6의 알킬, 시클로알킬, 헤테로시클로알킬, 알케닐, 알키닐, 아릴 및 헤테로아릴은 서로 독립적으로 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있으며;The cycloalkylene, arylene, heteroarylene of L 1 and L 2 and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R 1 to R 6 are each independently deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2-C30 Alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (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) arylsilyl , Tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;
상기 헤테로아릴렌, 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함하고;The heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;
단, 
only,
본 발명에 기재된 「알킬」, 「알콕시」 및 그 외 「알킬」부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함하고, 「시클로알킬」은 단일 고리계 뿐만 아니라 치환 또는 비치환된 아다만틸 또는 치환 또는 비치환된 (C7-C30)바이시클로알킬과 같은 여러 고리계 탄화수소도 포함한다. 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.Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all linear or pulverized forms, and "cycloalkyl" is not only a monocyclic system but also substituted or unsubstituted adamantyl Or several ring-based hydrocarbons such as substituted or unsubstituted (C7-C30) bicycloalkyl. "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’기는 (C1-C20)알킬 또는 (C1-C10)알킬을 포함하고, ‘(C6-C30)아릴’기는 (C6-C20)아릴 또는 (C6-C12)아릴을 포함한다. ‘(C3-C30)헤테로아릴’기는 (C3-C20)헤테로아릴 또는 (C3-C12)헤테로아릴을 포함하고, ‘(C3-C30)시클로알킬’기는 (C3-C20)시클로알킬 또는 (C3-C7)시클로알킬을 포함한다. ‘(C2-C30)알케닐 또는 알키닐’기는 (C2-C20)알케닐 또는 알키닐, (C2-C10)알케닐 또는 알키닐을 포함한다.In addition, the '(C1-C30) alkyl' groups described herein include (C1-C20) alkyl or (C1-C10) alkyl, and the '(C6-C30) aryl' group is a (C6-C20) aryl or (C6-C12) aryl. '(C3-C30) heteroaryl' group includes (C3-C20) heteroaryl or (C3-C12) heteroaryl, and the '(C3-C30) cycloalkyl' group is (C3-C20) cycloalkyl or (C3- C7) cycloalkyl. '(C2-C30) alkenyl or alkynyl' groups include (C2-C20) alkenyl or alkynyl, (C2-C10) alkenyl or alkynyl.
본 발명에 따른 유기 전자재료용 화합물은 하기 화학식 2 또는 3으로 표시될 수 있다.The compound for an organic electronic material according to the present invention may be represented by the following Chemical Formula 2 or 3.
[화학식 2][Formula 2]
[화학식 3](3)
[상기 L1 및 L2는 서로 독립적으로 화학결합, (C3-C30)시클로알킬렌, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며; R1는 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며; R2 내지 R6는 화학식 1에서의 정의와 동일하고; 상기 L1 및 L2의 시클로알킬렌, 아릴렌, 헤테로아릴렌 및 상기 R1의 아릴 및 헤테로아릴은 서로 독립적으로 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.][Wherein L 1 and L 2 are each independently a chemical bond, (C3-C30) cycloalkylene, (C6-C30) arylene or (C3-C30) heteroarylene; R 1 is (C6-C30) aryl or (C3-C30) heteroaryl; R 2 to R 6 are the same as defined in Formula 1; The cycloalkylene, arylene, heteroarylene of L 1 and L 2 and the aryl and heteroaryl of R 1 are each independently deuterium, (C 1 -C 30) alkyl, halo (C 1 -C 30) alkyl, halogen, cyan Furnace, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or Group consisting of di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy It may be further substituted with one or more selected from.]
상기 R1의 헤테로아릴은 하기 구조에서 선택될 수 있다.The heteroaryl of R 1 may be selected from the following structures.
[상기 Y는 NR13, O 또는 S이고; Z는 NR13, CR14R15, O 또는 S이고; R11 내지 R15는 서로 독립적으로 수소, 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 하이드록시이고; A는 단일환 또는 다환의 방향족고리이거나 단일환 또는 다환의 헤테로방향족고리이다.][Y is NR 13 , O or S; Z is NR 13 , CR 14 R 15 , O or S; R 11 to R 15 are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (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) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy; A is a monocyclic or polycyclic aromatic ring or a monocyclic or polycyclic heteroaromatic ring.]
구체적으로, 상기 R1은 하기 구조에서 선택되며;Specifically, R 1 is selected from the following structures;
R2, R3, R4, R5 및 R6는 서로 독립적으로 수소이고;R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen;
L1은 화학결합이거나 하기 구조에서 선택되고;L 1 is a chemical bond or is selected from the following structures;
L2는 화학결합, 페닐렌 또는 시클로헥실렌이다.L 2 is a chemical bond, phenylene or cyclohexylene.
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.
