KR102091727B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof Download PDF

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KR102091727B1
KR102091727B1 KR1020190102723A KR20190102723A KR102091727B1 KR 102091727 B1 KR102091727 B1 KR 102091727B1 KR 1020190102723 A KR1020190102723 A KR 1020190102723A KR 20190102723 A KR20190102723 A KR 20190102723A KR 102091727 B1 KR102091727 B1 KR 102091727B1
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문성윤
이선희
최연희
이범성
여승원
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덕산네오룩스 주식회사
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Abstract

본 발명은 소자의 발광효율, 안정성 및 수명을 향상시킬 수 있는 신규 화합물 및 이를 이용한 유기전기소자, 그 전자 장치를 제공한다.The present invention provides a novel compound capable of improving the luminous efficiency, stability and lifespan of a device, an organic electrical device using the same, and an electronic device thereof.

Description

유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치{COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF}Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF}

본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다. In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. Materials used as the organic material layer in the organic electric device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function.

유기 전기 발광소자에 있어 가장 문제시되는 것은 수명과 효율인데, 디스플레이가 대면적화 되면서 이러한 효율이나 수명 문제는 반드시 해결해야 되는 상황이다.The most important issues in organic electroluminescent devices are life and efficiency, and as the display becomes larger, these efficiency and life problems must be solved.

효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동시 발생되는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다. Efficiency, life, and driving voltage are related to each other, and when the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, and as a result, It shows a tendency to increase the life.

하지만 상기 유기물층을 단순히 개선한다고 하여 효율을 극대화시킬 수는 없다. 왜냐하면 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있기 때문이다. However, simply improving the organic layer does not maximize efficiency. This is because long life and high efficiency can be achieved at the same time when the optimum combination of energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) is achieved.

또한, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 반드시 정공수송층과 발광층 사이에 발광보조층이 존재하여야 하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광 보조층의 개발이 필요한 시점이다. In addition, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, there must be a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and different light emission assists according to each light emitting layer (R, G, B) It is time to develop the layer.

일반적으로 전자수송층에서 발광층으로 전자(electron)이 전달되고 정공(hole)이 정공수송층에서 발광층으로 전달되어 재조합(recombination)에 의해 엑시톤(exciton)이 생성된다. In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

하지만 정공수송층에 사용되는 물질의 경우 낮은 HOMO 값을 가져야 하기 때문에 대부분 낮은 T1 값을 가지며, 이로 인해 발광층에서 생성된 엑시톤(exciton)이 정공수송층으로 넘어가게 되어 결과적으로 발광층 내 전하불균형(charge unbalance)을 초래하여 정공수송층 계면에서 발광하게 된다.However, in the case of the material used for the hole transport layer, since it has to have a low HOMO value, most of them have a low T1 value, and as a result, the exciton generated in the light emitting layer is transferred to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission at the hole transport layer interface.

정공수송층 계면에서 발광될 경우, 유기전기소자의 색순도 및 효율이 저하되고 수명이 짧아지는 문제점이 발생하게 된다. 따라서 높은 T1 값을 가지며, 정공 수송층 HOMO 에너지 level과 발광층의 HOMO 에너지 level 사이의 HOMO level를 갖는 발광보조층이 개발이 절실히 요구된다. When emitting light at the interface of the hole transport layer, a problem arises in that the color purity and efficiency of the organic electric device decreases and the life is shortened. Therefore, a light emitting auxiliary layer having a high T1 value and having a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.

한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투확산되는 것을 지연시키면서, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 정공수송층 재료의 낮은 유리전이 온도는 소자 구동시, 박막 표면의 균일도를 저하시키는 특성이 있는바, 이는 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자는 주로 증착방법에 의해 형성되는데, 증착시 오랫동안 견딜 수 있는 재료, 즉 내열특성이 강한 재료 개발이 필요한 실정이다. On the other hand, while delaying the diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electric device, into the organic layer, stable properties against Joule heating generated during device driving, that is, high glass transition There is a need to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the thin film surface when driving the device, which has been reported to have a great influence on the device life. In addition, the OLED device is mainly formed by a vapor deposition method, and it is necessary to develop a material that can withstand a long time during vapor deposition, that is, a material having strong heat resistance.

전술한 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광보조층 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 따라서 새로운 재료의 개발이 계속 요구되고 있다.In order to fully exhibit the excellent characteristics of the above-mentioned organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light-emitting auxiliary layer material, a light emitting material, an electron transport material, an electron injection material, are stable and efficient Although it should be preceded by the material, the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently developed, and thus, the development of a new material is still required.

본 발명은 소자의 높은 발광효율, 낮은 구동전압, 고내열성, 색순도 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a compound capable of improving the device's high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifetime, and an organic electric device using the same and its electronic device.

일측면에서, 본 발명은 하기 화학식으로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by the following formula.

Figure 112019086099118-pat00001
Figure 112019086099118-pat00001

다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.

본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다.By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifetime of the device can be greatly improved.

도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.1 is an exemplary view of an organic electroluminescent device according to the present invention.

이하, 본 발명의 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".

한편, 본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소, 염소, 브롬, 및 요오드를 포함한다. On the other hand, the terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine unless otherwise specified.

본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkyl" or "alkyl group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto unless otherwise specified.

본 발명에 사용된 용어 "알케닐" 또는 "알키닐"은 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 여기에 제한되는 것은 아니다. The terms "alkenyl" or "alkynyl" used in the present invention have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto.

본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다. As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

본 발명에 사용된 용어 "알콕시기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkoxy group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto, unless otherwise specified.

본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified.

본 발명에서 아릴기 또는 아릴렌기는 단일환 또는 복소환의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 링을 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다. In the present invention, the aryl group or arylene group means a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, or spirofluorene group.

본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 3 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다.As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 3 to 60 carbon atoms, each of which contains one or more heteroatoms, unless otherwise specified. No, it includes a heterocycle as well as a single ring, and may be formed by combining adjacent groups.

본 발명에 사용된 용어 "헤테로시클로알킬", "헤테로고리기"는 다른 설명이 없는 한 하나 또는 그 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다. 또한, "헤테로고리기"는 헤테로원자를 포함하는 지환족 및/또는 방향족을 의미할 수 있다.The terms "heterocycloalkyl" and "heterocyclic group" used in the present invention include one or more heteroatoms, have 2 to 60 carbon atoms, and include heterocycles as well as monocycles, unless otherwise specified. , Adjacent groups may be formed by combining. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic group containing heteroatoms.

본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 및 Si를 나타낸다. The term “heteroatom” as used herein refers to N, O, S, P and Si unless otherwise noted.

다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다. Unless otherwise specified, the term "aliphatic" as used herein refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

다른 설명이 없는 한, 본 발명에 사용된 용어 "포화 또는 불포화 고리"는 포화 또는 불포화 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 헤테로고리를 의미한다.Unless otherwise stated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or heterocycle having 6 to 60 carbon atoms.

전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다. Other hetero compounds or hetero radicals other than the above-described hetero compounds include one or more hetero atoms, but are not limited thereto.

또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, 및 C5~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 arylthiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, deuterium substituted C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C 5 to C 20 heterocyclic groups, and is not limited to these substituents.

도 1은 본 발명에 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

도 1을 참조하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(110)과 제 2전극(180) 사이에 화학식 1로 표시되는 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 and a second electrode 180 formed on the substrate 110. ) Is provided with an organic material layer containing the compound represented by Formula 1. At this time, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다. The organic material layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 sequentially on the first electrode 120. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light-emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 may also serve as a hole blocking layer.

또한, 미도시하였지만, 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다. In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

상기 유기물층에 적용되는 본 발명에 따른 화합물은 정공주입층(130), 정공수송층(140), 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트 또는 캐핑층의 재료로 사용될 수 있을 것이다. 바람직하게는, 본 발명의 화합물은 발광층(150) 및/또는 발광보조층(151)으로 사용될 수 있을 것이다.The compound according to the present invention applied to the organic layer is the material of the host or dopant or capping layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the light emitting layer 150 Could be used as Preferably, the compound of the present invention may be used as the light emitting layer 150 and / or the light emitting auxiliary layer 151.

한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.On the other hand, even in the same core, the band gap, electrical properties, and interfacial properties may vary depending on which substituents are attached to which positions, so the selection of the core and the combination of sub-substituents coupled thereto are also very good. It is important, especially when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

이미 설명한 것과 같이, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 정공수송층과 발광층 사이에 발광보조층이 형성하는 것이 바람직하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광 보조층의 개발이 필요한 시점이다. 한편, 발광보조층의 경우 정공수송층 및 발광층(호스트)과의 상호관계를 파악해야하므로 유사한 코어를 사용하더라도 사용되는 유기물층이 달라지면 그 특징을 유추하기는 매우 어려울 것이다. As already described, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, it is preferable that a light-emitting auxiliary layer is formed between the hole transport layer and the light emitting layer, depending on each light emitting layer (R, G, B) It is time to develop different light-emitting auxiliary layers. On the other hand, in the case of the light-emitting auxiliary layer, since it is necessary to grasp the relationship between the hole transport layer and the light-emitting layer (host), even if a similar core is used, it will be very difficult to infer the characteristics of the organic layer used.

따라서, 본 발명에서는 화학식 1로 표시되는 화합물을 사용하여 발광층 또는 발광보조층을 형성함으로써 각 유기물층 간의 에너지 레벨(level) 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다. Therefore, in the present invention, by forming a light emitting layer or a light emitting auxiliary layer using the compound represented by Chemical Formula 1, the energy level (level) and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the material are optimized and organic It is possible to simultaneously improve the lifespan and efficiency of the electric device.

본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form the anode 120, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer are formed thereon. 160) and after forming an organic material layer including the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer is less by a method such as a solution process or a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), which is not a vapor deposition method using various polymer materials. It can be prepared by a number of layers. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

본 발명에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

또한, 본 발명에 따른 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.In addition, the organic electric device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), a monochromatic or white lighting device.

본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다.Hereinafter, a compound according to an aspect of the present invention will be described.

본 발명의 일측면에 따른 화합물은 하기 화학식 1로 표시된다.The compound according to an aspect of the present invention is represented by the following formula (1).

