[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

KR102401913B1 - Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device - Google Patents

Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device Download PDF

Info

Publication number
KR102401913B1
KR102401913B1 KR1020210075918A KR20210075918A KR102401913B1 KR 102401913 B1 KR102401913 B1 KR 102401913B1 KR 1020210075918 A KR1020210075918 A KR 1020210075918A KR 20210075918 A KR20210075918 A KR 20210075918A KR 102401913 B1 KR102401913 B1 KR 102401913B1
Authority
KR
South Korea
Prior art keywords
substituted
unsubstituted
group
organic
layer
Prior art date
Application number
KR1020210075918A
Other languages
Korean (ko)
Inventor
최돈수
Original Assignee
최돈수
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 최돈수 filed Critical 최돈수
Priority to KR1020210075918A priority Critical patent/KR102401913B1/en
Priority to KR1020220035270A priority patent/KR20220167743A/en
Priority to KR1020220035274A priority patent/KR102573956B1/en
Priority to KR1020220035271A priority patent/KR20220167744A/en
Priority to KR1020220035272A priority patent/KR20220167745A/en
Priority to KR1020220035273A priority patent/KR102624591B1/en
Application granted granted Critical
Publication of KR102401913B1 publication Critical patent/KR102401913B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • C07D241/48—Phenazines with hydrocarbon radicals, substituted by nitrogen atoms, directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

발광 파장 조절 및 발광 효율이 우수한 말로노나이트릴(malononitrile) 화합물, 그의 제조방법 및 상기 말로노나이트릴(malononitrile) 화합물을 포함하는 유기전자소자를 제시한다.Provided are a malononitrile compound having excellent emission wavelength control and luminous efficiency, a manufacturing method thereof, and an organic electronic device including the malononitrile compound.

Description

유기 전기 발광 소자용 발광 재료, 이를 이용한 유기 전기 발광 소자 및 유기 전기 발광 소자용 재료{LIGHT-EMITTING MATERIAL FOR ORGANIC ELECTROLUMINESCENT DEVICE, ORGANIC ELECTROLUMINESCENT DEVICE USING SAME, AND MATERIAL FOR ORGANIC ELECTROLUMINESCENT DEVICE}Light-emitting material for organic electroluminescent device, and material for organic electroluminescent device and organic electroluminescent device using same

본 발명은 말로노나이트릴(malononitrile) 화합물, 이의 제조방법 및 이를 이용한 유기전자소자의 발전에 기여하고자 하는 기술에 관한 것이다.The present invention relates to a malononitrile (malononitrile) compound, a method for manufacturing the same, and a technology to contribute to the development of an organic electronic device using the same.