본 발명에 따른 유기 전자재료용 화합물은 하기 반응식 1에 나타난 바와 같이, 제조될 수 있으나, 이에 한정되지는 않고 공지되어 있는 유기합성방법을 이용하여 제조될 수도 있다.The compound for an organic electronic material according to the present invention may be prepared as shown in Scheme 1, but is not limited thereto and may be prepared using a known organic synthesis method.
[반응식 1]Scheme 1
[상기 반응식 1에서 상기 화학식 1에서, L1, L2, X1, X2 및 R1 내지 R5는 화학식 1에서 정의한 바와 동일하고, X는 할로겐이다.][In Reaction Formula 1, in Formula 1, L 1 , L 2 , X 1 , X 2 and R 1 to R 5 are the same as defined in Formula 1, and X is halogen.]
또한, 본 발명은 유기 전계 발광 소자를 제공하며, 본 발명에 따른 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극 및 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어진 유기 전계 발광 소자에 있어서, 상기 유기물층은 상기 화학식 1의 유기 전자재료용 화합물을 하나 이상 포함하는 것을 특징으로 한다. 상기 유기물층은 발광층을 포함하고, 상기 발광층에서 상기 화학식 1의 유기 전자재료용 화합물은 호스트 물질로 사용되어진다. In addition, 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 organic material layer includes a light emitting layer, and the compound for the organic electronic material of Chemical Formula 1 is used as a host material in the light emitting layer.
상기 발광층에서 상기 화학식 1의 유기 전자재료용 화합물이 호스트로 사용되어질 때 하나 이상의 인광 도판트를 포함하는 것을 특징으로 한다. 본 발명의 유기 전계 발광 소자에 적용되는 인광 도판트는 특별히 제한되지는 않으나, 본 발명의 유기 전계 발광 소자에 적용되는 인광 도판트는 하기 화학식 4로 표시되는 화합물로부터 선택되는 것이 바람직하다.When the compound for the organic electronic material of Formula 1 is used as a host in the light emitting layer is characterized in that it comprises at least one phosphorescent dopant. The phosphorescent dopant applied to the organic electroluminescent device of the present invention is not particularly limited, but the phosphorescent dopant applied to the organic electroluminescent device of the present invention is preferably selected from compounds represented by the following formula (4).
[화학식 4][Formula 4]
MM 1One LL 101101 LL 102102 LL 103103
여기서 M1은 7족, 8족, 9족, 10족, 11족, 13족, 14족, 15족 및 16족의 금속으로 이루어진 군으로부터 선택되고, 리간드 L101, L102 및 L103 는 서로 독립적으로 하기 구조로부터 선택되어진다.Wherein M 1 is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, and the ligands L 101 , L 102 and L 103 Are independently selected from the following structures.
[상기 화학식 4에서, [In Formula 4,
R201 내지 R203은 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬, (C1-C30)알킬이 치환되거나 치환되지 않은 (C6-C30)아릴 또는 할로겐이고;R 201 to R 203 are independently of each other hydrogen, deuterium, (C1-C30) alkyl with or without halogen, (C6-C30) aryl or halogen with or without (C1-C30) alkyl;
R204 내지 R219는 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C1-C30)알콕시, 치환 또는 비치환된(C3-C30)시클로알킬, 치환 또는 비치환된(C2-C30)알케닐, 치환 또는 비치환된(C6-C30)아릴, 치환 또는 비치환된 모노 또는 치환 또는 비치환된 디-(C1-C30)알킬아미노, 치환 또는 비치환된 모노 또는 디-(C6-C30)아릴아미노, SF5, 치환 또는 비치환된 트리(C1-C30)알킬실릴, 치환 또는 비치환된 디(C1-C30)알킬(C6-C30)아릴실릴, 치환 또는 비치환된 트리(C6-C30)아릴실릴, 시아노 또는 할로겐이고;R 204 to R 219 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, Substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted mono or substituted or unsubstituted di- (C1-C30) alkylamino, substituted or unsubstituted Substituted mono or di- (C6-C30) arylamino, SF 5 , substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl , Substituted or unsubstituted tri (C6-C30) arylsilyl, cyano or halogen;
R220 내지 R223는 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬 또는 (C1-C30)알킬이 치환되거나 치환되지 않은 (C6-C30)아릴이고;R 220 to R 223 are each independently hydrogen, deuterium, (C1-C30) alkyl with or without halogen, or (C6-C30) aryl with or without (C1-C30) alkyl;
R224 및 R225는 서서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴 또는 할로겐이거나, R224와 R225는 융합고리를 포함하거나 포함하지 않는 (C3-C12)알킬렌 또는 (C3-C12)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성하며; R 224 and R 225 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R 224 and R 225 are fused to Linked with (C3-C12) alkylene or (C3-C12) alkenylene with or without formation to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
R226은 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴, 치환 또는 비치환된(C5-C30)헤테로아릴 또는 할로겐이고;R 226 is substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C5-C30) heteroaryl or halogen;
R227 내지 R229은 서로 독립적으로 수소, 중수소, 치환 또는 비치환된(C1-C30)알킬, 치환 또는 비치환된(C6-C30)아릴 또는 할로겐이고;R 227 to R 229 are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen;
Q는 
Q is
상기 화학식 4의 인광도판트 화합물은 하기 구조의 화합물로 예시될 수 있으나 이에 한정하는 것은 아니다.The phosphorescent dopant compound of Formula 4 may be exemplified as a compound having the following structure, but is not limited thereto.