Figure 112019086099118-pat00002
Figure 112019086099118-pat00002

상기 화학식 1에서,In Chemical Formula 1,

A환은 이웃한 N(질소)을 포함하는 오각링에 융합된(fused) 방향족고리 또는 헤테로고리일 수 있다. 즉, A환은 N을 포함하는 오각링과 한변을 공유한다. 또한, A환은 단환 또는 다환고리일 수 있다. 다환고리인 경우 서로 융합된(fused) 형태일 수도 있고 복수개의 환이 서로 융합되지 않은 형태일 수도 있으며, 융합된 형태와 비융합된 형태가 혼합된 환일 수도 있다. 여기서, 방향족고리 및 헤테로고리는 탄소수 6 내지 60일 수 있고, 바람직하게는 탄소수 6~14일 수 있다. 즉, A환은 벤젠, 나프탈렌, 페난트렌 등일 수 있다.The A ring may be an aromatic ring or a heterocycle fused to a pentagonal ring containing neighboring N (nitrogen). That is, the A ring shares one side with a pentagonal ring containing N. Further, the A ring may be a monocyclic or polycyclic ring. In the case of a polycyclic ring, it may be a fused form, a plurality of rings may not be fused with each other, or a fused form and a non-fused form may be mixed. Here, the aromatic ring and the heterocycle may have 6 to 60 carbon atoms, preferably 6 to 14 carbon atoms. That is, the A ring may be benzene, naphthalene, phenanthrene, and the like.

또한, A환이 헤테로고리인 경우, 탄소수 2 내지 60의 헤테로고리일 수 있고, 예시적으로 싸이오펜, 퓨란, 피리딘, 인돌, 퀴놀린 등일 수 있다.In addition, when the A ring is a heterocycle, it may be a heterocycle having 2 to 60 carbon atoms, and may be, for example, thiophene, furan, pyridine, indole, quinoline, or the like.

상기 화학식 1에서, X는 CR′R″, NR′, S 또는 O이며, 여기서 R′ 및 R″은 서로 독립적으로 C6~C60의 아릴기; C2~C60의 헤테로고리기; 또는 C1~C50의 알킬기이다.In Formula 1, X is CR'R ″, NR ′, S or O, wherein R ′ and R ″ are independently of each other C 6 ~ C 60 aryl group; C 2 ~ C 60 heterocyclic group; Or an alkyl group of C 1 ~ C 50.

또한, 상기 화학식 1에서, R1은

Figure 112019086099118-pat00003
로 표시될 수 있다.In addition, in Chemical Formula 1, R 1 is
Figure 112019086099118-pat00003
It may be indicated by.

상기 l과 o는 0 또는 1의 정수이며, l+o는 1이상일 수 있다. l이 0인 경우, L은 부존재(직접결합 또는 단일결합이라고도 함)함을 의미한다.The l and o are integers of 0 or 1, and l + o may be 1 or more. When l is 0, it means that L is absent (also called a direct bond or a single bond).

한편, 상기 식에서 L은 o의 값에 따라 1가 또는 2가일 수 있다. 예컨대, o가 0이고, l이 1인 경우 L은 1가일 수 있고, o=l=1인 경우 L은 2가일 수 있다. 따라서, L은 ⅰ) C6~C60의 아릴기, C2~C60의 1가의 헤테로고리기 및 플루오렌일기로 이루어진 1가의 치환기 군에서 선택되거나, 또는 ⅱ) C6~C60의 아릴렌기, C2~C60의 2가의 헤테로고리기 및 플루오렌일렌기로 이루어진 2가의 치환기 군에서 선택될 수 있을 것이다.Meanwhile, in the above formula, L may be monovalent or divalent depending on the value of o. For example, when o is 0 and l is 1, L may be monovalent, and when o = l = 1, L may be divalent. Accordingly, L is selected from the group consisting of: i) C 6 ~ C 60 aryl groups, C 2 ~ C 60 monovalent heterocyclic groups and fluorenyl groups, or ii) C 6 ~ C 60 aryl. It may be selected from the group of divalent substituents consisting of a alkylene group, a C 2 to C 60 divalent heterocyclic group, and a fluorenylene group.

또한, 상기 식에서 Y는 수소, 중수소, 삼중수소, 할로겐기, -N(Ar3)(Ar4), 니트로기, 니트릴기, 아미드기, 실란기, C1~C50의 알킬기, C6~C60의 아릴기, C2~C20의 알케닐기, C2~C60의 헤테로고리기, 및 C6~C60의 방향족 고리와 C3~C60의 지방족고리의 축합고리기로 이루어진 군에서 선택될 수 있다. In the above formula, Y is hydrogen, deuterium, tritium, halogen group, -N (Ar 3 ) (Ar 4 ), nitro group, nitrile group, amide group, silane group, C 1 ~ C 50 alkyl group, C 6 ~ In the group consisting of C 60 aryl group, C 2 ~ C 20 alkenyl group, C 2 ~ C 60 heterocyclic group, and C 6 ~ C 60 aromatic ring and C 3 ~ C 60 aliphatic ring condensed ring group Can be selected.

그리고, R1의 p는 1이상의 정수이다. 이때, p는 A환에 따라 결정될 수 있을 것이다. 예컨대, A환이 벤젠링인 경우 벤젠링의 치환가능한 탄소수가 4개이므로 p는 1 내지 4의 정수일 수 있고, A환이 나프틸인 경우 1 내지 6이 될 수 있을 것이다. In addition, p of R 1 is an integer of 1 or more. At this time, p may be determined according to the A ring. For example, when the A ring is a benzene ring, p may be an integer of 1 to 4 because the number of carbon atoms of the benzene ring is 4, and if the A ring is a naphthyl, it may be 1 to 6.

이때, p가 2이상인 경우 복수의 R1은 서로 같거나 상이할 수 있으며, p가 2이상인 경우 이웃한 R1끼리 서로 결합하여 하나 이상의 고리를 형성할 수 있다. 즉, p가 2이상인 경우 이웃한 R1끼리 서로 결합함으로써 A환과 융합된 형태를 형성할 수도 있다. 따라서, 즉, A환 자체가 다환고리일 수도 있지만, A환이 단환고리이더라도 치환기 R1이 서로 결합하여 A환에 융합된 다환고릴를 형성할 수도 있을 것이다.At this time, when p is 2 or more, a plurality of R 1 may be the same or different from each other, and when p is 2 or more, adjacent R 1 may be bonded to each other to form one or more rings. That is, when p is 2 or more, adjacent R 1 may be bonded to each other to form a fused form with the A ring. Thus, that is, although the A ring itself may be a polycyclic ring, even if the A ring is a monocyclic ring, the substituents R 1 may be bonded to each other to form a polycyclic Goryl fused to the A ring.

R2 내지 R5는 R1과 동일하게 정의될 수 있다. 즉, 이들은

Figure 112019086099118-pat00004
로 표시될 수 있고, 여기서 L, Y, l, o 등은 R1에서 정의된 것과 동일하게 정의될 수 있다.R 2 to R 5 may be defined the same as R 1 . That is, these
Figure 112019086099118-pat00004
It may be represented by, where L, Y, l, o, etc. may be defined as defined in R 1 .

한편, 상기 화학식 1에서, m과 n은 각각 0 또는 1일 수 있으나, 단 m+n은 1이상인 것이 바람직하다. 즉, Ar1 과 Ar2 중 적어도 하나는 존재해야 한다.Meanwhile, in Chemical Formula 1, m and n may be 0 or 1, respectively, but m + n is preferably 1 or more. That is, at least one of Ar 1 and Ar 2 must be present.

한편, Ar1은 m과 n에 따라 치환기 정의가 달라질 수 있는데, 예컨대, m=0인 경우 Ar1은 직접결합(즉, Ar1이 부존재함)에 해당하고, m=1, n=0인 경우 Ar1은 C6~C60의 아릴기, C2~C20의 알케닐기, C2~C60의 헤테로고리기, C6~C60의 방향족 고리와 C3~C60의 지방족 고리의 축합고리기, C1~C50의 알킬기 및 플루오렌일기 등과 같은 1가 치환기로 이루어진 군에서 선택되며, m=n=1인 경우 Ar1은 C6~C60의 아릴렌기, C2~C20의 알케닐렌기, C2~C60의 2가의 헤테로고리기, C6~C60의 방향족 고리와 C3~C60의 지방족 고리의 축합고리기, C2~C20의 알킬렌기 및 플루오렌일렌기 등과 같은 2가 치환기로 이루어진 군에서 선택될 수 있다.Meanwhile, Ar 1 may have different substituent definitions depending on m and n. For example, when m = 0, Ar 1 corresponds to a direct bond (that is, Ar 1 is absent), and m = 1, n = 0. In case Ar 1 is C 6 ~ C 60 aryl group, C 2 ~ C 20 alkenyl group, C 2 ~ C 60 heterocyclic group, C 6 ~ C 60 aromatic ring and C 3 ~ C 60 aliphatic ring It is selected from the group consisting of monovalent substituents such as a condensed ring group, an alkyl group of C 1 to C 50 and a fluorenyl group, and when m = n = 1, Ar 1 is an arylene group of C 6 to C 60 , C 2 to C Alkenylene group of 20 , C 2 ~ C 60 divalent heterocyclic group, C 6 ~ C 60 aromatic ring and C 3 ~ C 60 aliphatic ring condensed ring group, C 2 ~ C 20 alkylene group and flu It may be selected from the group consisting of divalent substituents such as an orylene group.

그리고, 화학식 1에서 Ar2는 n=0인 경우에는 부존재하는 경우이며, n=1인 경우 Ar2는 할로겐기; 시아노기; 니트로기; 니트릴기; 아미드기; 실란기; C6~C60의 아릴기; C2~C20의 알케닐기; C2~C60의 헤테로고리기; C1~C50의 알킬기; -N(Ar3)(Ar4) 및 C6~C60의 방향족 고리와 C3~C60의 지방족 고리의 축합고리기로 이루어진 1가의 치환기 군에서 선택될 수 있다.In addition, in Formula 1, Ar 2 is absent when n = 0, and Ar 2 is halogen when n = 1; Cyano group; Nitro group; Nitrile group; Amide group; Silane group; C 6 ~ C 60 Aryl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 60 heterocyclic group; C 1 ~ C 50 alkyl group; It may be selected from the group of monovalent substituents consisting of -N (Ar 3 ) (Ar 4 ) and a condensed ring group of an aromatic ring of C 6 ~ C 60 and an aliphatic ring of C 3 ~ C 60 .