일반적으로 유기발광 다이오드(OLED: Organic Light Emitting Diodes)는 음극, 양극 및 음극과 양극 사이에 개재된 유기물 층으로 구성되어 있다. 소자의 구성을 전체적으로 보면 투명 ITO 양극, 정공주입층(HIL), 정공전달층(HTL), 발광층(EL), 정공저지층(HBL), 전자전달층(ETL), 전자주입층(EIL) 및 LiAl 등의 음극으로 형성되며, 필요에 따라 유기물 층의 1~2 개를 생략하는 경우도 있다. 구성된 양 전극 사이에 전계가 인가되면 음극 측으로부터 전자가 주입되고 양극 측으로부터 정공이 주입된다. 또한, 이 전자가 발광층에 정공과 재결합하여 여기상태를 생성하고, 여기상태가 기저상태로 되돌아갈 때에 에너지를 빛으로서 방출한다. 이러한 발광 재료는 크게 형광과 인광으로 나뉘며, 발광층 형성방법은 형광 호스트(순수 유기물)에 인광(유기금속)을 도핑하는 방법과 형광 호스트에 형광 도판트(질소 등을 포함하는 유기물)를 도핑하는 방법 및 발광체에 도판트 (DCM, Rubrene, DCJTB 등)를 이용하여 장파장을 구현하는 방법 등이 있다. 이러한 도핑을 통해 발광 파장, 효율, 구동전압, 수명 등을 개선하려 하고 있다. 일반적으로 발광층 및 공동층 형성용 리간드 재료들은 벤젠, 나프탈렌, 플로렌, 스파이로플로렌, 안트라센, 파이렌, 카바졸 등의 중심체와 페닐, 바이페닐, 나프탈렌, 헤테로사이클 등의 리간드 그리고 오르소, 메타, 파라 등의 결합 위치 및 아민, 시안, 불소, 메틸, 트리메틸 등이 치환된 구조들을 갖는다.In general, organic light emitting diodes (OLEDs: Organic Light Emitting Diodes) are composed of a cathode, an anode, and an organic material layer interposed between the cathode and the anode. Looking at the structure of the device as a whole, a transparent ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL) and It is formed as a cathode such as LiAl, and if necessary, one or two of the organic layer may be omitted. When an electric field is applied between the configured positive electrodes, electrons are injected from the negative electrode side and holes are injected from the positive electrode side. Further, these electrons recombine with holes in the light emitting layer to generate an excited state, and when the excited state returns to the ground state, energy is emitted as light. These light emitting materials are largely divided into fluorescence and phosphorescence. The method of forming the light emitting layer is a method of doping phosphorescence (organometal) into a fluorescent host (pure organic material) and a method of doping a fluorescent host with a fluorescent dopant (organic material containing nitrogen, etc.) and a method of implementing a long wavelength using a dopant (DCM, Rubrene, DCJTB, etc.) in the light emitting body. Through this doping, it is trying to improve the emission wavelength, efficiency, driving voltage, lifespan, and the like. In general, the ligand materials for forming the light emitting layer and the cavity layer include central bodies such as benzene, naphthalene, fluorene, spiroflorene, anthracene, pyrene, and carbazole, and ligands such as phenyl, biphenyl, naphthalene, and heterocycle, and ortho, meta , and has structures substituted with bonding positions such as para and amine, cyan, fluorine, methyl, trimethyl, and the like.

현재 디스플레이의 화면이 대형화 방향으로 진행되면서 OLED의 경우 더 섬세하며, 더 선명한 색들의 재료들이 요구되고 있다. 또한 발광파장의 색 좌표 이외에, 소자의 낮은 구동전압에서 높은 발광효율 및 재료의 화학 구조적 열 안정성이 높은 유리전이온도 등을 요구한다. As the screen of the current display progresses in the direction of enlargement, in the case of OLED, materials with more delicate and vivid colors are required. In addition to the color coordinates of the emission wavelength, high luminous efficiency at a low driving voltage of the device and a high glass transition temperature, etc., are required for chemical structural and thermal stability of the material.

본 발명은 성능이 우수한 평면형 구조의 유기발광 소자의 성능 향상을 위한 말로노나이트릴(malononitrile) 화합물을 제공하는 것을 목적으로 한다. 본 발명은 말로노나이트릴(malononitrile) 화합물을 이용하여, 평면형 구조의 재료 개발을 통해 성능이 우수한 유기전기소자의 제공하는 것을 목적으로 한다. 본 발명은 말로노나이트릴(malononitrile) 화합물을 이용한 유기발광소자 재료 개발을 목적으로 한다.An object of the present invention is to provide a malononitrile compound for improving the performance of an organic light emitting diode having a planar structure having excellent performance. An object of the present invention is to provide an organic electric device having excellent performance through the development of a material having a planar structure by using a malononitrile compound. An object of the present invention is to develop an organic light emitting device material using a malononitrile compound.