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 발광층 및 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 include one or more metals or complex compounds selected from the group consisting of, the organic material layer may include a light emitting layer and a charge generating layer.
또한, 상기 유기물층에 상기 유기 전자재료용 화합물 이외에 청색, 적색 또는 녹색 발광 화합물을 포함하는 유기발광층 하나 이상을 동시에 포함하여 백색 발광을 하는 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, an organic electroluminescent device that emits white light may be formed by simultaneously including one or more organic light emitting layers including blue, red, or green light emitting compounds in addition to the organic electronic material compound. 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 발광소자를 제작할 수 도 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, the reducing dopant layer The white organic electroluminescent device having two or more light emitting layers may be manufactured using the charge generating layer.
본 발명에 따른 유기 전자재료용 화합물은 발광 효율이 좋고 소자의 구동전압을 저하시키고 동시에 전력효율이 향상된 OLED 소자를 제조할 수 있는 장점이 있다.The compound for an organic electronic material according to the present invention has an advantage of being able to manufacture an OLED device having good luminous efficiency and lowering driving voltage of the device and at the same time improving power efficiency.
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 4의 제조Preparation Example 1 Preparation of Compound 4
화합물 compound 1-11-1 의 제조Manufacture
1-브로모-2-니트로벤젠 10g(49.5mmol), 1-나프탈렌보론산 10.2g(59.3mmol), 톨루엔 200mL, 에탄올 50mL 및 물 50 mL을 혼합한 후 Pd(PPh3)4 2.9g(2.5mmol)과 탄산칼륨 20.5g(148.3 mmol)을 첨가하였다. 상기 혼합물을 120℃에서 5시간동안 교반시킨 후 실온으로 식히고 염화암모늄 수용액 40mL로 반응을 종결시켰다. 상기 혼합물을 EA 500mL로 추출한 후, 증류수 100mL로 씻어주었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 실리카겔 컬럼크로마토그래피로 정제하여 화합물 1-1 (10 g, 81%)을 얻었다.10 g (49.5 mmol) of 1-bromo-2-nitrobenzene, 10.2 g (59.3 mmol) of 1-naphthaleneboronic acid, 200 mL of toluene, 50 mL of ethanol and 50 mL of water, followed by 2.9 g (2.5) of Pd (PPh 3 ) 4 mmol) and 20.5 g (148.3 mmol) of potassium carbonate were added. The mixture was stirred at 120 ° C. for 5 hours, then cooled to room temperature and terminated with 40 mL of aqueous ammonium chloride solution. The mixture was extracted with EA 500 mL and washed with distilled water 100 mL. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. Purification by silica gel column chromatography gave Compound 1-1 (10 g, 81%).
화합물 compound 1-21-2 의 제조Manufacture
화합물 1-1 10g(40.1mmol)을 1,2-디클로로벤젠 100mL에 녹인 후 트리에톡시포스핀 100mL를 첨가하였다. 상기 반응혼합물을 150℃에서 20시간동안 교반시킨 후 상온으로 냉각하고 용매인 1,2-디클로로벤젠과 트리에톡시포스핀은 감압 증류를 통해서 제거하였다. 남겨진 유기물은 EA 300mL로 추출한 후, 증류수 40mL로 씻어주었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 실리카겔 컬럼크로마토그래피로 정제하여 화합물 1-2 (7 g, 80%)을 얻었다.10 g (40.1 mmol) of Compound 1-1 was dissolved in 100 mL of 1,2-dichlorobenzene, and then 100 mL of triethoxyphosphine was added thereto. The reaction mixture was stirred at 150 ° C. for 20 hours, cooled to room temperature, and solvents 1,2-dichlorobenzene and triethoxyphosphine were removed by distillation under reduced pressure. The remaining organics were extracted with EA 300mL and washed with 40mL of distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. Purification by silica gel column chromatography gave Compound 1-2 (7 g, 80%).
