KR20140035737A - Novel organic electroluminescence compounds and organic electroluminescence device containing the same - Google Patents

Novel organic electroluminescence compounds and organic electroluminescence device containing the same Download PDF

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KR20140035737A
KR20140035737A KR1020120102392A KR20120102392A KR20140035737A KR 20140035737 A KR20140035737 A KR 20140035737A KR 1020120102392 A KR1020120102392 A KR 1020120102392A KR 20120102392 A KR20120102392 A KR 20120102392A KR 20140035737 A KR20140035737 A KR 20140035737A
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substituted
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안희춘
문두현
김승애
이경주
이태진
권혁주
김봉옥
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롬엔드하스전자재료코리아유한회사
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Priority to KR1020120102392A priority Critical patent/KR20140035737A/en
Priority to PCT/KR2013/008206 priority patent/WO2014042420A1/en
Priority to TW102133122A priority patent/TW201420582A/en
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Abstract

The present invention relates to a new organic electroluminescence compound and an organic electroluminescence diode containing the same. The organic electroluminescence compound, according to the present invention, is excellent in light emitting properties, and can be used to manufacture an organic light emitting diode (OLED) having enhanced energy efficiency, by reducing the driving voltage of the diode. The electroluminescence compound is represented in the below chemical formula 1. L1, and L2 are respectively and independently, single-bonded, substituted or non-substituted C6-C30 arylene, or a substituted or non-substituted heteroarylene. Ar1 and Ar2 are respectively and independently, substituted, or non-substituted C6-C30 Aryl, or substituted, or non-substituted C5-C30 heteroarylene. X stands for oxygen atom, sulfur atom, or CR5CR6.

Description

신규한 유기 전계 발광 화합물 및 이를 포함하는 유기 전계 발광 소자{Novel organic electroluminescence compounds and organic electroluminescence device containing the same}Novel organic electroluminescence compounds and organic electroluminescence device containing the same

본 발명은 신규한 유기 전계 발광 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다. The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same.

표시 소자 중, 전계 발광 소자(electroluminescence device: EL 소자)는 자체 발광형 표시 소자로서 시야각이 넓고 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다. 1987년 이스트만 코닥(Eastman Kodak)사는 발광층 형성용 재료로서 저분자인 방향족 디아민과 알루미늄 착물을 이용하고 있는 유기 EL 소자를 처음으로 개발하였다[참조: Appl. Phys. Lett. 51, 913, 1987].Among display devices, an electroluminescence device (EL device) is a self-luminous display device having a wide viewing angle, excellent contrast, and fast response speed. In 1987, Eastman Kodak Company first developed an organic EL device using an aromatic diamine and an aluminum complex having a low molecular weight as a material for forming a light emitting layer (Appl. Phys. Lett. 51, 913, 1987].

유기 EL 소자에서 발광 효율을 결정하는 가장 중요한 요인은 발광 재료이다. 발광 재료로는 현재까지 형광 발광 재료가 널리 사용되고 있으나, 전계 발광의 메커니즘상 형광 발광 재료에 비해 인광 발광 재료가 이론적으로 4배까지 발광 효율을 개선시킬 수 있다는 점에서 인광 발광 재료의 개발 연구가 널리 수행되고 있다. 현재까지 이리듐(III) 착물 계열이 인광 발광 재료로 널리 알려져 있으며, 각 RGB 별로는 비스(2-(2'-벤조티에닐)-피리디네이토-N,C-3')이리듐(아세틸아세토네이트)[(acac)Ir(btp)2], 트리스(2-페닐피리딘)이리듐 [Ir(ppy)3] 및 비스(4,6-디플루오로페닐피리디네이토-N,C2)피콜리네이토이리듐 [Firpic] 등의 재료가 알려져 있다.The most important factor for determining the luminous efficiency in the organic EL device is the luminescent material. As a luminescent material, a fluorescent luminescent material has been widely used, but the development of a phosphorescent luminescent material has been extensively studied in view of the fact that phosphorescent luminescent material can improve luminescent efficiency up to 4 times theoretically compared to a fluorescent luminescent material in the mechanism of electroluminescence . To date, iridium (III) complexes are widely known as phosphorescent materials, and bis (2- (2'-benzothienyl) -pyridinate-N, C-3 ') iridium (acetylacetonate) for each RGB ) [(acac) Ir (btp) 2 ], tris (2-phenylpyridine) iridium [Ir (ppy) 3 ] and bis (4,6-difluorophenylpyridinato-N, C2) picoline Materials such as Toyridium [Firpic] are known.

발광 재료는 색순도, 발광 효율 및 안정성을 향상시키기 위해 호스트 재료에 발광 재료(도펀트)를 혼합하여 사용하기도 한다. 이와 같은 발광 재료(도펀트)/호스트 재료 체계를 사용할 때, 호스트 재료는 발광 소자의 효율과 성능에 큰 영향을 미치므로, 그 선택이 중요하다. 종래 기술에서, 인광용 호스트 재료로는 4,4’-N,N'-디카르바졸-비페닐(CBP)이 가장 널리 알려져 있었다. 최근에는, 일본의 파이오니어 등이 정공 차단층의 재료로 사용되던 바토큐프로인(Bathocuproine, BCP) 및 알루미늄(III)비스(2-메틸-8-퀴놀리네이트)(4-페닐페놀레이트)(Balq) 등을 호스트 재료로 이용해 고성능의 유기 EL 소자를 개발한 바 있다.The light emitting material may be a mixture of a light emitting material (dopant) and a host material in order to improve color purity, luminous efficiency and stability. When using such a light emitting material (dopant) / host material system, the selection is important because the host material has a great influence on the efficiency and performance of the light emitting device. In the prior art, 4,4'-N, N'-dicarbazole-biphenyl (CBP) was most widely known as a phosphorescent host material. In recent years, Pioneer et al. Of Japan have been using bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenyl phenolate) Balq) as a host material to develop a high-performance organic EL device.

그러나 기존의 이러한 인광용 호스트 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 다음과 같은 단점이 있다: (1) 유리 전이 온도가 낮고 열적 안정성이 낮아서, 진공 하에서 고온 증착 공정을 거칠 때, 물질이 변한다. (2) 유기 EL 소자에서 전력효율 = [(π/전압) × 전류효율]의 관계에 있으므로 전력 효율은 전압에 반비례한다. 그러나, 인광용 호스트 재료를 사용한 유기 EL 소자는 형광 재료를 사용한 유기 EL 소자에 비해 전류 효율(cd/A)은 높으나, 구동 전압 역시 상당히 높기 때문에 전력 효율(lm/w) 면에서 큰 이점이 없다. (3) 또한, 유기 EL 소자에 사용할 경우, 작동 수명 측면에서도 만족스럽지 못하며, 발광 효율도 여전히 개선이 요구된다.However, the conventional phosphorescent host materials are advantageous from the viewpoint of luminescence characteristics, but they have the following disadvantages: (1) the material is changed when the glass transition temperature is low and the thermal stability is low and the high temperature deposition process is performed under vacuum . (2) Since the power efficiency = [(π / voltage) x current efficiency] in the organic EL device, the power efficiency is inversely proportional to the voltage. However, the organic EL device using the phosphorescent host material has a higher current efficiency (cd / A) than the organic EL device using the fluorescent material, but the driving voltage is also very high, so there is no great advantage in terms of power efficiency (lm / w) . (3) In addition, when used in an organic EL device, it is unsatisfactory in terms of operating life, and luminous efficiency is still required to be improved.

한편, 유기 EL 소자에서 정공 주입 및 수송 재료로서 구리 프탈로시아닌(CuPc), 4,4'-비스[N-(1-나프틸)-N-페닐아미노]비페닐(NPB), N,N'-디페닐-N,N'-비스(3-메틸페닐)-(1,1'-비페닐)-4,4'-디아민(TPD), 4,4',4"-트리스(3-메틸페닐페닐아미노)트리페닐아민(MTDATA) 등이 사용되어 왔으나, 이러한 물질을 사용한 경우 유기 EL 소자는 양자 효율 및 수명이 저하되는 문제가 있었다. 그 이유는 유기 EL 소자를 높은 전류에서 구동하게 되면, 양극과 정공 주입층 사이에서 열 스트레스(thermal stress)가 발생하고, 이러한 열 스트레스에 의해 소자의 수명이 급격히 저하되기 때문이다. 또한, 정공 주입층에 사용되는 유기물질은 정공의 운동성이 매우 크기 때문에, 정공과 전자의 전하 밸런스(hole-electron charge balance)가 깨지고 이로 인해 양자 효율(cd/A)이 낮아지게 된다. Meanwhile, copper phthalocyanine (CuPc), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB), N, N'- as hole injecting and transporting materials in organic EL devices. Diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD), 4,4 ', 4 "-tris (3-methylphenylphenylamino Although triphenylamine (MTDATA) has been used, organic EL devices have a problem of deterioration of quantum efficiency and lifespan when such materials are used. This is because thermal stress occurs between the injection layers, and the lifespan of the device is drastically reduced due to such thermal stress.In addition, since the organic material used in the hole injection layer has very high hole mobility, The hole-electron charge balance is broken, resulting in lower quantum efficiency (cd / A).

한국 공개특허공보 제2009-0035729호는 카바졸을 포함하는 아민 화합물을 유기 전계 발광 소자용 화합물로 개시하고 있다. 또한, 한국 공개특허공보 제2011-0129766호는 융합된 카바졸을 포함하는 아민 화합물을 유기 전계 발광 소자용 화합물로 개시하고 있다. 그러나, 상기 문헌들에 개시된 화합물들을 포함한 유기 EL 소자들은 전력 효율, 발광 효율, 양자 효율 및 수명 등의 측면에서 여전히 만족스럽지 않다. Korean Laid-Open Patent Publication No. 2009-0035729 discloses an amine compound containing carbazole as a compound for an organic electroluminescent device. In addition, Korean Laid-Open Patent Publication No. 2011-0129766 discloses an amine compound including a fused carbazole as a compound for an organic EL device. However, the organic EL devices including the compounds disclosed in the above documents are still unsatisfactory in terms of power efficiency, luminous efficiency, quantum efficiency and lifetime.