이때, 상기 Ar3 및 Ar4는 서로 독립적으로 C6~C60의 아릴기, C2~C60의 헤테로고리기, 플루오렌일기, C1~C50의 알킬기 및 C2~C20의 알케닐기로 이루어진 군에서 선택되거나, 또는 Ar3 및 Ar4가 서로 결합하여 N과 함께 헤테로고리를 형성할 수도 있을 것이다.At this time, Ar 3 and Ar 4 are independently of each other C 6 ~ C 60 aryl group, C 2 ~ C 60 heterocyclic group, fluorenyl group, C 1 ~ C 50 alkyl group and C 2 ~ C 20 eggs It may be selected from the group consisting of kenyl groups, or Ar 3 and Ar 4 may combine with each other to form a heterocycle together with N.

한편, 상기 A환의 방향족고리, R1~R5, X의 R′, R″, Ar1 내지 Ar4등은 다른 치환기로 더 치환될 수 있을 것이다.On the other hand, the aromatic ring of the A ring, R 1 ~ R 5 , R ′, R ″ of X, Ar 1 to Ar 4, etc. may be further substituted with other substituents.

구체적으로, 상기 A환의 방향족고리, L, Y, Ar1 내지 Ar4, R′ 및 R″이 C6~C60의 아릴기인 경우와, 상기 Y, Ar1 및 Ar2의 축합고리기인 경우와, 상기 L 및 Ar1의 C6~C60가 아릴렌기인 경우, 이들은 중수소; 할로겐기; C1~C20의 알킬기; C1~C20의 알콕시기; C6~C20의 아릴기 또는 C2~C20의 헤테로고리기로 치환된 아민기; C1~C20의 알킬아민기; C1~C20의 알킬티오기; C6~C20의 아릴티오기; C2~C20의 알케닐기; C2~C20의 알키닐기; C3~C20의 시클로알킬기; 중수소로 치환된 C6~C20의 아릴기; C8~C20의 아릴알케닐기; 실란기; 붕소기; 게르마늄기; 및 C2~C20의 헤테로고리기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Specifically, when the aromatic ring of the A ring, L, Y, Ar 1 to Ar 4 , R ′ and R ″ are C 6 to C 60 aryl groups, and Y, Ar 1 and Ar 2 are condensed ring groups , When C 6 ~ C 60 of the L and Ar 1 are arylene groups, they are deuterium; Halogen group; C 1 ~ C 20 alkyl group; C 1 ~ C 20 Alkoxy group; An amine group substituted with an aryl group of C 6 to C 20 or a heterocyclic group of C 2 to C 20 ; C 1 ~ C 20 alkylamine group; C 1 ~ C 20 alkylthio group; C 6 ~ C 20 Arylthio group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 3 ~ C 20 cycloalkyl group; C 6 ~ C 20 aryl group substituted with deuterium; C 8 ~ C 20 arylalkenyl group; Silane group; Boron group; Germanium group; And C 2 ~ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group.

또한, 상기 A, L, Y, Ar1 내지 Ar4, R′및 R″의 C2~C60의 헤테로고리기는, 할로겐기; C1~C20의 알킬기; C2~C20의 알케닐기; C1~C20의 알콕시기; C6~C20의 아릴기 또는 C2~C20의 헤테로고리기로 치환된 아민기; C6~C60의 아릴기; 중수소로 치환된 C6~C20의 아릴기; C7~C20의 아릴알킬기; C8~C20의 아릴알케닐기; 니트릴기; 및 아세틸렌기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.In addition, the heterocyclic group of C 2 ~ C 60 of A, L, Y, Ar 1 to Ar 4 , R ′ and R ″ is a halogen group; C 1 ~ C 20 alkyl group; C 2 ~ C 20 alkenyl group; C 1 ~ C20 Alkoxy group; An amine group substituted with an aryl group of C 6 to C 20 or a heterocyclic group of C 2 to C 20 ; C 6 ~ C 60 Aryl group; C 6 ~ C 20 aryl group substituted with deuterium; C 7 ~ C 20 Arylalkyl group; C 8 ~ C 20 arylalkenyl group; Nitrile group; And it may be substituted with one or more substituents selected from the group consisting of acetylene groups.

또한, 상기 L, Ar1, Ar3 및 Ar4의 플루오렌일기와, 상기 L 및 Ar1의 플루오렌일렌기는, 중수소, 할로겐기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C1~C50의 알킬기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.In addition, the fluorenyl group of L, Ar 1 , Ar 3 and Ar 4 , and the fluorenylene group of L and Ar 1 are deuterium, halogen group, C 2 to C 20 alkenyl group, C 1 to C 20 Alkoxy group, C 6 ~ C 20 aryl group, C 7 ~ C 20 arylalkyl group, C 8 ~ C 20 arylalkenyl group, C 1 ~ C 50 alkyl group, C 2 ~ C 20 heterocyclic group, nitrile It may be substituted with one or more substituents selected from the group consisting of groups and acetylene groups.

또한, 상기 Y, Ar1 내지 Ar4, R′및 R″의 C1~C50의 알킬기와, 상기 Ar1의 C2~C20의 알킬렌기는, C2~C20의 알케닐기; C1~C20의 알콕시기; C6~C20의 아릴기; 중수소로 치환된 C6~C20의 아릴기; C7~C20의 아릴알킬기; C8~C20의 아릴알케닐기; C2~C20의 헤테로 고리기; 니트릴기; 및 아세틸렌기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Further, the alkenyl group of the Y, Ar 1 to Ar4, R 'and R "of the C 1 ~ C 50 alkyl group, and a group of C 2 ~ C 20 alkylene group of said Ar 1, C 2 ~ C 20 of; C 1 ~ C 20 Alkoxy group; C 6 ~ C 20 aryl group; C 6 ~ C 20 aryl group substituted with deuterium; C 7 ~ C 20 Arylalkyl group; C 8 ~ C 20 arylalkenyl group; C 2 ~ C 20 heterocyclic group; Nitrile group; And it may be substituted with one or more substituents selected from the group consisting of acetylene groups.

또한, 상기 Y, Ar1 내지 Ar4 의 C2~C20의 알케닐기와, 상기 Ar1의 C2~C20의 알케닐렌기는, 중수소; 할로겐기; C1~C20의 알킬기; C1~C20의 알콕시기; C6~C20의 아릴기 또는 C2~C20의 헤테로고리기로 치환된 아민기; C6~C60의 아릴기; 중수소로 치환된 C6~C20의 아릴기; C7~C20의 아릴알킬기; C8~C20의 아릴알케닐기; C3~C20의 헤테로 고리기; 니트릴기; 및 아세틸렌기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Also, the Y, Ar 1 to alkenylene group, heavy hydrogen of Ar 4 of C 2 ~ C 20 alkenyl group, said Ar 1 of C 2 ~ C 20 of; Halogen group; C 1 ~ C 20 alkyl group; C 1 ~ C 20 Alkoxy group; An amine group substituted with an aryl group of C 6 to C 20 or a heterocyclic group of C 2 to C 20 ; C 6 ~ C 60 Aryl group; C 6 ~ C 20 aryl group substituted with deuterium; C 7 ~ C 20 Arylalkyl group; C 8 ~ C 20 arylalkenyl group; C 3 ~ C 20 heterocyclic group; Nitrile group; And it may be substituted with one or more substituents selected from the group consisting of acetylene groups.

한편, 상기 화학식 1은 하기 화학식 중 하나로 표시될 수 있다. Meanwhile, Chemical Formula 1 may be represented by one of the following Chemical Formulas.

<화학식 2><Formula 2>

Figure 112019086099118-pat00005
Figure 112019086099118-pat00005

<화학식 3><Formula 3>

Figure 112019086099118-pat00006
Figure 112019086099118-pat00006

<화학식4><Formula 4>

Figure 112019086099118-pat00007
Figure 112019086099118-pat00007

화학식 1에서, A환이 벤젠링인 경우 상기 화학식 2로 표시될 수 있고, 화학식 1에서 A환이 벤젠링이면서 R1~R4 중 적어도 하나가 -L-N(Ar3)(Ar4)인 경우에는 상기 화학식 3으로 표시될 수 있으며, 화학식 1에서 A환이 벤젠링이고 (Ar2)m이 -N(Ar3)(Ar4)인 경우 상기 화학식 4로 표시될 수 있을 것이다.In Formula 1, when the A ring is a benzene ring, it may be represented by Formula 2, and in Formula 1, when the A ring is a benzene ring and at least one of R 1 to R 4 is -LN (Ar 3 ) (Ar 4 ), It may be represented by Formula 3, and in Formula 1, when the A ring is a benzene ring and (Ar 2 ) m is -N (Ar 3 ) (Ar 4 ), it may be represented by Formula 4 above.

상기 화학식 2 내지 4에서, R11~R14는 화학식 1의 ⅰ) R1과 동일하게 정의되거나, 또는 ⅱ) 이웃한 R11과 R12끼리, 이웃한 R12와 R13끼리 및/또는 이웃한 R13과 R14끼리 서로 결합하여 적어도 하나의 고리를 형성할 수 있을 것이다. 이때, R11~R14 중 서로 이웃한 쌍끼리 서로 결합할 수도 있고 일부 쌍만 또는 한 쌍만 서로 결합하여 적어도 하나의 고리를 형성할 수 있을 것이며, 이때 고리를 형성하지 않는 기는 ⅰ)에서 정의된 것과 같이 R1과 동일하게 정의될 수 있을 것이다.In Formulas 2 to 4, R 11 to R 14 are defined as the same as iii) R 1 in Formula 1, or ii) neighboring R 11 and R 12 , neighboring R 12 and R 13, and / or neighboring One R 13 and R 14 may be bonded to each other to form at least one ring. At this time, among R 11 to R 14 , neighboring pairs may be combined with each other, or only some pairs or only one pair may be combined with each other to form at least one ring, wherein groups not forming a ring are those defined in iii). Likewise, it may be defined identically to R 1 .

한편, 상기 화학식 2 내지 화학식 4에서, 상기 Ar1~Ar4, R2 ~R5, X, L, m 및 n은 화학식 1에서 정의된 것과 동일하게 정의될 수 있을 것이다.Meanwhile, in Chemical Formulas 2 to 4, Ar 1 to Ar 4 , R 2 to R 5 , X, L, m, and n may be defined as defined in Chemical Formula 1.