화합물 compound 1-31-3 의 제조Manufacture
화합물 1-2 20g(92mmol)과 1-브로모-4-요오드벤젠 43.5g(184mmol)을 톨루엔 500mL에 녹인 후 CuI 8.8g(46 mmol), 디아미노에탄 6.2mL(92mmol)과 K3PO4 58.7g(276mmol)을 첨가하고 30시간동안 환류시켰다. 상기 반응혼합물을 상온으로 냉각한 후 2.0M 염산수용액 50mL로 반응을 종결시키고 EA 1L로 추출한 후, 증류수 200mL로 씻어었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 실리카겔 컬럼크로마토그래피로 정제하여 화합물 1-3 (19 g, 56%)을 얻었다.20 g (92 mmol) of Compound 1-2 and 43.5 g (184 mmol) of 1-bromo-4-iodinebenzene were dissolved in 500 mL of toluene, followed by 8.8 g (46 mmol) of CuI, 6.2 mL (92 mmol) of diaminoethane, and K 3 PO 4. 58.7 g (276 mmol) was added and refluxed for 30 h. After cooling the reaction mixture to room temperature, the reaction was terminated with 50 mL of 2.0M aqueous hydrochloric acid solution, extracted with EA 1L, and washed with distilled water 200mL. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. Purification by silica gel column chromatography gave Compound 1-3 (19 g, 56%).
화합물 compound 1-41-4 의 제조Manufacture
화합물 1-3 19g(51mmol)을 THF 250mL에 녹인 후 -78℃로 냉각시킨 후 n-BuLi(2.5 M in hexane) 24.5mL를 -78℃에서 첨가하였다. 상기 혼합물을 -78℃ 에서 1시간동안 교반한 후 B(OMe)3 8.5mL를 첨가하고 2시간동안 교반시키고 염화암모늄 수용액 100mL로 반응을 종결시켰다. 그 다음, EA 500mL로 추출한 후, 증류수 100mL로 씻어었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 재결정하여 화합물 1-4 (14 g, 81%)을 얻었다.19 g (51 mmol) of Compound 1-3 was dissolved in 250 mL of THF, and then cooled to −78 ° C., and then 24.5 mL of n-BuLi (2.5 M in hexane) was added at −78 ° C. The mixture was stirred at −78 ° C. for 1 h, then 8.5 mL of B (OMe) 3 was added, stirred for 2 h and the reaction was terminated with 100 mL of aqueous ammonium chloride solution. Then, after extracting with EA 500mL, and washed with distilled water 100mL. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. Recrystallization gave compound 1-4 (14 g, 81%).
화합물 compound 2-12-1 의 제조Manufacture
플루오란센 50g(247mmol)을 니트로벤젠 1L에 녹인 후 니트로벤젠 200mL에 묽혀진 브롬 12mL(234.7mmol)를 천천히 적가하였다. 모든 용액이 적가된 후 20시간동안 실온에서 교반시켰다. 상기 반응용액에 포화된 티오황산염화나트륨 수용액 500mL를 첨가하여 반응을 종결시켰다. 상기 혼합물을 EA 3L로 추출한 후, 증류수 1L로 씻어주었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 실리카겔 필터 후 재결정하여 화합물 2-1 (65 g, 94%)을 얻었다.50 g (247 mmol) of fluoranthene was dissolved in 1 L of nitrobenzene, and 12 mL (234.7 mmol) of bromine diluted in 200 mL of nitrobenzene was slowly added dropwise. After all the solution was added dropwise it was stirred for 20 hours at room temperature. 500 mL of saturated sodium thiosulfate aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with EA 3L and washed with distilled water 1L. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. After recrystallization after silica gel filter compound 2-1 (65 g, 94%) was obtained.
화합물 compound 2-22-2 의 제조Manufacture
화합물 2-1 24.5g(87.1mmol)을 THF 500mL에 녹인 후 -78℃로 냉각시키고 n-BuLi(2.5 M in hexane) 45mL를 첨가하고 1시간동안 교반하였다. 그런 다음, B(OMe)3 15mL를 첨가하고 2시간동안 교반시키고 염화암모늄 수용액 250mL로 반응을 종결시켰다. EA 1L로 추출한 후, 증류수 200mL로 씻어준다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 재결정하여 화합물 2-2 (14 g, 65%) 을 얻었다.24.5 g (87.1 mmol) of Compound 2-1 was dissolved in 500 mL of THF, cooled to −78 ° C., and 45 mL of n-BuLi (2.5 M in hexane) was added thereto, followed by stirring for 1 hour. Then, 15 mL of B (OMe) 3 was added, stirred for 2 hours, and the reaction was terminated with 250 mL of aqueous ammonium chloride solution. After extracting with EA 1L, wash with distilled water 200mL. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. Recrystallization gave compound 2-2 (14 g, 65%).