한국 공개특허공보 제2009-0035729호 (2009.04.10 공개)Korean Unexamined Patent Publication No. 2009-0035729 (published Apr. 10, 2009) 한국 공개특허공보 제2011-0129766호 (2011.12.02 공개)Korean Unexamined Patent Publication No. 2011-0129766 (published Dec. 2, 2011)

따라서 본 발명의 목적은 첫째, 기존의 재료보다 발광 효율 및 소자 수명이 좋은 유기 전계 발광 화합물을 제공하는 것이며, 둘째, 상기 유기 전계 발광 화합물을 포함하는 고효율 및 장수명의 유기 전계 발광 소자를 제공하는 것이다. Accordingly, an object of the present invention is to firstly provide an organic electroluminescent compound having better luminous efficiency and device life than conventional materials, and secondly, to provide a high efficiency and long life organic electroluminescent device including the organic electroluminescent compound. .

상기의 기술적 과제를 해결하기 위해 예의 연구한 결과, 본 발명자들은 하기 화학식 1로 표시되는, 디아릴아미노 또는 디헤테로아릴아미노로 치환된 디벤조티오펜 유도체 화합물이 상술한 목적을 달성함을 발견하여 본 발명을 완성하였다.[화학식 1] As a result of earnest research to solve the above technical problem, the present inventors have found that the dibenzothiophene derivative compound substituted with diarylamino or diheteroarylamino represented by the following general formula (1) achieves the above-mentioned object. The present invention has been completed.

Figure pat00001
Figure pat00001

L1 및 L2은 각각 독립적으로 단일결합, 치환 또는 비치환된 (C6-C30)아릴렌, 또는 치환 또는 비치환된 (5-30원)헤테로아릴렌이고;L 1 and L 2 are each independently a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5- to 30-membered) heteroarylene;

Ar1및 Ar2는 각각 독립적으로 치환 또는 비치환된 (C6-C30)아릴, 또는 치환 또는 비치환된 (5-30원)헤테로아릴이고;Ar 1 and Ar 2 are each independently substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5- to 30-membered) heteroaryl;

X는 산소 원자, 황 원자 또는 -CR5R6이고;X is oxygen atom, sulfur atom or -CR 5 R 6 ;

R1 내지 R6는 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C2-C30)알케닐, 치환 또는 비치환된 (C2-C30)알키닐, 치환 또는 비치환된 (C1-C30)알콕시, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C3-C30)시클로알케닐, 치환 또는 비치환된 (3-7원)헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (5-30원)헤테로아릴, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 또는 -B(OR19)(OR20)이거나, 인접한 치환체와 연결되어 (3-30원) 단일환 또는 다환의 지환족 또는 방향족 고리를 형성할 수 있고; 상기 형성된 지환족 또는 방향족 환의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 대체될 수 있고;R 1 to R 6 are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl , Substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cyclo Alkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5--30 membered) heteroaryl, -NR 11 R 12 , -SiR 13 R 14 R 15 , -SR 16 , -OR 17 , -COR 18 or -B (OR 19 ) (OR 20 ) or linked to an adjacent substituent (3- to 30-membered) monocyclic or polycyclic alicyclic Or can form an aromatic ring; The carbon atoms of the alicyclic or aromatic rings formed may be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur;

R11 내지 R20는 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C2-C30)알케닐, 치환 또는 비치환된 (C2-C30)알키닐, 치환 또는 비치환된 (C1-C30)알콕시, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C3-C30)시클로알케닐, 치환 또는 비치환된 (3-7원)헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아릴, 또는 치환 또는 비치환된 (5-30원)헤테로아릴이거나, 인접한 치환체와 연결되어 (3-30원) 단일환 또는 다환의 지환족 또는 방향족 고리를 형성할 수 있고;R 11 to R 20 are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl , Substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cyclo Alkenyl, substituted or unsubstituted (3- to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5- to 30-membered) heteroaryl or linked to an adjacent substituent To form a (3- to 30-membered) monocyclic or polycyclic alicyclic or aromatic ring;

a는 1 내지 4의 정수이며, 2 이상의 정수인 경우 각각의 R1은 동일하거나 상이할 수 있고; b 내지 d는 각각 독립적으로 1 내지 3의 정수이며, 2 이상의 정수인 경우 각각의 R2, 각각의 R3 및 각각의 R4는 동일하거나 상이할 수 있고;a is an integer from 1 to 4, and when it is an integer of 2 or more, each R 1 may be the same or different; b to d are each independently integers of 1 to 3, and each integer of 2 or more, each R 2 , each R 3 and each R 4 may be the same or different;

상기 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함하고;The heteroaryl comprises one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;

상기 헤테로시클로알킬은 O, S 및 N에서 선택되는 하나 이상의 헤테로원자를 포함한다.The heterocycloalkyl includes one or more heteroatoms selected from O, S and N.

본 발명에 따른 화합물은 발광 효율이 우수하고 재료의 수명 특성이 뛰어나 소자의 구동 수명이 우수한 유기 전계 발광 소자를 제조할 수 있다. 또한, 본 발명에 따른 화합물은 소자의 구동전압을 저하시켜 전력효율이 향상되고 또한 전류효율이 우수한 유기 전계 발광 소자를 제조할 수 있다.The compound according to the present invention can be produced an organic electroluminescent device excellent in the luminous efficiency and excellent life characteristics of the material excellent in the driving life of the device. In addition, the compound according to the present invention can reduce the driving voltage of the device to improve the power efficiency and can produce an organic EL device having excellent current efficiency.

이하에서 본 발명을 더욱 상세히 설명하나, 이는 설명을 위한 것으로 본 발명의 범위를 제한하는 방법으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail, but this is for explanation and should not be construed as a method of limiting the scope of the present invention.

본 발명은 상기 화학식 1로 표시되는 유기 전계 발광 화합물, 상기 유기 전계 발광 화합물을 포함하는 유기 전계 발광 재료, 및 상기 재료를 포함하는 유기 전계 발광 소자에 관한 것이다. The present invention relates to an organic electroluminescent compound represented by Formula 1, an organic electroluminescent material including the organic electroluminescent compound, and an organic electroluminescent device comprising the material.

본 발명의 상기 화학식 1로 표시되는 화합물에 대해 보다 구체적으로 설명하면 다음과 같다. Hereinafter, the compound represented by Chemical Formula 1 of the present invention will be described in more detail.

상기 화학식 1에서, L1 및 L2은 각각 독립적으로 단일결합, 치환 또는 비치환 (C6-C30)아릴렌, 또는 치환 또는 비치환 (5-30원)헤테로아릴렌이고, 바람직하게는 단일결합, 치환 또는 비치환된 (C6-C15)아릴렌, 또는 치환 또는 비치환된 (5-15원)헤테로아릴렌이고, 더욱 바람직하게는 단일결합, 비치환된 (C6-C15)아릴렌, (C6-C15)아릴로 치환된 (C6-C15)아릴렌, 또는 비치환된 (5-10원)헤테로아릴렌이다. In Formula 1, L 1 and L 2 are each independently a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5- to 30-membered) heteroarylene, preferably a single bond , Substituted or unsubstituted (C6-C15) arylene, or substituted or unsubstituted (5- to 15-membered) heteroarylene, more preferably a single bond, unsubstituted (C6-C15) arylene, ( (C6-C15) arylene substituted with C6-C15) aryl, or unsubstituted (5- to 10-membered) heteroarylene.

상기 화학식 1에서, Ar1 및 Ar2 는 각각 독립적으로 치환 또는 비치환된 (C6-C30)아릴 또는 치환 또는 비치환된 (5-30원)헤테로아릴이고, 바람직하게는 치환 또는 비치환된 (C6-C15)아릴, 또는 치환 또는 비치환된 (5-15원)헤테로아릴이고, 더욱 바람직하게는 비치환된 (C6-C15)아릴; (C1-C6)알킬, (C6-C15)아릴, (C6-C15) 아릴아미노 또는 (C6-C15)아릴(5-10원)헤테로아릴아미노로 치환된 (C6-C15)아릴; 비치환된 (5-10원)헤테로아릴; 또는 (C6-C15)아릴 또는 (C6-C15)아릴아미노로 치환된 (5-10원)헤테로아릴이다.In Formula 1, Ar 1 and Ar 2 are each independently substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (5- to 30-membered) heteroaryl, preferably substituted or unsubstituted ( C6-C15) aryl or substituted or unsubstituted (5- to 15-membered) heteroaryl, more preferably unsubstituted (C6-C15) aryl; (C6-C15) aryl substituted with (C1-C6) alkyl, (C6-C15) aryl, (C6-C15) arylamino or (C6-C15) aryl (5--10 membered) heteroarylamino; Unsubstituted 5-10 membered heteroaryl; Or (5-10 membered) heteroaryl substituted with (C6-C15) aryl or (C6-C15) arylamino.