예컨대, 상기 화학식 3에서, L은 단일결합; C6~C60의 아릴렌기; C2~C60의 헤테로고리기; 및 2가의 지방족 탄화수소로 이루어진 군에서 선택될 수 있으며, Ar3 및 Ar4는 서로 독립적으로 ⅰ)C6~C60의 아릴기; C2~C60의 헤테로고리기; 플루오렌일기; C1~C50의 알킬기;및 C2~C20의 알케닐기로 이루어진 군에서 선택되거나, 또는 ⅱ)Ar3과 Ar4가 서로 결합하여 N과 함께 헤테로고리를 형성할 수 있을 것이다.For example, in Chemical Formula 3, L is a single bond; C 6 ~ C 60 Arylene group; C 2 ~ C 60 heterocyclic group; And it may be selected from the group consisting of divalent aliphatic hydrocarbons, Ar 3 and Ar 4 are independently of each other ⅰ) C 6 ~ C 60 aryl group; C 2 ~ C 60 heterocyclic group; Fluorenyl group; C 1 ~ C 50 alkyl group; and C 2 ~ C 20 alkenyl group selected from the group consisting of, or ii) Ar 3 And Ar 4 may be bonded to each other to form a heterocycle with N.

이때, 상기 L의 아릴렌기, 헤테로고리기, 지방족 탄화수소기와, Ar3 및 Ar4의 아릴기, 헤테로고리기, 풀루오렌일기, 알킬기 및 알케닐기는, 치환기로 더 치환될 수 있을 것이다. 예컨대, 이들은 중수소, 할로겐기, C1~C20의 알킬기, C1~C20의 알콕시기, C6~C20의 아릴기 또는 C2~C20의 헤테로고리기로 치환된 아민기, C1~C20의 알킬아민기, C1~C20 의 알킬티오기, C6~C20의 아릴티오기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기; 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, 및 C3~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다.At this time, the arylene group, heterocyclic group, aliphatic hydrocarbon group of L, Ar 3 and Ar 4 of the aryl group, heterocyclic group, pullorenyl group, alkyl group and alkenyl group may be further substituted with a substituent. For example, these are deuterium, halogen groups, C 1 ~ C 20 alkyl groups, C 1 ~ C 20 alkoxy groups, C 6 ~ C 20 aryl groups or C 2 ~ C 20 heterocyclic group substituted amine groups, C 1 ~ C 20 coming of the alkyl amine group, C 1 ~ alkyl group of C 20, C 6 ~ of the C 20 arylthio group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C 3 ~ C of 20 cycloalkyl group, C 6 ~ C 60 aryl group; At least one substituent selected from the group consisting of an aryl group of C 6 to C 20 substituted with deuterium, an arylalkenyl group of C 8 to C 20 , a silane group, a boron group, a germanium group, and a C 3 to C 20 heterocyclic group. It can be substituted with.

또한, 상기 화학식 1로 표시되는 화학식은 하기 화학식 중 하나로 표시될 수 있을 것이다.In addition, the formula represented by Formula 1 may be represented by one of the following formulas.

<화학식5> <화학식6> <화학식7><Formula 5> <Formula 6> <Formula 7>

Figure 112019086099118-pat00008
Figure 112019086099118-pat00008

<화학식8> <화학식9> <화학식10><Formula 8> <Formula 9> <Formula 10>

Figure 112019086099118-pat00009
Figure 112019086099118-pat00009

<화학식11> <화학식12> <화학식13><Formula 11> <Formula 12> <Formula 13>

Figure 112019086099118-pat00010
Figure 112019086099118-pat00010

<화학식14> <화학식15><Formula 14> <Formula 15>

Figure 112019086099118-pat00011
Figure 112019086099118-pat00011

상기 화학식 5 내지 15에서, Ar1~Ar4, R1~R5, m, n, L, X 및 p는 화학식 1에서 정의된 것과 동일하다.In Formulas 5 to 15, Ar 1 to Ar 4 , R 1 to R 5 , m, n, L, X and p are the same as defined in Formula 1.

또한, 상기 화학식 1은 하기 화학식 중 하나로 표시될 수 있다.In addition, Chemical Formula 1 may be represented by one of the following Chemical Formulas.

<화학식16> <화학식17> <화학식18><Formula 16> <Formula 17> <Formula 18>

Figure 112019086099118-pat00012
Figure 112019086099118-pat00012

<화학식19> <화학식20> <화학식21> <Formula 19> <Formula 20> <Formula 21>

Figure 112019086099118-pat00013
Figure 112019086099118-pat00013

<화학식22> <화학식23> <화학식24><Formula 22> <Formula 23> <Formula 24>

Figure 112019086099118-pat00014
Figure 112019086099118-pat00014

<화학식25> <화학식26> <화학식27><Formula 25> <Formula 26> <Formula 27>

Figure 112019086099118-pat00015
Figure 112019086099118-pat00015

Figure 112019086099118-pat00016
Figure 112019086099118-pat00016

Figure 112019086099118-pat00017
Figure 112019086099118-pat00017

상기 화학식 16 내지 51에서, Ar1 ~Ar4, R′, R″, m, n, R2 ~R5 및 L 은 화학식 1에서 정의된 것과 동일하다.In Formulas 16 to 51, Ar 1 to Ar 4 , R ′, R ″, m, n, R 2 to R 5 and L are the same as defined in Formula 1.

구체적으로, 상기 화학식 1은 하기 화합물 중 하나일 수 있다.

Figure 112019086099118-pat00018
Specifically, Formula 1 may be one of the following compounds.
Figure 112019086099118-pat00018

Figure 112019086099118-pat00019
Figure 112019086099118-pat00019

Figure 112019086099118-pat00020
Figure 112019086099118-pat00020

Figure 112019086099118-pat00021
Figure 112019086099118-pat00021

Figure 112019086099118-pat00022
Figure 112019086099118-pat00022

Figure 112019086099118-pat00023
Figure 112019086099118-pat00023

Figure 112019086099118-pat00024
Figure 112019086099118-pat00024

Figure 112019086099118-pat00025
Figure 112019086099118-pat00025

Figure 112019086099118-pat00026
Figure 112019086099118-pat00026

Figure 112019086099118-pat00027
Figure 112019086099118-pat00027

Figure 112019086099118-pat00028
Figure 112019086099118-pat00028

Figure 112019086099118-pat00029
Figure 112019086099118-pat00029

Figure 112019086099118-pat00030
Figure 112019086099118-pat00030

Figure 112019086099118-pat00031
Figure 112019086099118-pat00031

이하, 상기 화학식으로 표시되는 본 발명 화합물의 합성예 및 유기전기소자의 제조예에 대하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis example of the compound of the present invention represented by the above formula and the production example of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

유기전기소자의 제조평가Manufacturing evaluation of organic electric devices

합성예Synthetic example

예시적으로 본 발명에 따른 화합물은 하기 반응식 1과 같이, Sub 1 또는 Sub 3 중 하나와 Sub 2를 반응시켜 제조되거나, Sub 1과 Sub 4를 반응시켜 반응시켜 제조한다.Illustratively, the compound according to the present invention is prepared by reacting one of Sub 1 or Sub 3 with Sub 2, or by reacting Sub 1 with Sub 4 as shown in Reaction Scheme 1 below.

<반응식 1><Scheme 1>

Figure 112019086099118-pat00032
Figure 112019086099118-pat00032

Sub 1 합성법 예시 :Sub 1 synthesis example:

<반응식 2-a><Reaction Scheme 2-a>

Figure 112019086099118-pat00033
Figure 112019086099118-pat00033

(1)(One) Sub 1-1-1의 예시Example of Sub 1-1-1

Sub 1-1-1의 예시는 다음과 같으며 이들의 FD-MS 값은 표 1과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 1-1-1 are as follows, and their FD-MS values are shown in Table 1, but are not limited thereto.

Figure 112019086099118-pat00034
Figure 112019086099118-pat00034

Figure 112019086099118-pat00035
Figure 112019086099118-pat00035

[표1][Table 1]

Figure 112019086099118-pat00036
Figure 112019086099118-pat00036

(2)(2) Sub 1-1-2의 합성법Synthesis of Sub 1-1-2

Sub 1-1-1 (1당량)을 무수 Ether에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane) (1.1당량)을 천천히 적가하고 난 후, 반응물을 30분동안 교반시켰다. 그 후 다시 반응물의 온도를 -78℃로 낮추고 Triisopropylborate (1.5당량)를 적가하였다. 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl을 넣어준다. 반응이 완료되면 ethyl acetate와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub1-1-2를 얻었다. Sub 1-1-1 (1 eq.) Was dissolved in anhydrous Ether, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 eq.) Was slowly added dropwise, and the reaction mass was added for 30 minutes. While stirring. After that, the temperature of the reactant was again lowered to -78 ° C and Triisopropylborate (1.5 eq) was added dropwise. After stirring at room temperature, dilute it with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain Sub1-1-2.

(3)(3) Sub 1-1-4의 합성법Synthesis of Sub 1-1-4

상기 합성에서 얻어진 Sub 1-1-2 (1당량)를 THF에 녹인 후에, Sub 1-1-3 (1.1당량), Pd(PPh3)4(0.03당량), NaOH(3당량), 물을 첨가한 후, 교반환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Sub 1-1-4를 얻었다.After dissolving Sub 1-1-2 (1 eq) obtained in the above synthesis in THF, Sub 1-1-3 (1.1 eq), Pd (PPh 3 ) 4 (0.03 eq), NaOH (3 eq), water After adding, it was stirred and refluxed. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product Sub 1-1-4.

(4)(4) Sub 1-1 합성법Sub 1-1 synthesis method

얻은 Sub 1-1-4와 (1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1-1을 얻었다.The obtained Sub 1-1-4 and (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 1-1.

Sub 1-1의 예시는 다음과 같으며, FD-MS 값은 표 2와 같으나, 이에 한정되는 것은 아니다.Examples of Sub 1-1 are as follows, and the FD-MS values are shown in Table 2, but are not limited thereto.

Figure 112019086099118-pat00037
Figure 112019086099118-pat00037

[표2][Table 2]

Figure 112019086099118-pat00038
Figure 112019086099118-pat00038

<반응식 2-b><Reaction Scheme 2-b>

Figure 112019086099118-pat00039
Figure 112019086099118-pat00039

(1)(One) Sub 1-2-2의 합성법Synthesis of Sub 1-2-2

Sub 1-2-1 (1당량)을 무수 Ether에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane) (1.1당량)을 천천히 적가하고 난 후, 반응물을 30분동안 교반시켰다. 그 후 다시 반응물의 온도를 -78℃로 낮추고 Triisopropylborate (1.5당량)를 적가하였다. 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl을 넣어준다. 반응이 완료되면 ethyl acetate와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub1-2-2를 얻었다. Sub 1-2-1 (1 eq.) Was dissolved in anhydrous Ether, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 eq.) Was slowly added dropwise, and the reaction mass was added for 30 minutes. While stirring. After that, the temperature of the reactant was again lowered to -78 ° C and Triisopropylborate (1.5 eq) was added dropwise. After stirring at room temperature, dilute it with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain Sub1-2-2.