화합물 compound 2-32-3 의 제조Manufacture
2,4-디클로로퀴나졸린 8.1g(40.6mmol), 화합물 2-2 10g(40.6mmol), 톨루엔 200mL, 에탄올 50mL 및 물 50mL를 혼합한 후 Pd(PPh3)4 1.9g(1.64mmol)과 K2CO3 12.9g(122mmol)을 첨가하였다. 상기 혼합물을 120℃에서 5시간동안 교반시킨 후 실온으로 식히고 염화암모늄 수용액 200mL로 반응을 종결시켰다. 상기 혼합물을 EA 500mL로 추출한 후, 증류수 50 mL로 씻어주었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 실리카겔 필터 후 재결정하여 화합물 2-3 (10 g, 68%)을 얻었다.8.1 g (40.6 mmol) of 2,4-dichloroquinazoline, 10 g (40.6 mmol) of Compound 2-2 , 200 mL of toluene, 50 mL of ethanol and 50 mL of water, followed by 1.9 g (1.64 mmol) of Pd (PPh 3 ) 4 and K 12.9 g (122 mmol) of 2 CO 3 were added. The mixture was stirred at 120 ° C. for 5 hours, then cooled to room temperature and terminated with 200 mL of aqueous ammonium chloride solution. The mixture was extracted with EA 500mL and washed with 50 mL of distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. After recrystallization after silica gel filter compound 2-3 (10 g, 68%) was obtained.
화합물 compound 44 의 제조Manufacture
화합물 2-3 5.0g(13.7mmol), 화합물 1-4 5.54g(16.4mmol)을 톨루엔 100mL, 에탄올 20mL 및 물 20mL를 혼합한 후 Pd(PPh3)4 1.6g(1.4mmol)과 K2CO3 5.7g(41.1mmol)을 첨가하였다. 상기 혼합물을 120℃에서 5시간동안 교반시킨 후 실온으로 식히고 염화암모늄 수용액 20mL로 반응을 종결시켰다. 상기 혼합물을 EA 250mL로 추출한 후, 증류수 30mL로 씻어주었다. 얻어진 유기층을 무수MgSO4로 건조하고, 유기용매는 감압하에서 제거하였다. 실리카겔 필터 후 재결정하여 화합물 4 (5.9 g, 69%)을 얻었다.5.0 g (13.7 mmol) of Compound 2-3 , 5.54 g (16.4 mmol) of Compound 1-4 were mixed with 100 mL of toluene, 20 mL of ethanol and 20 mL of water, followed by 1.6 g (1.4 mmol) of Pd (PPh 3 ) 4 and K 2 CO. 3 5.7 g (41.1 mmol) was added. The mixture was stirred at 120 ° C. for 5 hours, then cooled to room temperature and terminated with 20 mL of aqueous ammonium chloride solution. The mixture was extracted with EA 250mL and washed with distilled water 30mL. The obtained organic layer was dried over anhydrous MgSO 4 , and the organic solvent was removed under reduced pressure. Compound 4 (5.9 g, 69%) was obtained by recrystallization after a silica gel filter.
MS/FAB: 621.22(found), 621.73(calculated)
MS / FAB: 621.22 (found), 621.73 (calculated)
[실시예 1] 본 발명에 따른 유기 전자재료용 화합물을 이용한 OLED 소자 제작Example 1 Fabrication of an OLED Device Using a Compound for Organic Electronic Materials 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 2-TNATA (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine)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 NPB (N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine)을 넣고, 셀에 전류를 인가하여 NPB를 증발시켜 정공주입층 위에 20 nm 두께의 정공전달층을 증착하였다. 진공 증착 장비 내의 한쪽 셀에 호스트 재료로 10-6 torr하에서 진공 승화 정제된 본 발명에 따른 화합물 3을 넣고, 다른쪽 셀에는 발광 도판트로서 (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate]를 각각 넣은 후, 두 물질을 다른 속도로 증발시켜 4 내지 20 중량%로 도핑함으로써 상기 정공 전달층 위에 30 nm 두께의 발광층을 증착하였다. 이어서 전자전달층으로써 Alq (tris(8-hydroxyquinoline)-aluminum(III))를 20 nm 두께로 증착한 다음, 전자주입층으로 Liq (lithium quinolate)를 1 내지 2 nm 두께로 증착한 후, 다른 진공 증착 장비를 이용하여 Al 음극을 150 nm의 두께로 증착하여 OLED를 제작하였다. 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, the ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 2-TNATA (4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine) is installed in the cell in the vacuum deposition apparatus. And evacuated until the vacuum in the chamber reached 10 −6 torr, followed by applying a current to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate. ( '-bis (α-naphthyl) - N, N' N, N -diphenyl-4,4'-diamine) NPB to another cell of the vapor deposition devices placed to evaporate NPB to apply a current to the cell, the hole injection layer A 20 nm-thick hole transport layer was deposited on one side of the vacuum deposition equipment, and the compound 3 according to the present invention was vacuum sublimated under 10 -6 torr as a host material, and the other cell (piq) was used as a light emitting dopant. ) of 2 Ir (acac) [bis- ( 1-phenylisoquinolyl) iridium (III) acetylacetonate] after loading, respectively, the two materials were evaporated at different rates from 4 to 20 A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping at%, followed by deposition of Alq (tris (8-hydroxyquinoline) -aluminum (III)) having a thickness of 20 nm as an electron transport layer, followed by an electron injection layer. After depositing Liq (lithium quinolate) to a thickness of 1 to 2 nm, an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED.