상기 화학식 1에서, X는 산소 원자, 황 원자 또는 -CR5R6이고,In Formula 1, X is an oxygen atom, a sulfur atom or -CR 5 R 6 ,

상기 화학식 1에서, R1 및 R6는 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C2-C30)알케닐, 치환 또는 비치환된 (C2-C30)알키닐, 치환 또는 비치환된 (C1-C30)알콕시, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C3-C30)시클로알케닐, 치환 또는 비치환된 (3-7원)헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (5-30원)헤테로아릴, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 또는 -B(OR19)(OR20)이거나, 인접한 치환체와 연결되어 (3-30원) 단일환 또는 다환의 지환족 또는 방향족 고리를 형성할 수 있고, 바람직하게는 수소, 할로겐, 치환 또는 비치환된 (C1-C15)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (5-30원)헤테로아릴, -NR11R12 또는 -SiR13R14R15 이고, 더욱 바람직하게는 수소, 할로겐, 비치환된 (C1-C6)알킬, 비치환된 (C6-C20)아릴, 비치환된 (5-15원)헤테로아릴, 또는 (C1-C6) 알킬 또는 (C6-C15)아릴로 치환된 (C6-C20)아릴이고;In Formula 1, R 1 and R 6 are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2 Alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted ( C3-C30) cycloalkenyl, substituted or unsubstituted (3- to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) heteroaryl,- NR 11 R 12 , -SiR 13 R 14 R 15 , -SR 16 , -OR 17 , -COR 18 or -B (OR 19 ) (OR 20 ) or linked to an adjacent substituent (3- to 30-membered) monocyclic ring Or a polycyclic alicyclic or aromatic ring, preferably hydrogen, halogen, substituted or unsubstituted (C1-C15) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted Heteroaryl, -NR 1 1 R 12 or —SiR 13 R 14 R 15 , more preferably hydrogen, halogen, unsubstituted (C1-C6) alkyl, unsubstituted (C6-C20) aryl, unsubstituted (5- to 15-membered) Heteroaryl or (C6-C20) aryl substituted with (C1-C6) alkyl or (C6-C15) aryl;

R11 및 R12는 바람직하게는 각각 독립적으로 치환 또는 비치환된 (C6-C15)아릴, 또는 치환 또는 비치환된 (5-15원)헤테로아릴이고, R13 내지 R15는 바람직하게는 각각 독립적으로 치환 또는 비치환된 (C1-C10)알킬 또는 (C6-C15)아릴이다. R 11 and R 12 are preferably each independently substituted or unsubstituted (C6-C15) aryl, or substituted or unsubstituted (5- to 15-membered) heteroaryl, and R 13 to R 15 are each preferably Independently substituted or unsubstituted (C1-C10) alkyl or (C6-C15) aryl.

본 발명에 기재되어 있는 “(C1-C30)알킬”은 탄소수가 1 내지 30개인 직쇄 또는 분지쇄 알킬을 의미하고, 여기에서 탄소수가 1 내지 15개인 것이 바람직하고, 1 내지 6개인 것이 더 바람직하다. 상기 알킬의 구체적인 예로서, 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸 및 3급-부틸 등이 있다. 본원에서 “(C2-C30)알케닐”은 탄소수가 2 내지 30개인 직쇄 또는 분지쇄 알케닐을 의미하고, 여기에서 탄소수가 2 내지 20개인것이 바람직하고, 2 내지 10개인 것이 더 바람직하다. 상기 알케닐의 구체적인 예로서, 비닐, 1-프로페닐, 2-프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 2-메틸부트-2-에닐 등이 있다. 본원에서 “(C2-C30)알키닐”은 탄소수가 2 내지 30개인 직쇄 또는 분지쇄 알키닐을 의미하고, 여기에서 탄소수가 2 내지 20개인 것이 바람직하고, 2 내지 10개인 것이 더 바람직하다. 상기 알키닐의 예로서, 에티닐, 1-프로피닐, 2-프로피닐, 1-부티닐, 2-부티닐, 3-부티닐, 1-메틸펜트-2-이닐 등이 있다. 본원에서 “(C3-C30)시클로알킬”은 탄소수가 3 내지 30개인 단일환 또는 다환 탄화수소를 의미하고, 여기에서 탄소수가 3 내지 20개인 것이 바람직하고, 3 내지 7개인 것이 더 바람직하다. 상기 시클로알킬의 예로서, 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실 등이 있다. 본원에서 “(3-7원) 헤테로시클로알킬”은 환 골격 원자수가 3 내지 7개이고, B, N, O, S, P(=O), Si 및 P로 이루어진 군에서 선택된 하나 이상의 헤테로원자, 바람직하게는 O, S 및 N에서 선택되는 하나 이상의 헤테로원자를 포함하는 시클로알킬을 의미하고, 예를 들어, 테트라히드로푸란, 피롤리딘, 티올란, 테트라히드로피란 등이 있다. 본원에서 “(C6-C30)아릴(렌)”은 탄소수가 6 내지 30개인 방향족 탄화수소에서 유래된 단일환 또는 융합환계 라디칼을 의미하고, 여기에서 환 골격 탄소수가 6 내지 20개인 것이 바람직하고, 6 내지 15개인 것이 더 바람직하다. 상기 아릴의 예로서, 페닐, 비페닐, 터페닐, 나프틸, 플루오레닐, 페난트레닐, 안트라세닐, 인데닐, 트리페닐레닐, 피레닐, 테트라세닐, 페릴레닐, 크라이세닐, 나프타세닐, 플루오란테닐 등이 있다. 본원에서 “(5-30원) 헤테로아릴(렌)”은 환 골격 원자수가 5 내지 30개이고, B, N, O, S, P(=O), Si 및 P로 이루어진 군에서 선택된 하나 이상의 헤테로원자를 포함하는 아릴기를 의미한다. 여기에서 환 골격 원자수가 5 내지 21개인 것이 바람직하고, 5 내지 15개인 것이 더 바람직하다. 헤테로원자수는 바람직하게는 1 내지 4개이고, 단일 환계이거나 하나 이상의 벤젠환과 축합된 융합 환계일 수 있으며, 부분적으로 포화될 수도 있다. 또한, 본원에서 상기 헤테로아릴(렌)은 하나 이상의 헤테로아릴기 또는 아릴기가 단일 결합에 의해 헤테로아릴기와 연결된 형태도 포함한다. 상기 헤테로아릴의 예로서, 푸릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아졸릴, 테트라졸릴, 푸라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단일 환계 헤테로아릴, 벤조푸란일, 벤조티오펜일, 이소벤조푸란일, 디벤조푸란일, 디벤조티오펜일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴녹살리닐, 카바졸릴, 페녹사진일, 페난트리딘일, 벤조디옥솔릴 등의 융합 환계 헤테로아릴 등이 있다. 본원에서 “할로겐”은 F, Cl, Br 및 I 원자를 포함한다.“(C 1 -C 30) alkyl” described in the present invention means straight or branched chain alkyl having 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 6 carbon atoms. . Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As used herein, "(C2-C30) alkenyl" means a straight or branched chain alkenyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. Specific examples of the alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl and the like. As used herein, " (C2-C30) alkynyl " means straight or branched chain alkynyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. Examples of the alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methylpent-2-onyl. As used herein, "(C3-C30) cycloalkyl" means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 7 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. As used herein, “(3-7 membered) heterocycloalkyl” has 3 to 7 ring skeleton atoms, and at least one heteroatom selected from the group consisting of B, N, O, S, P (═O), Si and P, Preferred are cycloalkyls comprising at least one heteroatom selected from O, S and N, for example tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. As used herein, "(C6-C30) aryl (ene)" means a monocyclic or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein 6 to 20 ring skeleton carbon atoms are preferable, and 6 More preferably 15. Examples of such aryls include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, , Fluoranthenyl, and the like. As used herein, the term "(5-30) heteroaryl (phenylene)" refers to a heteroaryl group having 5 to 30 ring skeletal atoms and one or more heteroatoms selected from the group consisting of B, N, O, S, P Quot; means an aryl group containing an atom. Here, the number of atoms of the ring skeleton is preferably 5 to 21, more preferably 5 to 15. The number of heteroatoms is preferably 1 to 4, and may be a monocyclic ring system or a fused ring system condensed with at least one benzene ring, and may be partially saturated. In addition, the heteroaryl (phenylene) in the present invention also includes a form in which one or more heteroaryl groups or aryl groups are linked to a heteroaryl group by a single bond. Examples of such heteroaryls include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl , Monocyclic heteroaryl such as triazolyl, tetrazolyl, furanzyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzoimidazolyl, benzothiazolyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, Fused heterocyclic heteroaryl such as norbornyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxaphyl, phenanthridinyl, benzodioxolyl and the like. "Halogen" herein includes F, Cl, Br and I atoms.

또한 본 발명에 기재되어 있는 “치환 또는 비치환”이라는 기재에서 “치환”은 어떤 작용기에서 수소 원자가 다른 원자 또는 다른 작용기(즉, 치환체)로 대체되는 것을 뜻한다. 상기 화학식 1 에서, 치환 (C1-C30)알킬, 치환 (C2-C30)알케닐, 치환 (C2-C30)알키닐, 치환 (C1-C30)알콕시, 치환 (C3-C30)시클로알킬, 치환 (C3-C30)시클로알케닐, 치환 (3-7원)헤테로시클로알킬, 치환(C6-C30)아릴(렌), 또는 치환 (5-30원)헤테로아릴(렌)의 치환체는 각각 독립적으로 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, (C1-C30)알킬, 할로(C1-C30)알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C1-C30)알콕시, (C1-C30)알킬티오, (C3-C30)시클로알킬, (C3-C30)시클로알케닐, (3-7원)헤테로시클로알킬, (C6-C30)아릴옥시, (C6-C30)아릴티오, (C6-C30)아릴로 치환되거나 비치환된 (5-30원)헤테로아릴, (5-30원)헤테로아릴로 치환되거나 비치환된 (C6-C30)아릴, 트리(C1-C30)알킬실릴, 트리(C6-C30)아릴실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, (C1-C30)알킬디(C6-C30)아릴실릴, 아미노, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, (C1-C30)알킬(C6-C30)아릴아미노, (C1-C30)알킬카보닐, (C1-C30)알콕시카보닐, (C1-C30)아릴카보닐, 디(C6-C30)아릴보로닐, 디(C1-C30)알킬보로닐, (C1-C30)알킬(C6-C30)아릴보로닐, (C6-C30)아르(C1-C30)알킬 및 (C1-C30)알킬(C6-C30)아릴로 이루어진 군으로부터 선택되는 1종 이상인 것이 바람직하다. Also, in the term "substituted or unsubstituted" described in the present invention, "substituted" means that a hydrogen atom is replaced by another atom or another functional group (ie, a substituent) in a certain functional group. In Formula 1, substituted (C1-C30) alkyl, substituted (C2-C30) alkenyl, substituted (C2-C30) alkynyl, substituted (C1-C30) alkoxy, substituted (C3-C30) cycloalkyl, substituted ( Substituents of C3-C30) cycloalkenyl, substituted (3- to 7-membered) heterocycloalkyl, substituted (C6-C30) aryl (ene), or substituted (5- to 30-membered) heteroaryl (ene) are each independently deuterium , Halogen, cyano, carboxyl, nitro, hydroxy, (C1-C30) alkyl, halo (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) Alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) cycloalkenyl, (3-7 membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) (5- to 30-membered) heteroaryl unsubstituted or substituted with arylthio, (C6-C30) aryl (C6-C30) aryl, tri (C1-C30) unsubstituted or substituted with (5--30 membered) heteroaryl ) Alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyldi (C6-C30) arylsilyl, amino, mono or di (C1) -C 30) alkylamino, Furnace or di (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C1-C30) arylcarbon Neyl, di (C6-C30) arylboronyl, di (C1-C30) alkylboronyl, (C1-C30) alkyl (C6-C30) arylboronyl, (C6-C30) ar (C1-C30) It is preferably at least one member selected from the group consisting of) alkyl and (C1-C30) alkyl (C6-C30) aryl.