본 발명은 하기 화학식 1-1에서 화학식 1-10 중 어느 하나로 표시되는 말로노나이트릴(malononitrile) 화합물:The present invention relates to a malononitrile compound represented by any one of Chemical Formulas 1-10 in the following Chemical Formula 1-1:

[화학식 1-1][Formula 1-1]

Figure 112021067501219-pat00001
Figure 112021067501219-pat00001

[화학식 1-2][Formula 1-2]

Figure 112021067501219-pat00002
Figure 112021067501219-pat00002

[화학식 1-3][Formula 1-3]

Figure 112021067501219-pat00003
Figure 112021067501219-pat00003

[화학식 1-4][Formula 1-4]

Figure 112021067501219-pat00004
Figure 112021067501219-pat00004

[화학식 1-5][Formula 1-5]

Figure 112021067501219-pat00005
Figure 112021067501219-pat00005

[화학식 1-6][Formula 1-6]

Figure 112021067501219-pat00006
Figure 112021067501219-pat00006

[화학식 1-7][Formula 1-7]

Figure 112021067501219-pat00007
Figure 112021067501219-pat00007

[화학식 1-8][Formula 1-8]

Figure 112021067501219-pat00008
Figure 112021067501219-pat00008

[화학식 1-9][Formula 1-9]

Figure 112021067501219-pat00009
Figure 112021067501219-pat00009

[화학식 1-10][Formula 1-10]

Figure 112021067501219-pat00010
Figure 112021067501219-pat00010

상기 R1 내지 R6은 각각 서로 독립적으로 수소; Wherein R 1 To R 6 They are each independently hydrogen;

치환 또는 비치환된 탄소수 1 내지 40개의 알킬기; a substituted or unsubstituted C 1 to C 40 alkyl group;

치환 또는 비치환된 탄소수 2 내지 40개의 알킬알콕시기;a substituted or unsubstituted C2-C40 alkylalkoxy group;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; a substituted or unsubstituted C 6 to C 40 aryl group;

치환 또는 비치환된 탄소수 7 내지 40개의 아릴알킬기; a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; a substituted or unsubstituted C 6 to C 40 arylamine group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; a substituted or unsubstituted C 6 to C 30 aryl cyan group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴플루오로기; a substituted or unsubstituted C6-C30 arylfluoro group;

치환 또는 비치환된 탄소수 11 내지 40개의 헤테로아릴기; a substituted or unsubstituted C11 to C40 heteroaryl group;

치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기; a substituted or unsubstituted C6-C40 aminoaryl group;

치환 또는 비치환된 탄소수 5 내지 40개의 아미노헤테로아릴기; a substituted or unsubstituted aminoheteroaryl group having 5 to 40 carbon atoms;

중에서 선택되고,is selected from

상기 Ar1은 The Ar 1 is

치환 또는 비치환된 탄소수 1 내지 40개의 알킬기; a substituted or unsubstituted C 1 to C 40 alkyl group;

치환 또는 비치환된 탄소수 2 내지 40개의 알킬알콕시기;a substituted or unsubstituted C2-C40 alkylalkoxy group;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; a substituted or unsubstituted C 6 to C 40 aryl group;

치환 또는 비치환된 탄소수 7 내지 40개의 아릴알킬기; a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; a substituted or unsubstituted C 6 to C 40 arylamine group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; a substituted or unsubstituted C 6 to C 30 aryl cyan group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴플루오로기; a substituted or unsubstituted C6-C30 arylfluoro group;

치환 또는 비치환된 탄소수 11 내지 40개의 헤테로아릴기; a substituted or unsubstituted C11 to C40 heteroaryl group;

중에서 선택된다.is selected from

본 발명은 말로노나이트릴(malononitrile) 화합물을 이용한 유기 전자 소자를 제공한다.The present invention provides an organic electronic device using a malononitrile compound.

본 발명에 따르는 말로노나이트릴(malononitrile) 화합물은 대칭과 비대칭 및 평면형의 구조를 제공하며, 또한 본 발명의 대칭과 비대칭 및 평면형의 구조는 성능이 우수하며, 본 발명은 특정 구조의 말로노나이트릴(malononitrile) 화합물을 이용하여 유기발광 소자의 성능이 우수하다. The malononitrile compound according to the present invention provides a symmetric, asymmetric and planar structure, and the symmetric, asymmetric and planar structure of the present invention has excellent performance, and the present invention provides malononite of a specific structure The performance of the organic light emitting device is excellent by using a malononitrile compound.