재료 별로 각 화합물은 10-6 torr 하에서 진공 승화 정제하여 OLED 발광재료로 사용하였다.For each material, the compound was vacuum sublimated under 10-6 torr and used as an OLED light emitting material.
그 결과, 6.5 V의 전압에서 14.0 mA/cm2의 전류가 흘렀으며, 1052 cd/m2의 적색발광이 확인되었다.As a result, a current of 14.0 mA / cm 2 flowed at a voltage of 6.5 V, and red light emission of 1052 cd / m 2 was confirmed.
[실시예 2][Example 2]
발광층에서 호스트 재료로서 화합물 4를 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 4 was used as the host material in the light emitting layer.
그 결과, 7.5 V의 전압에서 14.0 mA/cm2의 전류가 흘렀으며, 1060 cd/m2의 적색발광이 확인되었다. As a result, a current of 14.0 mA / cm 2 flowed at a voltage of 7.5 V, and red emission of 1060 cd / m 2 was confirmed.
[실시예 3]Example 3
발광층에서 호스트 재료로서 화합물 8을 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 8 was used as the host material in the light emitting layer.
그 결과, 6.7 V의 전압에서 14.6 mA/cm2의 전류가 흘렀으며, 1022 cd/m2의 적색발광이 확인되었다. As a result, a current of 14.6 mA / cm 2 flowed at a voltage of 6.7 V, and red light emission of 1022 cd / m 2 was confirmed.
광이 확인되었다. The light was confirmed.
[실시예 4]Example 4
발광층에서 호스트 재료로서 화합물 14를 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 14 was used as the host material in the emission layer.
그 결과, 6.8 V의 전압에서 14.1 mA/cm2의 전류가 흘렀으며, 1030 cd/m2의 적색발광이 확인되었다. As a result, a current of 14.1 mA / cm 2 flowed at a voltage of 6.8 V, and red emission of 1030 cd / m 2 was confirmed.
[실시예 5]Example 5
발광층에서 호스트 재료로서 화합물 15를 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 15 was used as the host material in the emission layer.
그 결과, 6.5 V의 전압에서 13.9 mA/cm2의 전류가 흘렀으며, 1035 cd/m2의 적색발광이 확인되었다. As a result, a current of 13.9 mA / cm 2 flowed at a voltage of 6.5 V, and red emission of 1035 cd / m 2 was confirmed.
[실시예 6][Example 6]
발광층에서 호스트 재료로서 화합물 16을 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 16 was used as the host material in the light emitting layer.
그 결과, 6.3 V의 전압에서 14.6 mA/cm2의 전류가 흘렀으며, 1041 cd/m2의 적색발광이 확인되었다. As a result, a current of 14.6 mA / cm 2 flowed at a voltage of 6.3 V, and red light emission of 1041 cd / m 2 was confirmed.
[실시예 7]Example 7
발광층에서 호스트 재료로서 화합물 20을 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 20 was used as the host material in the light emitting layer.
그 결과, 6.4 V의 전압에서 14.2 mA/cm2의 전류가 흘렀으며, 1048 cd/m2의 적색발광이 확인되었다.As a result, a current of 14.2 mA / cm 2 flowed at a voltage of 6.4 V, and red light emission of 1048 cd / m 2 was confirmed.
[비교예 1]Comparative Example 1
발광층에서 호스트 재료로서 본 발명의 화합물 대신 4,4‘-bis(carbazol-9-yl)biphenyl(CBP)를 이용하고, 정공차단층으로 비스(2-메틸-8-퀴놀리네이토)(p-페닐페놀레이토)알루미늄(III) (Balq)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 OLED 소자를 제작하였다.4,4'-bis (carbazol-9-yl) biphenyl (CBP) was used as a host material in the light emitting layer instead of the compound of the present invention, and bis (2-methyl-8-quinolinate) (p) was used as the hole blocking layer. An OLED device was manufactured in the same manner as in Example 1, except that -phenylphenolrato) aluminum (III) (Balq) was used.
그 결과, 7.5 V의 전압에서 15.3 mA/cm2의 전류가 흘렀으며, 1000 cd/m2의 적색발광이 확인되었다.