본 발명에 따른 화합물로는 대표적으로 하기의 화합물을 들 수 있다.Representative examples of the compound according to the present invention include the following compounds.

Figure pat00002
Figure pat00002

Figure pat00003
Figure pat00003

Figure pat00004
Figure pat00004

Figure pat00005
Figure pat00005

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

Figure pat00028
Figure pat00028

Figure pat00029
Figure pat00029

Figure pat00030
Figure pat00030

Figure pat00031
Figure pat00031

본 발명에 따른 화합물은 당업자에게 공지된 합성 방법으로 제조할 수 있으며, 예를 들면 하기 반응식 1에 따라 제조할 수 있다.The compounds according to the invention can be prepared by synthetic methods known to those skilled in the art, for example, according to Scheme 1 below.

[반응식 1] [Reaction Scheme 1]

Figure pat00032
Figure pat00032

[상기 반응식 1에서 X, L1, L2, Ar1 , Ar2 , R1 내지 R4, a, b, c 및 d는 상기 화학식 1에서의 정의와 동일하고, Hal는 할로겐이다][X, L 1 , L 2 , Ar 1 , Ar 2 , R 1 to R 4 , a, b, c and d in Scheme 1 are the same as defined in Formula 1, and Hal is halogen.]

또한, 본 발명은 화학식 1의 유기 전계 발광 화합물을 포함하는 유기 전계 발광 재료 및 상기 재료를 포함하는 유기 전계 발광 소자를 제공한다. 상기 재료는 본 발명의 유기 전계 발광 화합물 단독으로 이루어질 수 있고, 유기 전계 발광 재료에 포함되는 통상의 물질들을 추가로 포함할 수도 있다. 본 발명에 따른 유기 전계 발광 소자는 제1 전극; 제2 전극; 및 상기 제1 전극 및 제2 전극 사이에 개재되는 1층 이상의 유기물층을 갖고, 상기 유기물층은 상기 화학식 1의 화합물을 하나 이상 포함한다. The present invention also provides an organic electroluminescent material comprising an organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the same. The material may be composed of the organic electroluminescent compound of the present invention alone, and may further include conventional materials included in the organic electroluminescent material. An organic electroluminescent device according to the present invention 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 includes at least one compound represented by Chemical Formula 1.

상기 제1 전극과 제2 전극 중 하나는 애노드이고 다른 하나는 캐소드일 수 있다. 상기 유기물층은 발광층을 포함하고, 정공 주입층, 정공 수송층, 전자 수송층, 전자 주입층, 계면층(interlayer) 및 정공 차단층에서 선택되는 1층 이상을 더 포함할 수 있다.One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer and a hole blocking layer.

본 발명의 화학식 1의 화합물은 상기 발광층 및 정공 수송층 중 하나 이상에 포함될 수 있다. 정공 수송층에 사용될 경우, 본 발명의 화학식 1의 화합물은 정공 수송재료로서 포함될 수 있다. 발광층에 사용될 경우, 본 발명의 화학식 1의 화합물은 호스트 재료로서 포함될 수 있다. 바람직하게는 상기 발광층은 하나 이상의 도펀트를 추가로 더 포함할 수 있으며, 필요한 경우, 본 발명의 화학식 1의 화합물 이외의 다른 화합물을 제2 호스트 재료로 추가로 포함할 수 있다.The compound of Formula 1 of the present invention may be included in at least one of the light emitting layer and the hole transporting layer. When used in a hole transporting layer, the compound of Formula 1 of the present invention can be included as a hole transporting material. When used in the light emitting layer, the compound of Formula 1 of the present invention can be included as a host material. Preferably, the light emitting layer may further include one or more dopants, and if necessary, may further include a compound other than the compound of Formula 1 of the present invention as a second host material.

상기 제2 호스트 재료는 공지된 인광 호스트라면 어느 것이든 사용 가능하나, 하기 화학식 2 내지 화학식 4로 표시되는 화합물로 구성된 군으로부터 선택되는 것이 발광 효율 면에서 특히 바람직하다. The second host material may be any known phosphorescent host, but is preferably selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4, in view of luminous efficiency.

[화학식 2](2)

H-(Cz-L4)h-M H- (Cz-L 4) h -M

[화학식 3](3)

H-(Cz)i-L4-MH- (Cz) i -L 4 -M

[화학식 4][Chemical Formula 4]

Figure pat00033
Figure pat00033

상기 화학식 2 내지 4에서,In the above Chemical Formulas 2 to 4,

Cz는 하기 구조이며, Cz has the following structure,

Figure pat00034
Figure pat00034

R21 내지 R24은 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (5-30원) 헤테로아릴 또는 R25R26R27Si- 이며, R25 내지 R27는 각각 독립적으로 치환 또는 비치환된 (C1-C30)알킬, 또는 치환 또는 비치환된 (C6-C30)아릴이고; L4은 단일결합, 치환 또는 비치환된 (C6-C30)아릴렌, 또는 치환 또는 비치환된 (5-30원) 헤테로아릴렌이고; M은 치환 또는 비치환된 (C6-C30)아릴, 또는 치환 또는 비치환된 (5-30원) 헤테로아릴이며; Y1 및 Y2는 -O-, -S-, -N(R31)- 또는 -C(R32)(R33)-이고, Y1과 Y2가 동시에 존재하지는 않으며; R31 내지 R33은 각각 독립적으로 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 또는 치환 또는 비치환된 (5-30원)헤테로아릴이고, R32 및 R33 은 동일하거나 상이할 수 있으며; h 및 i는 각각 독립적으로 1 내지 3의 정수이고, j, k, l 및 m 은 각각 독립적으로 0 내지 4의 정수이며, h, i, j, k, l 또는 m이 2 이상의 정수인 경우 각각의 (Cz-L4), 각각의 (Cz), 각각의 R21, 각각의 R22, 각각의 R23 또는 각각의 R24는 동일하거나 상이할 수 있다.R 21 to R 24 each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Heteroaryl or R 25 R 26 R 27 Si-, R 25 to R 27 are each independently substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; L 4 is a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (5-30 membered) heteroarylene; M is a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-30 membered) heteroaryl; Y 1 and Y 2 are —O—, —S—, —N (R 31 ) — or —C (R 32 ) (R 33 ) —, wherein Y 1 and Y 2 are not present simultaneously; R 31 to R 33 are each independently substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5- to 30-membered) heteroaryl, and R 32 and R 33 may be the same or different; each of h and i is independently an integer of 1 to 3, j, k, l and m are each independently an integer of 0 to 4, and when h, i, j, k, l or m is an integer of 2 or more, (Cz-L 4 ), each (Cz), each R 21 , each R 22 , each R 23, or each R 24 may be the same or different.

구체적으로 상기 제2호스트 재료의 바람직한 예는 다음과 같다.Specifically, preferred examples of the second host material are as follows.

Figure pat00035
Figure pat00035

Figure pat00036
Figure pat00036

Figure pat00037
Figure pat00037

Figure pat00038
Figure pat00038

Figure pat00039
Figure pat00039

Figure pat00040
Figure pat00040

Figure pat00041
Figure pat00041

Figure pat00042
Figure pat00042

Figure pat00043
Figure pat00043

Figure pat00044
Figure pat00044

Figure pat00045
Figure pat00045

Figure pat00046
Figure pat00046

Figure pat00047
Figure pat00047

본 발명의 유기 전계 발광 소자 제조에 사용되는 도펀트로는 하나 이상의 인광 도펀트가 바람직하다. 본 발명의 유기 전계 발광 소자에 적용되는 인광 도펀트 재료는 특별히 제한되지는 않으나, 이리듐(Ir), 오스뮴(Os), 구리(Cu) 및 백금(Pt)으로부터 선택되는 금속 원자의 착체 화합물이 바람직하고, 이리듐(Ir), 오스뮴(Os), 구리(Cu) 및 백금(Pt)으로부터 선택되는 금속 원자의 오르토 메탈화 착체 화합물이 더욱 바람직하며, 오르토 메탈화 이리듐 착체 화합물이 더더욱 바람직하다.As the dopant used in the organic electroluminescent device of the present invention, at least one phosphorescent dopant is preferable. The phosphorescent dopant material to be applied to the organic electroluminescent device of the present invention is not particularly limited, but is preferably a complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) , An iridium (Ir), an osmium (Os), a copper (Cu) and a platinum (Pt) are more preferable, and an orthometallated iridium complex compound is even more preferable.

상기 인광 도펀트는 하기 화학식 5 내지 화학식 7로 표시되는 화합물로 구성된 군으로부터 선택되는 것이 바람직하다.The phosphorescent dopant is preferably selected from the group consisting of compounds represented by the following formulas (5) to (7).