(2)(2) Sub 1-2-3 합성법Sub 1-2-3 synthesis method

상기 합성에서 얻어진 Sub 1-2-2 (1당량)를 THF에 녹인 후에, Sub 1-1-3 (1.1당량), Pd(PPh3)4(0.03당량), NaOH(3당량), 물을 첨가한후, 교반환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Sub 1-2-3을 얻었다.After dissolving Sub 1-2-2 (1 eq) obtained in the above synthesis in THF, Sub 1-1-3 (1.1 eq), Pd (PPh 3 ) 4 (0.03 eq), NaOH (3 eq), water After adding, it was stirred and refluxed. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the product Sub 1-2-3.

(3)(3) 1-2합성법1-2 Synthesis Method

상기 합성에서 얻어진 Sub 1-2-3와 (1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1-2을 얻었다. Sub 1-2-3 and (1 equivalent) and triphenylphosphine (2.5 equivalents) obtained in the above synthesis were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 1-2.

Sub 1-2의 예시는 다음과 같으며, FD-MS 값은 표 3과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 1-2 are as follows, and the FD-MS values are shown in Table 3, but are not limited thereto.

Figure 112019086099118-pat00040
Figure 112019086099118-pat00040

[표3][Table 3]

Figure 112019086099118-pat00041
Figure 112019086099118-pat00041

<반응식 2-c><Reaction Scheme 2-c>

Figure 112019086099118-pat00042
Figure 112019086099118-pat00042

(1)(One) Sub 1-3-2의 합성법Synthesis of Sub 1-3-2

Sub 1-3-1 (1당량)을 무수 Ether에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane) (1.1당량)을 천천히 적가하고 난 후, 반응물을 30분동안 교반시켰다. 그 후 다시 반응물의 온도를 -78℃로 낮추고 Triisopropylborate (1.5당량)를 적가하였다. 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl을 넣어준다. 반응이 완료되면 ethyl acetate와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub1-3-2를 얻었다. Sub 1-3-1 (1 eq.) Was dissolved in anhydrous Ether, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 eq.) Was slowly added dropwise, and the reaction mass was added for 30 minutes. While stirring. After that, the temperature of the reactant was again lowered to -78 ° C and Triisopropylborate (1.5 eq) was added dropwise. After stirring at room temperature, dilute it with water and add 2N HCl. After the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain Sub1-3-2.

(2)(2) Sub 1-3-3 합성법Sub 1-3-3 Synthesis Method

상기 합성에서 얻어진 Sub 1-3-2 (1당량)를 THF에 녹인 후에, Sub 1-1-3 (1.1당량), Pd(PPh3)4(0.03당량), NaOH(3당량), 물을 첨가한후, 교반환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Sub 1-3-3을 얻었다.After dissolving Sub 1-3-2 (1 eq) obtained in the above synthesis in THF, Sub 1-1-3 (1.1 eq), Pd (PPh 3 ) 4 (0.03 eq), NaOH (3 eq), water After adding, it was stirred and refluxed. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the product Sub 1-3-3.

(3)(3) Sub 1-3 합성법Sub 1-3 synthesis method

얻은 Sub 1-3-3와 (1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1-3을 얻었다.The obtained Sub 1-3-3 and (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 1-3.

Sub 1-3의 예시는 다음과 같으며, FD-MS 값은 표 4와 같으나, 이에 한정되는 것은 아니다.Examples of Sub 1-3 are as follows, and FD-MS values are as shown in Table 4, but are not limited thereto.

Figure 112019086099118-pat00043
Figure 112019086099118-pat00043

[표4][Table 4]

Figure 112019086099118-pat00044
Figure 112019086099118-pat00044

<반응식 2-d><Reaction Scheme 2-d>

Figure 112019086099118-pat00045
Figure 112019086099118-pat00045

(1)(One) Sub 1-4-2의 합성법Synthesis of Sub 1-4-2

Sub 1-4-1 (1당량)을 무수 Ether에 녹이고, 반응물의 온도를 -78℃로 낮추고, n-BuLi (2.5M in hexane) (1.1당량)을 천천히 적가하고 난 후, 반응물을 30분동안 교반시켰다. 그 후 다시 반응물의 온도를 -78℃로 낮추고 Triisopropylborate (1.5당량)를 적가하였다. 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl을 넣어준다. 반응이 완료되면 ethyl acetate와 물로 추출한 후, 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 1-4-2를 얻었다. Sub 1-4-1 (1 eq.) Was dissolved in anhydrous Ether, the temperature of the reactant was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 eq.) Was slowly added dropwise, and the reaction mass was added for 30 minutes. While stirring. After that, the temperature of the reactant was again lowered to -78 ° C and Triisopropylborate (1.5 eq) was added dropwise. After stirring at room temperature, dilute it with water and add 2N HCl. After the reaction was completed, extraction was performed with ethyl acetate and water, and the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain Sub 1-4-2.

(2)(2) Sub 1-4-3의 합성법Synthesis of Sub 1-4-3

상기 합성에서 얻어진 Sub 1-4-2 (1당량)를 THF에 녹인 후에, Sub 1-1-3 (1.1당량), Pd(PPh3)4(0.03당량), NaOH(3당량), 물을 첨가한후, 교반환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Sub 1-4-3을 얻었다.After dissolving Sub 1-4-2 (1 eq) obtained in the above synthesis in THF, Sub 1-1-3 (1.1 eq), Pd (PPh 3 ) 4 (0.03 eq), NaOH (3 eq), water After adding, it was stirred and refluxed. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product Sub 1-4-3.

(3)(3) Sub 1-4의 합성법Synthesis of Sub 1-4

상기 합성에서 얻어진 Sub 1-4-3와 (1당량)과 triphenylphosphine(2.5당량)을 o-dichlorobenzene에 녹이고, 24시간 동안 환류시켰다. 반응이 종결되면 감압증류를 이용하여 용매를 제거한 후, 농축된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1-4를 얻었다.Sub 1-4-3 and (1 eq) and triphenylphosphine (2.5 eq) obtained in the above synthesis were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 1-4.

Sub 1-4의 예시는 다음과 같으며, FD-MS 값은 표 5와 같으나, 이에 한정되는 것은 아니다.Examples of Sub 1-4 are as follows, and the FD-MS values are shown in Table 5, but are not limited thereto.

Figure 112019086099118-pat00046
Figure 112019086099118-pat00046

[표 5][Table 5]

Figure 112019086099118-pat00047
Figure 112019086099118-pat00047

Sub 2 합성법 예시 :Sub 2 Synthesis Example:

Sub 2의 예시는 다음과 같으며, FD-MS 값은 표 6과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 2 are as follows, and the FD-MS values are shown in Table 6, but are not limited thereto.

Figure 112019086099118-pat00048
Figure 112019086099118-pat00048

[표 6][Table 6]

Figure 112019086099118-pat00049
Figure 112019086099118-pat00049

Sub 3 합성법 예시 :Sub 3 Synthesis Example:

반응식 1의 Sub 3은 하기 반응식3의 반응경로에 의해 합성될 수 있다.Sub 3 of Scheme 1 can be synthesized by the reaction route of Scheme 3 below.

<반응식 3><Scheme 3>

Figure 112019086099118-pat00050
Figure 112019086099118-pat00050

Sub 3-1 (1당량)를 THF에 녹인 후에, Sub 3-2 (1.1당량), Pd(PPh3)4(0.03당량), NaOH(3당량), 물을 첨가한후, 교반환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Sub 3을 얻었다.Sub 3-1 (1 eq.) Was dissolved in THF, Sub 3-2 (1.1 eq.), Pd (PPh 3 ) 4 (0.03 eq.), NaOH (3 eq.), Water was added, followed by stirring to reflux. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product Sub 3.

Sub 3의 예시는 다음과 같으며, FD-MS 값은 표 7과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 3 are as follows, and the FD-MS values are shown in Table 7, but are not limited thereto.

Figure 112019086099118-pat00051
Figure 112019086099118-pat00051

[표 7][Table 7]

Figure 112019086099118-pat00052
Figure 112019086099118-pat00052

Sub 4 합성법 예시 :Sub 4 Synthesis Example:

Sub 4의 예시는 다음과 같으며, FD-MS 값은 표 8과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 4 are as follows, and the FD-MS values are shown in Table 8, but are not limited thereto.

Figure 112019086099118-pat00053
Figure 112019086099118-pat00053

[표 8][Table 8]

Figure 112019086099118-pat00054
Figure 112019086099118-pat00054

Product 합성법 예시 :Product synthesis example:

Sub 1 또는 Sub 3 (1당량)과 Sub 2 또는 Sub 4 (1.1당량)을 톨루엔에 넣고 Pd2(dba)3 (0.05당량), PPh3 (0.1당량), NaOt-Bu (3당량)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product를 얻었다. Sub 1 or Sub 3 (1 eq) and Sub 2 or Sub 4 (1.1 eq) were added to toluene and Pd 2 (dba) 3 (0.05 eq), PPh 3 (0.1 eq), and NaO t -Bu (3 eq) After each addition, the mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the final product.

1-9의 합성예시Synthesis example of 1-9

Figure 112019086099118-pat00055
Figure 112019086099118-pat00055

7,7-dimethyl-7,12-dihydrobenzo[6,7]indeno[1,2-b]indole(5.7g, 20mmol) 과 5-bromo-2,4-diphenylpyrimidine(7.5g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 7.2g (수율 70%)를 얻었다.7,7-dimethyl-7,12-dihydrobenzo [6,7] indeno [1,2-b] indole (5.7g, 20mmol) and 5-bromo-2,4-diphenylpyrimidine (7.5g, 24mmol) in toluene Put Pd 2 (dba) 3 (1.0g, 1mmol), PPh 3 (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), respectively, and reflux with stirring at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the final product 7.2g (yield 70%).