As a result, a current of 15.3 mA / cm 2 flowed at a voltage of 7.5 V, and red light emission of 1000 cd / m 2 was confirmed.
본 발명에서 개발한 유기 발광 화합물들의 발광 특성이 종래의 재료 대비 우수한 특성을 보이는 것을 확인할 수 있었다. 또한 플루오란센이 치환기로 도입된 본 발명에 따른 유기 발광 화합물을 발광용 호스트 재료로 사용한 소자는 발광특성이 뛰어날 뿐만 아니라 구동전압을 0.7 ~ 1.2 V 강하시켜줌으로써 전력효율의 상승을 유도하여 소비전력을 개선시킬 수 있었다. It was confirmed that the luminescence properties of the organic light emitting compounds developed in the present invention showed superior properties compared to the conventional materials. In addition, the device using the organic light emitting compound according to the present invention, in which the fluoranthene is introduced as a substituent, is not only excellent in light emitting characteristics but also leads to an increase in power efficiency by lowering the driving voltage by 0.7 to 1.2 V. Could improve.
Claims (10)
[화학식 1]
[상기 화학식 1에서,
L1 및 L2는 서로 독립적으로 화학결합, (C3-C30)시클로알킬렌, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;
X1 및 X2는 서로 독립적으로 CR6 또는 N이고, 단, X1와 X2가 동시에 CR6는 아니고;
R1 내지 R6는 서로 독립적으로 수소, 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 하이드록시이며;
상기 L1 및 L2의 시클로알킬렌, 아릴렌, 헤테로아릴렌 및 상기 R1 내지 R6의 알킬, 시클로알킬, 헤테로시클로알킬, 알케닐, 알키닐, 아릴 및 헤테로아릴은 서로 독립적으로 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있으며;
상기 헤테로아릴렌, 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함하고;
단,
[Formula 1]
[In the above formula (1)
L 1 and L 2 are independently of each other a chemical bond, (C3-C30) cycloalkylene, (C6-C30) arylene or (C3-C30) heteroarylene;
X 1 and X 2 are independently of each other CR 6 or N, provided that X 1 and X 2 are not CR 6 simultaneously;
R 1 to R 6 are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (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) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy;
The cycloalkylene, arylene, heteroarylene of L 1 and L 2 and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R 1 to R 6 are each independently deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2-C30 Alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (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) arylsilyl , Tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;
The heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;
only,
하기 화학식 2 또는 3으로 표시되는 유기 전자재료용 화합물.
[화학식 2]
[화학식 3]
[상기 L1 및 L2는 서로 독립적으로 화학결합, (C3-C30)시클로알킬렌, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며; R1는 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며; R2 내지 R6는 화학식 1에서의 정의와 동일하고; 상기 L1 및 L2의 시클로알킬렌, 아릴렌, 헤테로아릴렌 및 상기 R1의 아릴 및 헤테로아릴은 서로 독립적으로 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 및 하이드록시로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.]The method of claim 1,
Compound for an organic electronic material represented by the following formula (2) or (3).
(2)
(3)
[Wherein L 1 and L 2 are each independently a chemical bond, (C3-C30) cycloalkylene, (C6-C30) arylene or (C3-C30) heteroarylene; R 1 is (C6-C30) aryl or (C3-C30) heteroaryl; R 2 to R 6 are the same as defined in Formula 1; The cycloalkylene, arylene, heteroarylene of L 1 and L 2 and the aryl and heteroaryl of R 1 are each independently deuterium, (C 1 -C 30) alkyl, halo (C 1 -C 30) alkyl, halogen, cyan Furnace, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or Group consisting of di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy It may be further substituted with one or more selected from.]
상기 R1은 하기 구조에서 선택되는 헤테로아릴인 것을 특징으로 하는 유기 전자재료용 화합물.
[상기 Y는 NR13, O 또는 S이고; Z는 NR13, CR14R15, O 또는 S이고; R11 내지 R15는 서로 독립적으로 수소, 중수소, (C1-C30)알킬, 할로(C1-C30)알킬, 할로겐, 시아노, (C3-C30)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C6-C30)아릴, (C1-C30)알콕시, (C6-C30)아릴옥시, (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 하이드록시이고; A는 단일환 또는 다환의 방향족고리이거나 단일환 또는 다환의 헤테로방향족고리이다.]The method of claim 1,
R 1 is a compound for organic electronic materials, characterized in that heteroaryl selected from the following structure.
[Y is NR 13 , O or S; Z is NR 13 , CR 14 R 15 , O or S; R 11 to R 15 are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (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) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy; A is a monocyclic or polycyclic aromatic ring or a monocyclic or polycyclic heteroaromatic ring.]