Figure pat00048
Figure pat00048

상기 화학식 5 내지 7에서, L은 하기 구조중에서 선택되고;In Formulas 5 to 7, L is selected from the following structures;

Figure pat00049
Figure pat00049

R100은 수소, 또는 치환 또는 비치환된 (C1-C30)알킬이며; R101 내지 R109 및 R111 내지 R123은 각각 독립적으로 수소, 중수소, 할로겐, 할로겐이 치환 또는 비치환된 (C1-C30)알킬, 시아노, 또는 치환 또는 비치환된 (C1-C30)알콕시이고; 또는 R120 내지 R123는 인접 치환기가 서로 연결되어 융합고리를 형성하는데, 예를 들어 퀴놀린 형성이 가능하며; R124 내지 R127은 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된(C1-C30)알킬, 또는 치환 또는 비치환된 (C1-C30)아릴이며; 또는 R124 내지 R127가 아릴기인 경우 인접기가 서로 연결되어 융합고리를 형성하는데, 예를 들어 플루오렌 형성이 가능하며; R201 내지 R211은 각각 독립적으로 수소, 중수소, 할로겐, 또는 할로겐으로 치환 또는 비치환된 (C1-C30)알킬이며; f 및 g는 각각 독립적으로 1 내지 3의 정수이며, f 또는 g가 각각 2이상의 정수인 경우 각각의 R100은 서로 동일하거나 상이할 수 있고; n은 1 내지 3의 정수이다. R 100 is hydrogen or substituted or unsubstituted (C 1 -C 30) alkyl; R 101 to R 109 And R 111 to R 123 are each independently hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, substituted or unsubstituted (C 1 -C 30) alkyl, cyano, or substituted or unsubstituted (C 1 -C 30) alkoxy; Or R 120 to R 123 are adjacent substituents connected to each other to form a fused ring, for example, quinoline formation is possible; R 124 to R 127 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 1 -C 30) aryl; Or when R 124 to R 127 are aryl groups, the adjacent groups are connected to each other to form a fused ring, for example fluorene formation is possible; R 201 To R < 211 > are each independently hydrogen, deuterium, halogen, or (C1-C30) alkyl unsubstituted or substituted with halogen; f and g are each independently an integer of 1 to 3, and when f or g is an integer of 2 or more, each R 100 may be the same or different from each other; n is an integer of 1 to 3;

상기 인광 도펀트 재료의 구체적인 예로는 다음과 같다.Specific examples of the phosphorescent dopant material are as follows.

Figure pat00050
Figure pat00050

Figure pat00051
Figure pat00051

Figure pat00052
Figure pat00052

Figure pat00053
Figure pat00053

Figure pat00054
Figure pat00054

Figure pat00055
Figure pat00055

Figure pat00056
Figure pat00056

Figure pat00057
Figure pat00057

Figure pat00058
Figure pat00058

Figure pat00059
Figure pat00059

Figure pat00060
Figure pat00060

Figure pat00061
Figure pat00061

본 발명은 추가의 양태로 유기 전계 발광소자 제조용 재료를 제공한다. 상기 재료는 제1호스트 재료 및 제2호스트 재료를 포함하며, 상기 제1호스트 재료로 본 발명의 화합물을 포함한다. 이때 제1 호스트 재료와 제 2호스트 재료의 중량비는 1:99 내지 99:1 범위이다.      The present invention further provides a material for manufacturing an organic electroluminescent device in a further aspect. The material includes a first host material and a second host material, and includes the compound of the present invention as the first host material. Wherein the weight ratio of the first host material to the second host material ranges from 1:99 to 99: 1.

또한, 본 발명의 유기 전계 발광 소자는 제1 전극; 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 개재되는 1층 이상의 유기물층을 가지며, 상기 유기물층은 발광층을 포함하며, 상기 발광층은 본 발명의 유기 전계 발광소자용 재료 및 인광 도펀트 재료를 포함하며, 상기 유기 전계발광 소자용 재료는 호스트 재료로 사용된다.In addition, the organic electroluminescent device of 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 a light emitting layer, and the light emitting layer includes the organic electroluminescent device material and the phosphorescent dopant material of the present invention. Electroluminescent device materials are used as host materials.

본 발명의 유기 전계 발광 소자는 유기물층이 화학식 1의 화합물을 포함하고, 이와 동시에 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 화합물을 포함할 수 있다. The organic electroluminescent device of the present invention may include at least one compound selected from the group consisting of an arylamine compound and a styrylarylamine compound.

또한, 본 발명의 유기 전계 발광 소자에 있어서, 유기물층에 상기 화학식 1의 화합물 이외에 1족, 2족, 4주기, 5주기 전이금속, 란탄 계열 금속 및 d-전이원소의 유기 금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 착체 화합물을 더 포함할 수도 있고, 나아가 상기 유기물층은 발광층 및 전하 생성층을 더 포함할 수 있다.In addition, in the organic electroluminescent device of the present invention, the organic material layer is selected from the group consisting of Group 1, Group 2, Group 4, Period 5 transition metals, Lanthanide-based metals and organic metals of d-transition elements in addition to the compound of Formula 1 One or more metal or complex compounds may be further included. Furthermore, the organic material layer may further include a light emitting layer and a charge generating layer.

또한, 본 발명의 상기 유기 전계 발광 소자는 본 발명의 화합물 이외에 당업계에 알려진 청색, 적색 또는 녹색 발광 화합물을 포함하는 발광층 하나 이상을 더 포함함으로써 백색 발광을 할 수 있다. 또한, 필요에 따라, 황색 또는 오렌지색 발광층을 더 포함할 수도 있다.In addition, the organic electroluminescent device of the present invention may emit white light by further including at least one light emitting layer containing a blue, red or green light emitting compound known in the art, in addition to the compound of the present invention. Further, if necessary, it may further include a yellow or orange light emitting layer.

본 발명의 유기 전계 발광 소자에 있어서, 한 쌍의 전극의 적어도 한쪽의 내측 표면에, 칼코제나이드(chalcogenide)층, 할로겐화 금속층 및 금속 산화물층으로부터 선택되는 1층(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 칼코제나이드의 바람직한 예로는 SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON 또는 SiAlON 등이 있고, 할로겐화 금속의 바람직한 예로는 LiF, MgF2, CaF2, 불화 희토류 금속 등이 있으며, 금속 산화물의 바람직한 예로는 Cs2O, Li2O, MgO, SrO, BaO, CaO 등이 있다.In the organic electroluminescent device of the present invention, one layer (hereinafter referred to as a " surface layer ") of a chalcogenide layer, a metal halide layer and a metal oxide layer is formed on at least one inner surface of a 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. Preferable examples of the chalcogenide include SiO X (1? X ? 2), AlO x (1? X ? 1.5), SiON or SiAlON. Preferred examples of the halogenated metal include LiF, MgF 2 , CaF 2 , Rare-earth metals, etc. Preferred 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 도펀트의 혼합 영역 또는 정공 수송 화합물과 산화성 도펀트의 혼합 영역을 배치하는 것도 바람직하다. 이러한 방식에 의해 전자 전달 화합물이 음이온으로 환원되므로 혼합 영역으로부터 발광 매체에 전자를 주입 및 전달하기 용이해진다. 또한, 정공 수송 화합물은 산화되어 양이온으로 되므로 혼합 영역으로부터 발광 매체에 정공을 주입 및 수송하기 용이해진다. 바람직한 산화성 도펀트로서는 각종 루이스산 및 억셉터(acceptor) 화합물을 들 수 있고, 바람직한 환원성 도펀트로는 알칼리 금속, 알칼리 금속 화합물, 알칼리 토류 금속, 희토류 금속 및 이들의 혼합물을 들 수 있다. 또한 환원성 도펀트층을 전하 생성층으로 사용하여 두 개 이상의 발광층을 가진 백색 유기 전계 발광소자를 제작할 수 있다.In the organic electroluminescent device of the present invention, it is also preferable to arrange a mixed region of the electron transfer compound and the reducing dopant or a mixed region of the hole transport compound and the oxidative dopant on at least one surface of the pair of electrodes thus fabricated . In this way, since the electron transfer compound is reduced to an anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transporting compound is oxidized and becomes a cation, it becomes easy to inject and transport holes from the mixed region into the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds, and preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. Further, a white organic electroluminescent device having two or more light emitting layers can be manufactured using a reductive dopant layer as a charge generation layer.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 들어 본 발명에 따른 화합물, 이의 제조방법 및 소자의 발광 특성을 설명한다.Hereinafter, for the purpose of a detailed understanding of the present invention, the compounds according to the present invention, the method for producing the same, and the luminescent characteristics of the device will be described with reference to representative compounds of the present invention.

[실시예 1] 화합물 C-80의 제조 Example 1 Preparation of Compound C-80

1-1: 화합물 3의 합성1-1: Synthesis of Compound 3

Figure pat00062
Figure pat00062

화합물 1, 63g(0.177mol), 화합물 2, 30g(0.177mol), 나트륨 3급-부톡사이드(NaOt-Bu)26g(0.266mol) 및 트리(o-톨릴)포스핀(P(o-Tol)3) 4.3g(0.014mol)을 톨루엔 1.7L에 녹인 후, 트리스(디벤질리덴아세톤)디팔라듐(O)(Pd2(dba)3) 3.2g(0.004mol)을 첨가했다. 이 혼합물을 120℃에서 3시간 동안 교반하였다. 반응물을 실온으로 식힌 후 에틸 아세테이트 1L로 추출하여, 얻어진 유기층을 증류수 400mL로 씻었다. 유기 용매는 감압하에서 제거하였다. 얻어진 고체는 메탄올로 씻어 필터한 후 건조시켰다. 실리카겔 컬럼크로마토그래피와 재결정법으로 분리하여 화합물 3, 41g(58%)을 수득하였다.Compound 1, 63 g (0.177 mol), compound 2, 30 g (0.177 mol), sodium tert-butoxide (NaOt-Bu) 26 g (0.266 mol) and tri (o-tolyl) phosphine (P (o-Tol) 3 ) 4.3 g (0.014 mol) was dissolved in 1.7 L of toluene, and then 3.2 g (0.004 mol) of tris (dibenzylideneacetone) dipalladium (O) (Pd 2 (dba) 3 ) was added. The mixture was stirred at 120 ° C. for 3 hours. The reaction was cooled to room temperature, extracted with 1 L of ethyl acetate, and the organic layer obtained was washed with 400 mL of distilled water. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol, filtered and dried. Silica gel column chromatography and recrystallization to give a compound 3, 41g (58%).