이하 본 발명을 보다 상세하게 설명한다. 하기의 구체적 설명은 본 발명의 일례를 들어 설명하는 것이므로 본 발명이 이에 한정되지 않는다.Hereinafter, the present invention will be described in more detail. Since the following detailed description is given by way of an example of the present invention, the present invention is not limited thereto.

본 발명의 일 측면에 따라, 하기 화학식 1-1에서 화학식 1-10 중 어느 하나로 표시되는 말로노나이트릴(malononitrile) 화합물:According to an aspect of the present invention, a malononitrile compound represented by any one of Formula 1-10 in Formula 1-1 below:

[화학식 1-1][Formula 1-1]

Figure 112021067501219-pat00011
Figure 112021067501219-pat00011

[화학식 1-2][Formula 1-2]

Figure 112021067501219-pat00012
Figure 112021067501219-pat00012

[화학식 1-3][Formula 1-3]

Figure 112021067501219-pat00013
Figure 112021067501219-pat00013

[화학식 1-4][Formula 1-4]

Figure 112021067501219-pat00014
Figure 112021067501219-pat00014

[화학식 1-5][Formula 1-5]

Figure 112021067501219-pat00015
Figure 112021067501219-pat00015

[화학식 1-6][Formula 1-6]

Figure 112021067501219-pat00016
Figure 112021067501219-pat00016

[화학식 1-7][Formula 1-7]

Figure 112021067501219-pat00017
Figure 112021067501219-pat00017

[화학식 1-8][Formula 1-8]

Figure 112021067501219-pat00018
Figure 112021067501219-pat00018

[화학식 1-9][Formula 1-9]

Figure 112021067501219-pat00019
Figure 112021067501219-pat00019

[화학식 1-10][Formula 1-10]

Figure 112021067501219-pat00020
Figure 112021067501219-pat00020

상기 R1 내지 R6은 각각 서로 독립적으로 수소; Wherein R 1 To R 6 They are each independently hydrogen;

치환 또는 비치환된 탄소수 1 내지 40개의 알킬기; a substituted or unsubstituted C 1 to C 40 alkyl group;

치환 또는 비치환된 탄소수 2 내지 40개의 알킬알콕시기;a substituted or unsubstituted C2-C40 alkylalkoxy group;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; a substituted or unsubstituted C 6 to C 40 aryl group;

치환 또는 비치환된 탄소수 7 내지 40개의 아릴알킬기; a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; a substituted or unsubstituted C 6 to C 40 arylamine group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; a substituted or unsubstituted C 6 to C 30 aryl cyan group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴플루오로기; a substituted or unsubstituted C6-C30 arylfluoro group;

치환 또는 비치환된 탄소수 11 내지 40개의 헤테로아릴기; a substituted or unsubstituted C11 to C40 heteroaryl group;

치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기; a substituted or unsubstituted C6-C40 aminoaryl group;

치환 또는 비치환된 탄소수 5 내지 40개의 아미노헤테로아릴기; a substituted or unsubstituted aminoheteroaryl group having 5 to 40 carbon atoms;

중에서 선택되고,is selected from

상기 Ar1은 The Ar 1 is

치환 또는 비치환된 탄소수 1 내지 40개의 알킬기; a substituted or unsubstituted C 1 to C 40 alkyl group;

치환 또는 비치환된 탄소수 2 내지 40개의 알킬알콕시기;a substituted or unsubstituted C2-C40 alkylalkoxy group;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴기; a substituted or unsubstituted C 6 to C 40 aryl group;

치환 또는 비치환된 탄소수 7 내지 40개의 아릴알킬기; a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms;

치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기; a substituted or unsubstituted C 6 to C 40 arylamine group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴시안기; a substituted or unsubstituted C 6 to C 30 aryl cyan group;