2-24의 합성예시Synthesis example of 2-24

Figure 112019086099118-pat00056
Figure 112019086099118-pat00056

12-phenyl-7,12-dihydrobenzo[e]indolo[3,2-b]indole(6.4g, 20mmol)과4-bromo-1,1'-biphenyl(5.6g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 7.2g (수율 74%)를 얻었다.12-phenyl-7,12-dihydrobenzo [e] indolo [3,2-b] indole (6.4g, 20mmol) and 4-bromo-1,1'-biphenyl (5.6g, 24mmol) were added to toluene and Pd 2 (dba) 3 (1.0 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), and NaO t -Bu (5.8 g, 60 mmol) were added respectively, followed by stirring and refluxing at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the final product 7.2g (yield 74%).

3-56의 합성예시Synthesis Example of 3-56

Figure 112019086099118-pat00057
Figure 112019086099118-pat00057

14H-phenanthro[9',10':4,5]thieno[3,2-b]indole(6.5g, 20mmol)과 2-bromo-4-phenylquinazoline(6.8g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 7.5g (수율 71%)를 얻었다. 14H-phenanthro [9 ', 10': 4,5] thieno [3,2-b] indole (6.5g, 20mmol) and 2-bromo-4-phenylquinazoline (6.8g, 24mmol) were added to toluene and Pd 2 ( dba) 3 (1.0 g, 1 mmol), PPh 3 (0.5 g, 2 mmol), and NaO t -Bu (5.8 g, 60 mmol) were added respectively, followed by stirring and refluxing at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain the final product 7.5g (yield 71%).

4-94의 합성예시Synthesis Example of 4-94

Figure 112019086099118-pat00058
Figure 112019086099118-pat00058

10H-benzofuro[3,2-b]indole(4.1g, 20mmol)과 2-(4-bromophenyl)triphenylene(9.2g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 6.6g (수율 65%)를 얻었다. 10H-benzofuro [3,2-b] indole (4.1g, 20mmol) and 2- (4-bromophenyl) triphenylene (9.2g, 24mmol) were added to toluene and Pd 2 (dba) 3 (1.0g, 1mmol), PPh 3 (0.5 g, 2 mmol) and NaO t -Bu (5.8 g, 60 mmol) were added respectively, followed by stirring and refluxing at 100 ° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 6.6 g of final product (65% yield).

1-61의 합성예시Synthesis example of 1-61

Figure 112019086099118-pat00059
Figure 112019086099118-pat00059

N-([1,1'-biphenyl]-4-yl)-N-(4-(7,7-dimethyl-7,12-dihydrobenzo[g]indeno[1,2-b]indol-9-yl)phenyl)-[1,1'-biphenyl]-4-amine(13.6g, 20mmol)과bromobenzene(3.8g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 11.5g (수율 76%)를 얻었다. N-([1,1'-biphenyl] -4-yl) -N- (4- (7,7-dimethyl-7,12-dihydrobenzo [g] indeno [1,2-b] indol-9-yl ) phenyl)-[1,1'-biphenyl] -4-amine (13.6g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd 2 (dba) 3 (1.0g, 1mmol), PPh 3 ( 0.5g, 2mmol) and NaO t -Bu (5.8g, 60mmol) were added respectively, followed by stirring and refluxing at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the final product 11.5g (yield 76%).

2-67의 합성예시Synthesis Example of 2-67

Figure 112019086099118-pat00060
Figure 112019086099118-pat00060

12-phenyl-7,12-dihydrobenzo[g]indolo[3,2-b]indole(6.6g, 20mmol)과N-([1,1'-biphenyl]-4-yl)-N-(4'-bromo-[1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine(14.2g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 10.1g (수율 60%)를 얻었다. 12-phenyl-7,12-dihydrobenzo [g] indolo [3,2-b] indole (6.6g, 20mmol) and N-([1,1'-biphenyl] -4-yl) -N- (4 ' -bromo- [1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine (14.2g, 24mmol) was added to toluene and Pd 2 (dba) 3 (1.0g, 1mmol), PPh 3 (0.5g, 2mmol) and NaO t -Bu (5.8g, 60mmol) were added respectively, followed by reflux with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the final product 10.1g (yield 60%).

3-85의 합성예시Synthesis example of 3-85

Figure 112019086099118-pat00061
Figure 112019086099118-pat00061

14H-phenanthro[9',10':4,5]thieno[3,2-b]indole(6.5g, 20mmol)과N-([1,1'-biphenyl]-4-yl)-7-bromo-N-(9,9-diphenyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine(18.2g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 12.8g (수율 64%)를 얻었다. 14H-phenanthro [9 ', 10': 4,5] thieno [3,2-b] indole (6.5g, 20mmol) and N-([1,1'-biphenyl] -4-yl) -7-bromo -N- (9,9-diphenyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine (18.2 g, 24 mmol) was added to toluene and Pd 2 (dba) 3 (1.0 g, 1mmol), PPh 3 (0.5g, 2mmol), and NaO t -Bu (5.8g, 60mmol) were added respectively, followed by reflux with stirring at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain a final product 12.8 g (yield 64%).

4-90의 합성예시Synthesis Example of 4-90

Figure 112019086099118-pat00062
Figure 112019086099118-pat00062

10H-benzofuro[3,2-b]indole(4.1g, 20mmol)과 N,N-di([1,1'-biphenyl]-4-yl)-4'-bromo-[1,1'-biphenyl]-4-amine(13.3g, 24mmol)을 톨루엔에 넣고 Pd2(dba)3 (1.0g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반환류 시킨다. ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 최종 Product 9.0g (수율 66%)를 얻었다. 10H-benzofuro [3,2-b] indole (4.1g, 20mmol) and N, N-di ([1,1'-biphenyl] -4-yl) -4'-bromo- [1,1'-biphenyl ] -4-amine (13.3g, 24mmol) was added to toluene, and Pd 2 (dba) 3 (1.0g, 1mmol), PPh 3 (0.5g, 2mmol), and NaO t -Bu (5.8g, 60mmol) were added, respectively. Then, the mixture was stirred and refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO 4 and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain the final product 9.0g (yield 66%).

상기와 같은 제조방법과 동일 또는 유사한 방법으로 제조된 본 발명에 따른 화합물의 FD-MS 값은 하기 표 9와 같다.FD-MS values of the compounds according to the present invention prepared by the same or similar method to the above preparation method are shown in Table 9 below.

[표 9][Table 9]

Figure 112019086099118-pat00063
Figure 112019086099118-pat00063

Figure 112019086099118-pat00064
Figure 112019086099118-pat00064

Figure 112019086099118-pat00065
Figure 112019086099118-pat00065

Figure 112019086099118-pat00066
Figure 112019086099118-pat00066

Figure 112019086099118-pat00067
Figure 112019086099118-pat00067

Figure 112019086099118-pat00068
Figure 112019086099118-pat00068

유기전기소자의 제조평가Manufacturing evaluation of organic electric devices

[실험예 1] (발광층)[Experimental Example 1] (Light emitting layer)

합성을 통해 얻은 본 발명의 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인방법에 따라 유기전계발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 형성하여 정공주입층을 형성한 이후 상기 정공주입층 상에 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐(이하 -NPD로 약기함)을 20 nm 두께로 진공증착 하여 정공수송층을 형성하였다. 그리고, 정공 수송층 상부에 본 발명의 화합물을 호스트 물질로, Ir(ppy)3[tris(2-phenylpyridine)-iridium] 를 도펀트 물질로 사용하여 95:5 중량으로 도핑함으로써 30nm 두께의 발광층을 형성하였다. 이어서, 상기 발광층 상에 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하여 정공저지층을 형성하고, 정공저지층 상에 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 약칭함)을 40 nm 두께로 성막하여 전자주입층을 형성하였다. 이후, 할로겐화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, Al을 150 nm의 두께로 증착하여, Al/LiF 음극을 형성함으로써 유기전계발광소자를 제작하였다.An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention obtained through synthesis as a light emitting host material of the light emitting layer. First, on the ITO layer (anode) formed on the glass substrate, N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1- After forming a hole injection layer by vacuum deposition of a phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film to a thickness of 60 nm, 4,4-bis [ N- (1-naph) on the hole injection layer Tyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. In addition, a 30 nm-thick light-emitting layer was formed by doping the compound of the present invention as a host material and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] as a dopant material on the hole transport layer at a weight of 95: 5. . Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) on the light emitting layer is vacuum deposited to a thickness of 10 nm to form a hole. A blocking layer was formed, and an electron injection layer was formed by depositing tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) on the hole blocking layer to a thickness of 40 nm. Thereafter, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm, and depositing Al to a thickness of 150 nm to form an Al / LiF cathode.

[비교예 1][Comparative Example 1]

발광층 형성시 호스트 물질로 본 발명의 화합물 대신 하기 비교 화합물 1(CBP)을 사용한 점을 제외하고 상기 실험예 1과 동일하게 유기전계발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the following Comparative Compound 1 (CBP) was used instead of the compound of the present invention as a host material when forming the emission layer.

<비교 화합물 1><Comparative Compound 1>

Figure 112019086099118-pat00069
Figure 112019086099118-pat00069

[비교예 2][Comparative Example 2]

발광층 형성시 호스트 물질로 본 발명의 화합물 대신 하기 비교 화합물 2를 사용한 점을 제외하고 상기 실험예 1과 동일한 방법으로 유기전계발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the following Comparative Compound 2 was used instead of the compound of the present invention as a host material when forming the emission layer.

<비교 화합물 2><Comparative Compound 2>

Figure 112019086099118-pat00070
Figure 112019086099118-pat00070

본 발명의 실험예 1, 비교예 1 및 비교예 2에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정한 결과는 하기 표 10같다. 이때, 300cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T90 수명을 측정하였다. As a result of measuring electroluminescence (EL) characteristics with PR-650 of photoresearch by applying a direct bias DC voltage to the organic electroluminescent elements manufactured by Experimental Example 1, Comparative Example 1 and Comparative Example 2 of the present invention Is shown in Table 10 below. At this time, the T90 life was measured through a life measurement equipment manufactured by Max Science at a reference luminance of 300 cd / m2.

한편, 본 발명의 실험예 1에 따라 제조된 유기전계발광소자를 하기 표 10에서 실시예 1 내지 269로 표시하였다.On the other hand, the organic electroluminescent device manufactured according to Experimental Example 1 of the present invention is shown in Examples 1 to 269 in Table 10 below.