1-2: 화합물 4의 합성1-2: Synthesis of Compound 4

Figure pat00063
Figure pat00063

화합물 3, 10g(25mmol)을 THF 150mL에 녹인 후 n-BuLi (2.5M, 헥산 중) 15mL(37.50mol)를 -78℃에서 첨가하였다. 이 혼합물을 -78℃에서 1시간 동안 교반한 후 트리메톡시보란(B(OCH3)3) 화합물 4.2mL(37.50mol)를 첨가하였다. 전체 반응물을 2시간 동안 교반한 후 NH4Cl 100mL로 반응을 종결시킨 후 에틸 아세테이트 200mL로 추출한 후, 얻어진 유기층을 증류수 100mL로 씻었다. 유기층을 MgSO4으로 건조시키고, 유기 용매는 감압하에서 제거하였다. 얻어진 고체는 재결정방법으로 분리하여 화합물 4, 5.4g(59%)을 수득하였다.10 g (25 mmol) of compound 3 were dissolved in 150 mL of THF, and then 15 mL (37.50 mol) of n-BuLi (2.5 M, in hexane) was added at -78 ° C. The mixture was stirred at −78 ° C. for 1 hour and then 4.2 mL (37.50 mol) of trimethoxyborane (B (OCH 3 ) 3 ) compound was added. After stirring the whole reaction for 2 hours, the reaction was terminated with 100 mL of NH 4 Cl and extracted with 200 mL of ethyl acetate, the organic layer obtained was washed with 100 mL of distilled water. The organic layer was dried over MgSO 4 and the organic solvent was removed under reduced pressure. The obtained solid was isolated by recrystallization to give 5.4 g (59%) of compound 4.

1-3: 화합물 7의 합성1-3: Synthesis of Compound 7

Figure pat00064
Figure pat00064

화합물 5, 6.7g(19.60mmol), 화합물 6, 4.1g(17.82mmol) 및 Na2CO3 4.7g(44.55mmol)을 톨루엔 90mL, 에탄올 20mL 및 증류수 20mL의 혼합 용액에 녹인 후, 테트라키스트리페닐포스핀 팔라듐 0.6g(0.53mmol)을 첨가하였다. 이 혼합물을 120℃에서 5시간 동안 교반하였다. 반응물을 실온으로 식힌 후 에틸 아세테이트 200mL로 추출하여, 얻어진 유기층을 증류수 100mL로 씻었다. 유기 용매를 감압하에서 제거하였다. 얻어진 고체는 메탄올로 씻어 필터한 후 건조시켰다. 실리카겔 컬럼크로마토그래피와 재결정법으로 분리하여 화합물 7, 3.7g(47%)을 수득하였다.Compound 5, 6.7 g (19.60 mmol), Compound 6, 4.1 g (17.82 mmol) and 4.7 g (44.55 mmol) of Na 2 CO 3 were dissolved in a mixed solution of 90 mL of toluene, 20 mL of ethanol, and 20 mL of distilled water, followed by tetrakistriphenyl 0.6 g (0.53 mmol) of phosphine palladium was added. The mixture was stirred at 120 ° C. for 5 hours. The reaction was cooled to room temperature and extracted with 200 mL of ethyl acetate, and the obtained organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol, filtered and dried. Silica gel column chromatography and recrystallization to give a compound 7, 3.7g (47%) was obtained.

1-4: 화합물 C-80의 합성1-4: Synthesis of Compound C-80

Figure pat00065
Figure pat00065

화합물 7, 3.7g(8.30mmol), 화합물 4, 3.3g(9.10mmol) 및 Na2CO3 2.2g(20.80mmol)을 톨루엔 44mL, 에탄올 11mL 및 증류수 11mL의 혼합 용액에 녹인 후, 테트라키스트리페닐포스핀 팔라듐 0.5g(0.4mmol)을 첨가하였다. 이 혼합물을 120℃에서 5시간 동안 교반하였다. 반응물을 실온으로 식힌 후 에틸 아세테이트 200mL로 추출하여, 얻어진 유기층을 증류수 100mL로 씻었다. 유기 용매는 감압하에서 제거하였다. 얻어진 고체는 메탄올로 씻어 필터한 후 건조시켰다. 실리카겔 컬럼크로마토그래피와 재결정법으로 분리하여 화합물 C-80, 1.8g(32%)을 수득하였다.Compound 7, 3.7 g (8.30 mmol), compound 4, 3.3 g (9.10 mmol) and 2.2 g (20.80 mmol) of Na 2 CO 3 were dissolved in a mixed solution of 44 mL of toluene, 11 mL of ethanol, and 11 mL of distilled water, followed by tetrakistriphenyl 0.5 g (0.4 mmol) of phosphine palladium was added. The mixture was stirred at 120 ° C. for 5 hours. The reaction was cooled to room temperature and extracted with 200 mL of ethyl acetate, and the obtained organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. The obtained solid was washed with methanol, filtered and dried. Silica gel column chromatography and recrystallization to give a compound C-80, 1.8g (32%) was obtained.

MS/ EIMS 측정치 685.90; 계산치 685.19, 녹는점(Mp): 211℃MS / EIMS Measurement 685.90; Calcd 685.19, Melting point (Mp): 211 ° C

[실시예 2] 화합물 C-99의 제조 Example 2 Preparation of Compound C-99

Figure pat00066
Figure pat00066

2-1: 화합물 9의 합성 2-1: Synthesis of Compound 9

4-(디페닐아미노)페닐보론산 15g(52mmol), 2,8-디브로모벤조[b,d]티오펜 103.8g(103.8mmol), 테트라키스(트리페닐포스핀)팔라듐(O)[Pd(PPh3)4] 3g(2.6mmol) 및 Na2CO3 14g(130mol)을 둥근 플라스크에 넣고, 톨루엔 250mL, EtOH 50mL 및 H2O 50mL를 넣었다. 반응 혼합물을 100℃ 상에서 2시간 교반하였다. 에틸 아세테이트(EA)/H2O로 추출하고 MgSO4로 수분을 제거한 후, 감압증류하였다. 컬럼 크로마토그래피하여 화합물 9, 13g(58%)을 수득하였다. 15 g (52 mmol) of 4- (diphenylamino) phenylboronic acid, 103.8 g (103.8 mmol) of 2,8-dibromobenzo [b, d] thiophene, tetrakis (triphenylphosphine) palladium (O) [ 3 g (2.6 mmol) of Pd (PPh 3 ) 4 ] and 14 g (130 mol) of Na 2 CO 3 were placed in a round flask, followed by 250 mL of toluene, 50 mL of EtOH, and 50 mL of H 2 O. The reaction mixture was stirred over 100 ° C. for 2 hours. Extraction with ethyl acetate (EA) / H 2 O, water removal with MgSO 4 , and distillation under reduced pressure. Column chromatography gave 13 g (58%) of compound 9.

2-2: 화합물 C-99의 합성 2-2: Synthesis of Compound C-99

4-(8-브로모디벤조[b,d]티오펜-2-일)-N,N-디페닐아닐린 6g(13.9mmol), 9,9-디메틸-9H-플루오렌-2-일보론산 4g(16.7mmol), Pd(PPh3)4 0.8g(0.7mmol) 및 K2CO3 4.8g(35mmol)을 둥근 플라스크에 넣고, 톨루엔 45 mL, EtOH 15 mL 및 H2O 15mL를 넣었다. 반응 혼합물은 120℃ 상에서 2시간 교반하였다. EA/H2O로 추출하고 MgSO4로 수분을 제거한 후, 감압증류하였다. 이후 컬럼 크로마토그래피하여 화합물 C-99, 3.9g(45%)를 얻었다. 6 g (13.9 mmol) of 4- (8-bromodibenzo [b, d] thiophen-2-yl) -N, N-diphenylaniline, 4 g of 9,9-dimethyl-9H-fluoren-2-ylboronic acid (16.7 mmol), 0.8 g (0.7 mmol) of Pd (PPh 3 ) 4 and 4.8 g (35 mmol) of K 2 CO 3 were placed in a round flask, and 45 mL of toluene, 15 mL of EtOH, and 15 mL of H 2 O were added thereto. The reaction mixture was stirred on 120 ° C. for 2 hours. Extraction with EA / H 2 O, water removal with MgSO 4 , and distillation under reduced pressure. After column chromatography to give the compound C-99, 3.9g (45%).