상기 R1은 하기 구조에서 선택되며;
R2, R3, R4, R5 및 R6는 서로 독립적으로 수소이고;
L1은 화학결합이거나 하기 구조에서 선택되고;
L2는 화학결합, 페닐렌 또는 시클로헥실렌인 것을 특징으로 하는 유기 전자재료용 화합물.The method of claim 1,
R 1 is selected from the following structures;
R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen;
L 1 is a chemical bond or is selected from the following structures;
L 2 is a chemical bond, phenylene or cyclohexylene, characterized in that the organic electronic material compound.
하기 화합물로부터 선택되는 유기 전자재료용 화합물.
A compound for organic electronic materials selected from the following compounds.
상기 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어져 있으며, 상기 유기물층은 상기 유기 전자재료용 화합물 하나 이상과 인광 도판트 하나 이상을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 6,
The organic electroluminescent device includes 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 comprises at least one compound for an organic electronic material and at least one phosphorescent dopant.
상기 유기물층에 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 아민계 화합물 또는 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 7, wherein
At least one amine compound selected from the group consisting of an arylamine compound or a styrylarylamine compound or an organic metal of Group 1, Group 2, 4 cycle, 5 cycle transition metal, lanthanide series metal and d-transition element in the organic layer An organic electroluminescent device further comprising at least one metal or complex compound selected from the group consisting of:
상기 유기물층은 발광층 및 전하생성층을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 7, wherein
The organic material layer is an organic electroluminescent device comprising a light emitting layer and a charge generating layer.
상기 유기물층에 청색, 적색 또는 녹색 발광을 하는 유기발광층 하나 이상을 더 포함하여 백색 발광을 하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 7, wherein
The organic light emitting device of claim 1, further comprising at least one organic light emitting layer for emitting blue, red or green light to the organic material layer.
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| KR1020100084679A KR20120020818A (en) | 2010-08-31 | 2010-08-31 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| CN2011800499936A CN103201273A (en) | 2010-08-31 | 2011-08-30 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| PCT/KR2011/006412 WO2012030145A1 (en) | 2010-08-31 | 2011-08-30 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| JP2013525846A JP5830097B2 (en) | 2010-08-31 | 2011-08-30 | Novel compounds for organic electronic materials and organic electroluminescent devices using the same |
| TW100131227A TW201217356A (en) | 2010-08-31 | 2011-08-31 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
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| KR20150035706A (en) * | 2012-07-05 | 2015-04-07 | 도레이 카부시키가이샤 | Light emitting elment material and light emitting element |
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| JPWO2012017680A1 (en) | 2010-08-05 | 2013-10-03 | 出光興産株式会社 | Organic electroluminescence device |
| KR20120038060A (en) * | 2010-10-13 | 2012-04-23 | 롬엔드하스전자재료코리아유한회사 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| WO2014081168A1 (en) * | 2012-11-21 | 2014-05-30 | 주식회사 엘지화학 | Fluoranthene compound, and organic electronic device comprising same |
| JP6430709B2 (en) * | 2013-03-15 | 2018-11-28 | ダウ グローバル テクノロジーズ エルエルシー | Quinazoline-derived compounds for electronic films and devices |
| WO2014178434A1 (en) | 2013-05-02 | 2014-11-06 | 出光興産株式会社 | Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device |
| CN106458899A (en) | 2014-05-28 | 2017-02-22 | 东丽株式会社 | Fluoranthene derivative, electronic device containing same, light-emitting element, and photoelectric conversion element |
| KR102360782B1 (en) * | 2017-07-20 | 2022-02-10 | 삼성디스플레이 주식회사 | Organic light emitting device |
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| JP2003109765A (en) * | 2001-09-28 | 2003-04-11 | Canon Inc | Organic light emitting element |
| JP4646494B2 (en) * | 2002-04-11 | 2011-03-09 | 出光興産株式会社 | Novel nitrogen-containing heterocyclic derivative and organic electroluminescence device using the same |
| US7867629B2 (en) * | 2003-01-10 | 2011-01-11 | Idemitsu Kosan Co., Ltd. | Nitrogenous heterocyclic derivative and organic electroluminescent element employing the same |
| CN1934906A (en) * | 2004-03-19 | 2007-03-21 | 出光兴产株式会社 | organic electroluminescent element |
| JP4585786B2 (en) * | 2004-04-01 | 2010-11-24 | キヤノン株式会社 | Light emitting element and display device |
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| JP2007261969A (en) * | 2006-03-28 | 2007-10-11 | Canon Inc | 2,6-fluorenyl-substituted pyridine compound and organic luminescent element using the same |
| JP2007308477A (en) * | 2006-04-20 | 2007-11-29 | Canon Inc | Compound and organic light-emitting device |
| CN102197027A (en) * | 2008-08-22 | 2011-09-21 | 株式会社Lg化学 | Material for organic electronic device, and organic electronic device using the same |
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