[표 10]Table 10

Figure 112019086099118-pat00071
Figure 112019086099118-pat00071

Figure 112019086099118-pat00072
Figure 112019086099118-pat00072

Figure 112019086099118-pat00073
Figure 112019086099118-pat00073

Figure 112019086099118-pat00074
Figure 112019086099118-pat00074

Figure 112019086099118-pat00075
Figure 112019086099118-pat00075

Figure 112019086099118-pat00076
Figure 112019086099118-pat00076

Figure 112019086099118-pat00077
Figure 112019086099118-pat00077

Figure 112019086099118-pat00078
Figure 112019086099118-pat00078

상기 결과로부터 알 수 있듯이, 본 발명에 따른 화합물을 발광층 재료로 이용한 유기전기발광소자는 비교예에 비하여 발광효율 및 수명이 현저히 개선되었을 뿐만 아니라, 색순도 또한 현저히 개선되었다. 특히, X가 S인 실시예(134)~ 실시예(201)에 따른 유기전계발광소자는 낮은 구동전압과 높은 효율, 고수명의 소자특성을 나타내는바, 인광 호스트로서 가장 좋은 결과를 보였다.As can be seen from the above results, the organic electroluminescent device using the compound according to the present invention as a light emitting layer material has not only improved luminous efficiency and lifespan, but also improved color purity significantly compared to the comparative example. In particular, the organic electroluminescent devices according to Examples 134 to 201 in which X is S exhibit low device voltage, high efficiency, and high lifespan device characteristics, and thus show the best results as a phosphorescent host.

또한, 비교예 2와 본 발명의 화합물인 실시예(69)~ 실시예(133)의 소자 결과를 비교해 보면, 코어에 고리가 접합되어 있는 구조인 본 발명의 화합물이 비교예 2보다 높은 효율과 높은 수명을 나타내는 것을 확인하였다. In addition, when comparing the device results of Comparative Example 2 and Examples (69) to Example (133), which are compounds of the present invention, the compound of the present invention, which is a structure in which a ring is bonded to the core, has higher efficiency and higher efficiency than Comparative Example 2. It was confirmed that it exhibited a high lifetime.

이는 상기 본 발명 및 비교예 2와 같은 다환 헤테로고리 코어의 경우 동일 또는 유사한 치환기를 적용하더라도 상기 표 10과 같이 핵심코어의 구조에 의해 효율 및 수명에 큰 차이를 나타내는 것을 확인할 수 있다. 이는 치환기 효과로 LUMO, HOMO 조절보다는, 코어의 밴드갭에 의해 효율과 수명이 결정되는 것을 보여주는 결과이다. 따라서, 치환기 효과와 코어의 유사성 만으로는 상기 표 10과 같은 결과를 쉽게 예측 할 수 없을 것이다.It can be seen that, in the case of the polycyclic heterocyclic cores of the present invention and Comparative Example 2, even if the same or similar substituents are applied, a large difference in efficiency and life is shown by the structure of the core as shown in Table 10 above. This is a result showing that efficiency and lifetime are determined by the band gap of the core, rather than controlling LUMO and HOMO as a substituent effect. Therefore, only the effect of the substituent and the similarity of the core cannot be easily predicted as shown in Table 10 above.

[실험예 2](발광보조층)[Experimental Example 2] (light emitting auxiliary layer)

먼저, 유리 기판에 형성된 ITO층(양극) 위에 2-TNATA막을 진공증착하여 60 nm 두께로 형성하여 정공 주입층을 형성한 이후, 상기정공 주입층 상에 NPD를 20 nm 두께로 진공증착하여 정공 수송층을 형성하였다. 그리고, 정공 수송층 상부에 본 발명의 화합물을 20nm의 두께로 진공증착하여 발광 보조층을 형성하였다. 그 후에발광 보조층 상부에 호스트로 CBP[4,4'-N,N'-dicarbazole-biphenyl], Ir(ppy)3 [tris(2-phenylpyridine)-iridium] 을 도펀트 물질로 사용하여 95:5 중량으로 도핑함으로써30nm 두께의 발광층을 증착하였다. 이어서, 상기 발광층 상에 BAlq를 10 nm 두께로 진공증착하여 정공저지층을 형성하고, Alq3를 40 nm 두께로 증착시켜 전자 주입층을 형성하였다. 이후, 할로겐화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, Al을 150 nm의 두께로 증착하여, Al/LiF 음극을 형성함으로써 유기전계 발광소자를 제조하였다.First, a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer with a thickness of 60 nm, and then a hole transport layer is vacuum-deposited with NPD on the hole injection layer to a thickness of 20 nm. Formed. Then, the compound of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light-emitting auxiliary layer. Subsequently, CBP [4,4'-N, N'-dicarbazole-biphenyl], Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] was used as a dopant as a host on the light-emitting auxiliary layer 95: 5 A light emitting layer having a thickness of 30 nm was deposited by doping by weight. Subsequently, a hole blocking layer was formed by vacuum-depositing BAlq to a thickness of 10 nm on the light emitting layer, and Alq 3 was deposited to a thickness of 40 nm to form an electron injection layer. Thereafter, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm, and depositing Al to a thickness of 150 nm to form an Al / LiF cathode.

[비교예 3][Comparative Example 3]

실험예 2에서 발광보조층을 형성하지 않은 점을 제외하면 실험예 2와 동일하게 유기전계발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 2, except that the emission auxiliary layer was not formed in Experimental Example 2.

[비교예 4][Comparative Example 4]

발광보조층 형성시 본 발명의 화합물 대신 하기 비교 화합물 3을 사용한 점을 제외하고 상기 실험예 2와 동일하게 유기전계발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 2, except that the following Comparative Compound 3 was used instead of the compound of the present invention when forming the light-emitting auxiliary layer.

<비교 화합물 3><Comparative Compound 3>

Figure 112019086099118-pat00079
Figure 112019086099118-pat00079

[비교예 5][Comparative Example 5]

발광보조층 형성시 본 발명의 화합물 대신 하기 비교 화합물 4를 사용한 점을 제외하고 상기 실험예 2와 동일하게 유기전계발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 2, except that the following Comparative Compound 4 was used instead of the compound of the present invention when forming the light-emitting auxiliary layer.

<비교 화합물 4><Comparative compound 4>

*

Figure 112019086099118-pat00080
*
Figure 112019086099118-pat00080

이와 같이 제조된 실시예 5 및 비교예 4 또는 5에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정한 결과는 하기 표 11과 같다. 이때, 300cd/m2 기준 휘도에서맥사이언스사에서 제조된 수명 측정 장비를 통해 T90 수명을 측정하였다. As a result of measuring the electroluminescence (EL) characteristics with the PR-650 of photoresearch by applying a net bias DC voltage to the organic electroluminescent elements manufactured in Example 5 and Comparative Examples 4 or 5 prepared as described above, Table 11 below. At this time, the T90 life was measured through a life measurement equipment manufactured by Max Science at a reference luminance of 300 cd / m2.

한편, 본 발명의 실험예 2에 따라 제조된 유기전계발광소자를 하기 표 11에서는 실시예 270 내지 385로 표시하였다.On the other hand, the organic electroluminescent device manufactured according to Experimental Example 2 of the present invention is shown in Examples 270 to 385 in Table 11 below.

[표 11][Table 11]

Figure 112019086099118-pat00081
Figure 112019086099118-pat00081

Figure 112019086099118-pat00082
Figure 112019086099118-pat00082

Figure 112019086099118-pat00083
Figure 112019086099118-pat00083

Figure 112019086099118-pat00084
Figure 112019086099118-pat00084

상기 결과로부터 알 수 있듯이, 본 발명에 따른 화합물을 발광 보조층의 재료로 이용한 유기전기발광소자의 경우, 비교예 3 내지 5에 비하여 구동전압이 낮으면서 발광효율 및 수명은 향상된 것을 확인할 수 있다. 즉, 본 발명에 따른 화합물을 적용한 유기전기소자의 경우 소자 특성이 향상됨을 확인할 수 있다.더As can be seen from the above results, in the case of the organic electroluminescent device using the compound according to the present invention as a material for the light-emitting auxiliary layer, it can be seen that the driving voltage is lower and the luminous efficiency and life are improved compared to Comparative Examples 3 to 5. That is, in the case of the organic electric device to which the compound according to the present invention is applied, it can be confirmed that the device characteristics are improved.More

특히, X가 S인 실시예(328)~실시예(356)의 경우, 구동전압이 현저히 낮고,낮효율 및 수명이 현저히 향상되었는바 소자특성이 아주 우수한 결과를 보였다. Particularly, in the case of Examples 328 to 356 in which X is S, the driving voltage is significantly low, and the efficiency and lifetime are significantly improved, so the device characteristics are very excellent.

또한, 비교예 4와 유사한 발명화합물 실시예(299)~실시예(327)의 소자 결과를 비교해 보면 코어가 고리에 접합되어 있는 구조인 본 발명의 화합물이 보다 높은 효율과 높은 수명을 나타내는 것을 확인하였다.In addition, when comparing the device results of Examples 299 to 327 of the Inventive Compounds similar to Comparative Example 4, it was confirmed that the compounds of the present invention having a structure in which a core is bonded to a ring exhibit higher efficiency and higher lifetime. Did.

이는 본 발명의 화합물이 단독으로 발광보조층으로 사용될 경우 높은 T1 에너지 레벨을 가지며, 깊은 HOMO 에너지 레벨로 인해 유기전기발광소자의 낮은 전압, 높은 발광효율 및 소자수명을 향상시키는 것으로 설명할 수 있을 것이다. It can be explained that the compound of the present invention has a high T1 energy level when used alone as a light-emitting auxiliary layer, and improves the low voltage, high luminous efficiency and device life of the organic electroluminescent device due to the deep HOMO energy level. .

본 발명의 화합물들을 유기전기발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있을 것이다.The same effects can be obtained even if the compounds of the present invention are used in other organic material layers of an organic electroluminescent device, for example, a light-emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer.