MS/EIMS 측정치 619.8; 계산치 619.23, 녹는점(Mp): 198℃MS / EIMS measurement 619.8; Calcd 619.23, Melting point (Mp): 198 ° C

[소자 실시예 1] 본 발명에 따른 유기 전계 발광 화합물을 이용한 OLED 소자 제작[Device Embodiment 1] Fabrication of OLED element using organic electroluminescent compound according to the present invention

본 발명의 발광 재료를 이용한 구조의 OLED 소자를 제작하였다. 우선, OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명 전극 ITO 박막(15Ω/□)을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. 다음으로 진공 증착 장비의 기판 홀더에 ITO기판을 장착한 후, 진공 증착장비 내의 셀에 N1,N1 ’-([1,1'-비페닐]-4,4'-디일)비스(N1-(나프탈렌-1-일)-N4,N4-디페닐벤젠-1,4-디아민)을 넣고 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 증발시켜 ITO 기판 위에 60nm 두께의 정공 주입층을 증착하였다. 이어서, 진공 증착 장비 내의 다른 셀에 C-99 를 넣고, 셀에 전류를 인가하여 증발시켜 정공 주입층 위에 20nm 두께의 정공 수송층을 증착하였다. 정공 주입층, 정공 수송층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 호스트로서 5-(4-([1,1':4',1"-터페닐]-3-일)피리미딘-2-일)-5H-벤조[4,5]티에노[3,2-c]카바졸을 넣고, 또 다른 셀에는 도펀트로서 D-1을 각각 넣은 후, 두 물질을 다른 속도로 증발시켜 도펀트와 호스트 합계량에 대해 도펀트를 15중량%의 양으로 도핑함으로써 상기 정공 수송층위에 30nm 두께의 발광층을 증착하였다. 이어서 상기 발광층 위에 전자 전달층으로써 한쪽 셀에 2-(4-(9,10-디(나프탈렌-2-일)안트라센-2-일)페닐)-1-페닐-1H-벤조[d]이미다졸을 넣고, 또다른 셀에는 리튬 퀴놀레이트(Lithium quinolate)를 각각 넣은 후, 두 물질을 같은 속도로 증발시켜 각각 50중량%의 양으로 도핑함으로써 30nm의 전자 전달층을 증착하였다. 이어서 전자 주입층으로 리튬 퀴놀레이트를 2nm 두께로 증착한 후, 다른 진공 증착장비를 이용하여 Al 음극을 150nm의 두께로 증착하여 OLED 소자를 제작하였다. 재료 별로 각 화합물은 10-6 torr 하에서 진공 승화 정제하여 사용하였다.An OLED device having a structure using the light emitting material of the present invention was fabricated. First, a transparent electrode ITO thin film (15? /?) Obtained from a glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned using trichlorethylene, acetone, ethanol and distilled water sequentially and stored in isopropanol Respectively. Next, the ITO substrate is mounted on the substrate holder of the vacuum deposition apparatus, and then N 1 , N 1 ' -([1,1'-biphenyl] -4,4'-diyl) bis (N 1- (naphthalen- 1 -yl) -N 4 , N 4 -diphenylbenzene-1,4-diamine) and evacuated until the vacuum in the chamber reaches 10 -6 torr, and then a current is applied to the cell. Evaporated to deposit a 60 nm thick hole injection layer on the ITO substrate. Subsequently, C-99 was placed in another cell in the vacuum deposition apparatus, and a 20 nm-thick hole transport layer was deposited on the hole injection layer by evaporation by applying a current to the cell. After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. 5- (4-([1,1 ': 4', 1 "-terphenyl] -3-yl) pyrimidin-2-yl) -5H-benzo [4,5 as host in one cell in the vacuum deposition equipment ] Add thieno [3,2-c] carbazole, add D-1 as a dopant in another cell, and then evaporate the two materials at different rates to obtain 15% by weight dopant relative to the total amount of dopant and host. A light emitting layer having a thickness of 30 nm was deposited on the hole transporting layer by doping, followed by 2- (4- (9,10-di (naphthalen-2-yl) anthracene-2-yl) in one cell as an electron transporting layer on the light emitting layer. Phenyl) -1-phenyl-1H-benzo [d] imidazole was added, and another cell was charged with lithium quinolate, respectively, and then the two materials were evaporated at the same rate and doped in an amount of 50% by weight each. The electron transport layer of 30 nm was deposited by depositing lithium quinolate with a thickness of 2 nm as the electron injection layer. The OLED device was manufactured by depositing unto each compound by each material was used, to obtain a vacuum sublimation under 10 -6 torr.

그 결과, 19.2 mA/cm2의 전류가 흘렀으며, 8020cd/m2의 녹색 발광이 확인되었다. As a result, a current of 19.2 mA / cm 2 flowed, and green light emission of 8020 cd / m 2 was confirmed.

[소자 실시예 2] 본 발명에 따른 유기 전계 발광 화합물을 이용한 OLED 소자 제작[Device Embodiment 2] Fabrication of OLED device using organic electroluminescent compound according to the present invention

정공 수송층으로서 C-80을 20nm 두께로 증착하고 발광층으로서 진공 증착 장비내의 한쪽 셀에 9-(4-([1,1':3',1''-터페닐]-4-일)피리미딘-2-일)-3-(디벤조[b,d]티오펜-4-일)-9H-카바졸을 넣고, 또 다른 셀에는 도펀트로서 D-25를 각각 넣은 후, 두 물질을 다른 속도로 증발시켜 도펀트와 호스트 합계량에 대해 도펀트를 15중량%의 양으로 도핑함으로써 상기 정공 수송층 위에 30nm 두께의 발광층을 증착한 것 이외에는 소자 실시예 1과 동일한 방법으로 OLED소자를 제작하였다.C-80 is deposited to a thickness of 20 nm as a hole transporting layer and 9- (4-([1,1 ': 3', 1 ''-terphenyl] -4-yl) pyrimidine as a light emitting layer in one cell in a vacuum deposition apparatus. 2-yl) -3- (dibenzo [b, d] thiophen-4-yl) -9H-carbazole, another cell with D-25 as a dopant, and then the two materials at different rates An OLED device was manufactured in the same manner as in Example 1, except that a 30 nm-thick light emitting layer was deposited on the hole transport layer by evaporating the dopant in an amount of 15 wt% based on the total amount of the dopant and the host.

그 결과, 6.4 mA/cm2의 전류가 흘렀으며, 2630 cd/m2의 녹색 발광이 확인되었다. As a result, a current of 6.4 mA / cm 2 flowed, and green light emission of 2630 cd / m 2 was confirmed.

[비교예 1] 종래의 발광 재료를 이용한 OLED 소자 제작[Comparative Example 1] OLED element fabrication using conventional light emitting material

정공 수송층으로서 N,N'-디(4-비페닐)-N,N'-디(4-비페닐)-4,4'-디아미노비페닐을 20nm 두께로 증착하였고 발광 재료로서 호스트로서 4,4‘-N,N'-디카바졸-비페닐을, 도펀트로서 화합물 D-15를 사용하고, 정공 수송층위에 30nm 두께의 발광층을 증착하고, 정공 저지층으로 알루미늄(III)비스(2-메틸-8-퀴놀리네이토)4-페닐페놀레이트를 10nm 두께로 증착한 것 외에는 소자 실시예 1과 동일한 방법으로 OLED소자를 제작하였다.N, N'-di (4-biphenyl) -N, N'-di (4-biphenyl) -4,4'-diaminobiphenyl as a hole transport layer was deposited to a thickness of 20 nm and 4 as a host as a light emitting material. A light emitting layer having a thickness of 30 nm was deposited on the hole transporting layer using compound D-15 as a dopant, using 4'-N, N'-dicarbazole-biphenyl, and aluminum (III) bis (2-methyl) as the hole blocking layer. An OLED device was manufactured in the same manner as in Example 1, except that -8-quinolinate) 4-phenylphenolate was deposited to a thickness of 10 nm.

그 결과, 9.7mA/cm2의 전류가 흘렀으며, 3350cd/m2의 녹색 발광이 확인되었다. As a result, a current of 9.7 mA / cm 2 flowed, and green light emission of 3350 cd / m 2 was confirmed.

본 발명에서 개발한 유기 전계 발광 화합물들의 발광 특성이 종래의 재료 대비 우수한 특성을 보이는 것을 확인할 수 있었다. 또한 본 발명에 따른 유기 전계 발광 화합물을 사용한 소자는 발광 특성, 전류 효율 및 전력 효율이 뛰어나다. It was confirmed that the organic electroluminescent compounds developed in the present invention exhibited excellent luminescent properties compared to the conventional materials. In addition, the device using the organic electroluminescent compound according to the present invention is excellent in light emission characteristics, current efficiency and power efficiency.

Claims (6)

하기 화학식 1로 표시되는 유기 전계 발광 화합물.
[화학식 1]
Figure pat00067

L1 및 L2은 각각 독립적으로 단일결합, 치환 또는 비치환된 (C6-C30)아릴렌, 또는 치환 또는 비치환된 (5-30원)헤테로아릴렌이고;
Ar1및 Ar2는 각각 독립적으로 치환 또는 비치환된 (C6-C30)아릴, 또는 치환 또는 비치환된 (5-30원)헤테로아릴이고;
X는 산소 원자, 황 원자 또는 -CR5R6이고;
R1 내지 R6는 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C2-C30)알케닐, 치환 또는 비치환된 (C2-C30)알키닐, 치환 또는 비치환된 (C1-C30) 알콕시, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C3-C30) 시클로알케닐, 치환 또는 비치환된 (3-7원)헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (5-30원)헤테로아릴, -NR11R12, -SiR13R14R15, -SR16, -OR17, -COR18 또는 -B(OR19)(OR20)이거나, 인접한 치환체와 연결되어 (3-30원)단일환 또는 다환의 지환족 또는 방향족 고리를 형성할 수 있고; 상기 형성된 지환족 또는 방향족 환의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 대체될 수 있고;
R11 내지 R20는 각각 독립적으로 수소, 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C2-C30)알케닐, 치환 또는 비치환된 (C2-C30)알키닐, 치환 또는 비치환된 (C1-C30)알콕시, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C3-C30)시클로알케닐, 치환 또는 비치환된 (3-7원)헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아릴 또는 치환 또는 비치환된 (5-30원)헤테로아릴이거나, 인접한 치환체와 연결되어 (3-30원)단일환 또는 다환의 지환족 또는 방향족 고리를 형성할 수 있고;
a는 1 내지 4의 정수이며, 2 이상의 정수인 경우 각각의 R1은 동일하거나 상이할 수 있고; b 내지 d는 각각 독립적으로 1 내지 3의 정수이며, 2 이상의 정수인 경우 각각의 R2, 각각의 R3 및 각각의 R4는 동일하거나 상이할 수 있고;
상기 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함하고;
상기 헤테로시클로알킬은 O, S 및 N에서 선택되는 하나 이상의 헤테로원자를 포함한다.
An organic electroluminescent compound represented by the following formula (1).
[Chemical Formula 1]
Figure pat00067

L 1 and L 2 are each independently a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5- to 30-membered) heteroarylene;
Ar 1 and Ar 2 are each independently substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5- to 30-membered) heteroaryl;
X is oxygen atom, sulfur atom or -CR 5 R 6 ;
R 1 to R 6 are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl Substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cyclo Alkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5--30 membered) heteroaryl, -NR 11 R 12 , -SiR 13 R 14 R 15 , -SR 16 , -OR 17 , -COR 18 or -B (OR 19 ) (OR 20 ) or linked to an adjacent substituent (3- to 30-membered) monocyclic or polycyclic alicyclic Or can form an aromatic ring; The carbon atoms of the alicyclic or aromatic rings formed may be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur;
R 11 to R 20 are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl , Substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cyclo Alkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5- to 30-membered) heteroaryl, or linked with adjacent substituents (3- to 30-membered) to form a monocyclic or polycyclic alicyclic or aromatic ring;
a is an integer from 1 to 4, and when it is an integer of 2 or more, each R 1 may be the same or different; b to d are each independently integers of 1 to 3, and each integer of 2 or more, each R 2 , each R 3 and each R 4 may be the same or different;
The heteroaryl comprises one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;
The heterocycloalkyl includes one or more heteroatoms selected from O, S and N.
제1항에 있어서, 상기 L1, L2, Ar1, Ar2, R1 내지 R6, 및 R11내지 R20에서 치환 (C1-C30)알킬, 치환 (C2-C30)알케닐, 치환 (C2-C30)알키닐, 치환 (C1-C30)알콕시, 치환 (C3-C30)시클로알킬, 치환 (C3-C30)시클로알케닐, 치환 (3-7원)헤테로시클로알킬, 치환 (C6-C30)아릴(렌), 및 치환 (5-30원)헤테로아릴(렌)의 치환체는 각각 독립적으로 중수소, 할로겐, 시아노, 카르복실, 니트로, 히드록시, (C1-C30)알킬, 할로(C1-C30)알킬, (C2-C30)알케닐, (C2-C30)알키닐, (C1-C30)알콕시, (C1-C30)알킬티오, (C3-C30)시클로알킬, (C3-C30)시클로알케닐, (3-7원)헤테로시클로알킬, (C6-C30)아릴옥시, (C6-C30)아릴티오, (C6-C30)아릴로 치환되거나 비치환된 (5-30원)헤테로아릴, (5-30원)헤테로아릴로 치환되거나 비치환된 (C6-C30)아릴, 트리(C1-C30)알킬실릴, 트리(C6-C30)아릴실릴, 디(C1-C30)알킬(C6-C30)아릴실릴, (C1-C30)알킬디(C6-C30)아릴실릴, 아미노, 모노 또는 디(C1-C30)알킬아미노, 모노 또는 디(C6-C30)아릴아미노, (C1-C30)알킬(C6-C30)아릴아미노, (C1-C30)알킬카보닐, (C1-C30)알콕시카보닐, (C1-C30)아릴카보닐, 디(C6-C30)아릴보로닐, 디(C1-C30)알킬보로닐, (C1-C30)알킬(C6-C30)아릴보로닐, (C6-C30)아르(C1-C30)알킬 및 (C1-C30)알킬(C6-C30)아릴로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 유기 전계 발광 화합물.The substituted (C1-C30) alkyl, substituted (C2-C30) alkenyl, substituted at L 1 , L 2 , Ar 1 , Ar 2 , R 1 to R 6 , and R 11 to R 20 . (C2-C30) alkynyl, substituted (C1-C30) alkoxy, substituted (C3-C30) cycloalkyl, substituted (C3-C30) cycloalkenyl, substituted (3-7 membered) heterocycloalkyl, substituted (C6- The substituents of C30) aryl (ene) and substituted (5- to 30-membered) heteroaryl (ene) are each independently deuterium, halogen, cyano, carboxyl, nitro, hydroxy, (C1-C30) alkyl, halo ( C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) (5- to 30-membered) heteroaryl unsubstituted or substituted with cycloalkenyl, (3- to 7-membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, (C6-C30) aryl (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-) substituted or unsubstituted with (5-30 membered) heteroaryl C30) arylsilyl, (C1-C30) alkyldi (C6-C) Arylsilyl, amino, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbo Neyl, (C1-C30) alkoxycarbonyl, (C1-C30) arylcarbonyl, di (C6-C30) arylboroyl, di (C1-C30) alkylboronyl, (C1-C30) alkyl (C6 -C30) arylboronyl, (C6-C30) ar (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl is at least one member selected from the group consisting of an organic electroluminescent compound . 제1항에 있어서,상기 L1 및 L2은 각각 독립적으로 단일결합, 치환 또는 비치환된 (C6-C15) 아릴렌, 또는 치환 또는 비치환된 (5-15원)헤테로아릴렌이고;
상기 Ar1및 Ar2 는 각각 독립적으로 치환 또는 비치환된 (C6-C15)아릴, 또는 치환 또는 비치환된 (5-15원)헤테로아릴이고;
상기 R1 및 R6는 각각 독립적으로 수소, 할로겐, 치환 또는 비치환된 (C1-C15)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (5-30원) 헤테로아릴, -NR11R12 또는 -SiR13R14R15 이고, 여기에서 R11 및 R12는 각각 독립적으로 치환 또는 비치환된 (C6-C15)아릴이고, R13 내지 R15는 각각 독립적으로 치환 또는 비치환된 (C1-C10)알킬인 것을 특징으로 하는 유기 전계 발광 화합물.The compound of claim 1, wherein L 1 and L 2 are each independently a single bond, a substituted or unsubstituted (C6-C15) arylene, or a substituted or unsubstituted (5- to 15-membered) heteroarylene;
Ar 1 and Ar 2 are each independently substituted or unsubstituted (C6-C15) aryl, or substituted or unsubstituted (5- to 15-membered) heteroaryl;
R 1 and R 6 are each independently hydrogen, halogen, substituted or unsubstituted (C1-C15) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5- to 30-membered) hetero Aryl, -NR 11 R 12 or -SiR 13 R 14 R 15 , wherein R 11 and R 12 are each independently substituted or unsubstituted (C6-C15) aryl, and R 13 to R 15 are each independently An organic electroluminescent compound, which is substituted or unsubstituted (C1-C10) alkyl. 제1항에 있어서, 상기 L1 및 L2은 각각 독립적으로 단일결합, 비치환된 (C6-C15)아릴렌, (C6-C15)아릴로 치환된 (C6-C15)아릴렌, 또는 비치환된 (5-10원)헤테로아릴렌이고;
상기 Ar1및 Ar2 은 각각 독립적으로 비치환된 (C6-C15)아릴; (C1-C6)알킬, (C6-C15)아릴, (C6-C15)아릴아미노 또는 (C6-C15)아릴(5-10원)헤테로아릴아미노로 치환된 (C6-C15)아릴; 비치환된 (5-10원)헤테로아릴; 또는 (C6-C15)아릴 또는 (C6-C15)아릴아미노로 치환된 (5-10원)헤테로아릴이고,
상기 R1 및 R6는 각각 독립적으로 수소, 할로겐, 비치환된 (C1-C6)알킬, 비치환된 (C6-C20)아릴, 비치환된 (5-15원)헤테로아릴, 또는 (C1-C6)알킬 또는 (C6-C15)아릴로 치환된 (C6-C20)아릴인 것을 특징으로 하는 유기 전계 발광 화합물.The method of claim 1, wherein L 1 and L 2 are each independently a single bond, unsubstituted (C6-C15) arylene, (C6-C15) arylene substituted with (C6-C15) aryl, or unsubstituted (5-10 membered) heteroarylene;
Ar 1 and Ar 2 are each independently unsubstituted (C 6 -C 15) aryl; (C6-C15) aryl substituted with (C1-C6) alkyl, (C6-C15) aryl, (C6-C15) arylamino or (C6-C15) aryl (5-10 membered) heteroarylamino; Unsubstituted 5-10 membered heteroaryl; Or (5-10 membered) heteroaryl substituted with (C6-C15) aryl or (C6-C15) arylamino,
R 1 and R 6 are each independently hydrogen, halogen, unsubstituted (C1-C6) alkyl, unsubstituted (C6-C20) aryl, unsubstituted (5- to 15-membered) heteroaryl, or (C1- C6) alkyl or (C6-C20) aryl substituted with (C6-C15) aryl. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화합물로부터 선택되는 것을 특징으로 하는 유기 전계 발광 화합물.
Figure pat00068

Figure pat00069

Figure pat00070

Figure pat00071

Figure pat00072

Figure pat00073

Figure pat00074

Figure pat00075

Figure pat00076

Figure pat00077

Figure pat00078

Figure pat00079

Figure pat00080

Figure pat00081

Figure pat00082

Figure pat00083

Figure pat00084

Figure pat00085

Figure pat00086

Figure pat00087

Figure pat00088

Figure pat00089

Figure pat00090

Figure pat00091

Figure pat00092

Figure pat00093

Figure pat00094

Figure pat00095

Figure pat00096

Figure pat00097
The organic electroluminescent compound according to claim 1, wherein the compound represented by Chemical Formula 1 is selected from the following compounds.
Figure pat00068

Figure pat00069

Figure pat00070

Figure pat00071

Figure pat00072

Figure pat00073

Figure pat00074

Figure pat00075

Figure pat00076

Figure pat00077

Figure pat00078

Figure pat00079

Figure pat00080

Figure pat00081

Figure pat00082

Figure pat00083

Figure pat00084

Figure pat00085

Figure pat00086

Figure pat00087

Figure pat00088

Figure pat00089

Figure pat00090

Figure pat00091

Figure pat00092

Figure pat00093

Figure pat00094

Figure pat00095

Figure pat00096

Figure pat00097
 제1항의 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.An organic electroluminescent device comprising the compound of claim 1.
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