이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100: 유기전기소자 110: 기판
120: 제 1전극 130: 정공주입층
140: 정공수송층 141: 버퍼층
150: 발광층 151: 발광보조층
160: 전자수송층 170: 전자주입층
180: 제 2전극100: organic electrical element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (11)

하기 화학식 중 하나로 표시되는 화합물:
<화학식 2>
Figure 112019086099118-pat00085

<화학식 3>
Figure 112019086099118-pat00086

상기 화학식 2 및 3에서,
X는 CR′R″, NR′ 또는 O이며(여기서, R′ 및 R″는 서로 독립적으로 C6~C30의 아릴기, C2~C20의 헤테로고리기 또는 C1~C10의 알킬기이다),
R2 내지 R5는
Figure 112019086099118-pat00087
표시되고,
R11 내지 R14 는 ⅰ)수소; 중수소; 또는
Figure 112019086099118-pat00088
이거나, ⅱ) R11과 R12끼리, R12와 R13끼리 및/또는 R13과 R14끼리 서로 결합하여 적어도 하나의 고리를 형성하며(단, R11~R14 중 고리를 형성하지 않는 기는 ⅰ)에서 정의된 것과 동일하게 정의됨), iii) R11과 R12끼리, R12와 R13끼리 및/또는 R13과 R14끼리 서로 결합하여 적어도 하나의 고리를 형성하지 않을 경우에는 R11 내지 R14 중 하나 이상은 수소가 아니며,
l과 o는 0 또는 1의 정수이며, l+o는 1이상이고,
L은 ⅰ) C6~C30의 아릴기; C2~C20의 1가의 헤테로고리기; 및 플루오렌일기로 이루어진 군에서 선택되거나, 또는 ⅱ) C6~C30의 아릴렌기; C2~C20의 2가의 헤테로고리기; 및 플루오렌일렌기로 이루어진 군에서 선택되며,
Y는 수소; 중수소; 삼중수소; -N(Ar3)(Ar4); C1~C10의 알킬기; C6~C30의 아릴기; 및 C6~C30의 방향족 고리와 C3~C30의 지방족고리의 축합고리기로 이루어진 군에서 선택되고,
m과 n은 각각 0 또는 1이며(단, m+n은 1이상임),
Ar1은 ⅰ) C6~C30의 아릴기; C2~C20의 1가의 헤테로고리기; C6~C30의 방향족 고리와 C3~C30의 지방족 고리의 1가의 축합고리기; 및 플루오렌일기로 이루어진 군에서 선택되거나, 또는 ⅱ) C6~C30의 아릴렌기; C2~C20의 2가의 헤테로고리기; C6~C30의 방향족 고리와 C3~C30의 지방족 고리의 2가의 축합고리기; 및 플루오렌일렌기로 이루어진 군에서 선택되며,
Ar2는 실란기; C6~C30의 아릴기; C2~C20의 헤테로고리기; 및 C6~C30의 방향족 고리와 C3~C30의 지방족 고리의 축합고리기로 이루어진 군에서 선택되고,
Ar3 및 Ar4는 서로 독립적으로 C6~C30의 아릴기; C2~C30의 헤테로고리기; 및 플루오렌일기로 이루어진 군에서 선택된다.
(이때, 상기 L, Y, Ar1, Ar3, Ar4, R′ 및 R″, R2 내지 R5 및 R11 내지 R14 각각은, C1~C20의 알킬기; C6~C20의 아릴기; 중수소로 치환된 C6~C20의 아릴기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로 원자를 포함하는 C2~C20의 헤테로고리기;로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다)Compound represented by one of the following formula:
<Formula 2>
Figure 112019086099118-pat00085

<Formula 3>
Figure 112019086099118-pat00086

In Chemical Formulas 2 and 3,
X is CR'R ″, NR ′ or O (where R ′ and R ″ are independently of each other C 6 ~ C 30 aryl group, C 2 ~ C 20 heterocyclic group or C 1 ~ C 10 alkyl group to be),
R 2 to R 5 are
Figure 112019086099118-pat00087
Being displayed,
R 11 to R 14 are iii) hydrogen; heavy hydrogen; or
Figure 112019086099118-pat00088
Or, ii) R 11 and R 12 , R 12 and R 13, and / or R 13 and R 14 are bonded to each other to form at least one ring (however, R 11 to R 14 do not form a ring) Groups are defined identically to those defined in iii)), iii) when R 11 and R 12 , R 12 and R 13 and / or R 13 and R 14 are not bonded to each other to form at least one ring. At least one of R 11 to R 14 is not hydrogen,
l and o are integers of 0 or 1, l + o is 1 or more,
L is iii) a C 6 ~ C 30 aryl group; C 2 ~ C 20 monovalent heterocyclic group; And a fluorenyl group, or ii) a C 6 to C 30 arylene group; C 2 ~ C 20 divalent heterocyclic group; And it is selected from the group consisting of fluorenylene group,
Y is hydrogen; heavy hydrogen; Tritium; -N (Ar 3 ) (Ar 4 ); C 1 ~ C 10 alkyl group; C 6 ~ C 30 Aryl group; And C 6 ~ C 30 It is selected from the group consisting of a condensed ring group of an aromatic ring and C 3 ~ C 30 aliphatic ring,
m and n are each 0 or 1 (however, m + n is 1 or more),
Ar 1 is iii) a C 6 ~ C 30 aryl group; C 2 ~ C 20 monovalent heterocyclic group; A monovalent condensed ring group of an aromatic ring of C 6 to C 30 and an aliphatic ring of C 3 to C 30 ; And a fluorenyl group, or ii) a C 6 to C 30 arylene group; C 2 ~ C 20 divalent heterocyclic group; A divalent condensed ring group of an aromatic ring of C 6 to C 30 and an aliphatic ring of C 3 to C 30 ; And it is selected from the group consisting of fluorenylene group,
Ar 2 is a silane group; C 6 ~ C 30 Aryl group; C 2 ~ C 20 heterocyclic group; And C 6 ~ C 30 It is selected from the group consisting of a condensed ring group of an aromatic ring and C 3 ~ C 30 aliphatic ring,
Ar 3 and Ar 4 are independently of each other C 6 ~ C 30 aryl group; C 2 ~ C 30 heterocyclic group; And fluorenyl groups.
(At this time, each of L, Y, Ar 1 , Ar 3 , Ar 4 , R ′ and R ″, R 2 to R 5 and R 11 to R 14 is an alkyl group of C 1 to C 20 ; C 6 to C 20 An aryl group of C 6 to C 20 substituted with deuterium; and a heterocyclic group of C 2 to C 20 including at least one hetero atom among O, N, S, Si and P; Can be substituted with one or more selected substituents) 제 1항에 있어서,
하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.
Figure 112019128081767-pat00109

(상기 화학식에서, Ar1, Ar2, R2~R5, m, n, X 및 L은 제 1항에서 정의된 것과 동일하다)According to claim 1,
A compound characterized by being represented by one of the following formulas.
Figure 112019128081767-pat00109

(In the above formula, Ar 1 , Ar 2 , R 2 ~ R 5 , m, n, X and L are the same as defined in claim 1) 제 1항에 있어서,
하기 화학식 중 하나인 것을 특징으로 하는 화합물.
<화학식16> <화학식17> <화학식18>
Figure 112019086099118-pat00092

<화학식19> <화학식20> <화학식21>
Figure 112019086099118-pat00093

<화학식25> <화학식26> <화학식27>
Figure 112019086099118-pat00094

(상기 화학식에서, Ar1, Ar2, R′, R″, R2~R5, m 및 n은 제 1항에서 정의된 것과 동일하다)According to claim 1,
A compound characterized in that it is one of the following formula.
<Formula 16><Formula17><Formula18>
Figure 112019086099118-pat00092

<Formula 19><Formula20><Formula21>
Figure 112019086099118-pat00093

<Formula 25><Formula26><Formula27>
Figure 112019086099118-pat00094

(In the above formula, Ar 1 , Ar 2 , R ′, R ″, R 2 ~ R 5 , m and n are the same as defined in claim 1) 제 1항에 있어서,
하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.
Figure 112019128081767-pat00110

(상기 화학식에서, R′, R″, Ar1~Ar4, L, m 및 n은 제 1항에서 정의된 것과 동일하다)According to claim 1,
A compound characterized by being represented by one of the following formulas.
Figure 112019128081767-pat00110

(In the above formula, R ′, R ″, Ar 1 ~ Ar 4 , L, m and n are the same as defined in claim 1) 제 1항에 있어서,
하기 화합물 중 하나인 것을 특징으로 하는 화합물.
Figure 112019086099118-pat00097

Figure 112019086099118-pat00098

Figure 112019086099118-pat00099

Figure 112019086099118-pat00100

Figure 112019086099118-pat00101

Figure 112019086099118-pat00102

Figure 112019086099118-pat00103

Figure 112019086099118-pat00104

Figure 112019086099118-pat00105

Figure 112019086099118-pat00106

Figure 112019086099118-pat00107
According to claim 1,
A compound characterized by being one of the following compounds.
Figure 112019086099118-pat00097

Figure 112019086099118-pat00098

Figure 112019086099118-pat00099

Figure 112019086099118-pat00100

Figure 112019086099118-pat00101

Figure 112019086099118-pat00102

Figure 112019086099118-pat00103

Figure 112019086099118-pat00104

Figure 112019086099118-pat00105

Figure 112019086099118-pat00106

Figure 112019086099118-pat00107
 제 1전극, 제 2전극, 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층을 포함하는 유기전기소자에 있어서,
상기 유기물층은 제 1항 내지 제 5항 중 어느 한 항의 화합물을 함유하는 것을 특징으로 하는 유기전기소자.In the organic electrical device including a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode,
The organic layer is an organic electrical device, characterized in that it contains the compound of any one of claims 1 to 5. 제 6항에 있어서,
상기 화합물을 용액공정(soluble process)에 의해 상기 유기물층으로 형성하는 것을 특징으로 하는 유기전기소자. The method of claim 6,
An organic electrical device characterized in that the compound is formed into the organic material layer by a soluble process. 제 6항에 있어서,
상기 유기물층은 발광층, 정공 주입층, 정공 수송층, 전자 주입층, 전자 수송층 및 발광보조층 중 적어도 하나를 포함하는 것을 특징으로 하는 유기전기소자.The method of claim 6,
The organic material layer comprises at least one of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer and a light emitting auxiliary layer. 제 8항에 있어서,
상기 발광층 또는 상기 발광보조층은 상기 화합물로 형성되는 것을 특징으로 하는 유기전기소자.The method of claim 8,
The light emitting layer or the light emitting auxiliary layer is an organic electric device, characterized in that formed of the compound. 제 6항의 유기전기소자를 포함하는 디스플레이장치; 및
상기 디스플레이장치를 구동하는 제어부; 를 포함하는 전자장치.A display device comprising the organic electroluminescent element of claim 6; And
A control unit for driving the display device; Electronic device comprising a. 제 10항에 있어서,
상기 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치.The method of claim 10,
The organic electric device is an electronic device, characterized in that at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a monochromatic or white lighting device.
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JP2010270084A (en) 2009-05-25 2010-12-02 Idemitsu Kosan Co Ltd Indole derivative, and solar cell of organic thin film by using the same

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