치환 또는 비치환된 탄소수 6 내지 30개의 아릴플루오로기; a substituted or unsubstituted C6-C30 arylfluoro group;

치환 또는 비치환된 탄소수 11 내지 40개의 헤테로아릴기; a substituted or unsubstituted C11 to C40 heteroaryl group;

중에서 선택된다.is selected from

상기 화학식 1-1 내지 화학식 1-10의 구체적 구조는 하기 화학식 2-1-1 내지 2-10-2 중 어느 하나로 표시되는 것을 특징으로 하는 말로노나이트릴(malononitrile) 화합물:The specific structure of Formulas 1-1 to 1-10 is a malononitrile compound, characterized in that it is represented by any one of the following Formulas 2-1-1 to 2-10-2:

[화학식 2-1-1][Formula 2-1-1]

Figure 112021067501219-pat00021
Figure 112021067501219-pat00021

[화학식 2-1-2][Formula 2-1-2]

Figure 112021067501219-pat00022
Figure 112021067501219-pat00022

[화학식 2-1-3][Formula 2-1-3]

Figure 112021067501219-pat00023
Figure 112021067501219-pat00023

[화학식 2-1-4][Formula 2-1-4]

Figure 112021067501219-pat00024
Figure 112021067501219-pat00024

[화학식 2-1-5][Formula 2-1-5]

Figure 112021067501219-pat00025
Figure 112021067501219-pat00025

[화학식 2-1-6][Formula 2-1-6]

Figure 112021067501219-pat00026
Figure 112021067501219-pat00026

[화학식 2-1-7][Formula 2-1-7]

Figure 112021067501219-pat00027
Figure 112021067501219-pat00027

[화학식 2-1-8][Formula 2-1-8]

Figure 112021067501219-pat00028
Figure 112021067501219-pat00028

[화학식 2-2-1][Formula 2-2-1]

Figure 112021067501219-pat00029
Figure 112021067501219-pat00029

[화학식 2-2-2][Formula 2-2-2]

Figure 112021067501219-pat00030
Figure 112021067501219-pat00030

[화학식 2-3-1][Formula 2-3-1]

Figure 112021067501219-pat00031
Figure 112021067501219-pat00031

[화학식 2-3-2][Formula 2-3-2]

Figure 112021067501219-pat00032
Figure 112021067501219-pat00032

[화학식 2-3-3][Formula 2-3-3]

Figure 112021067501219-pat00033
Figure 112021067501219-pat00033

[화학식 2-3-4][Formula 2-3-4]

Figure 112021067501219-pat00034
Figure 112021067501219-pat00034

[화학식 2-4-1][Formula 2-4-1]

Figure 112021067501219-pat00035
Figure 112021067501219-pat00035

[화학식 2-4-2][Formula 2-4-2]

Figure 112021067501219-pat00036
Figure 112021067501219-pat00036

[화학식 2-4-3][Formula 2-4-3]

Figure 112021067501219-pat00037
Figure 112021067501219-pat00037

[화학식 2-5-1][Formula 2-5-1]

Figure 112021067501219-pat00038
Figure 112021067501219-pat00038

[화학식 2-5-2][Formula 2-5-2]

Figure 112021067501219-pat00039
Figure 112021067501219-pat00039

[화학식 2-6-1][Formula 2-6-1]

Figure 112021067501219-pat00040
Figure 112021067501219-pat00040

[화학식 2-6-2][Formula 2-6-2]

Figure 112021067501219-pat00041
Figure 112021067501219-pat00041

[화학식 2-7-1][Formula 2-7-1]

Figure 112021067501219-pat00042
Figure 112021067501219-pat00042

[화학식 2-7-2][Formula 2-7-2]

Figure 112021067501219-pat00043
Figure 112021067501219-pat00043

[화학식 2-7-3][Formula 2-7-3]

Figure 112021067501219-pat00044
Figure 112021067501219-pat00044

[화학식 2-8-1][Formula 2-8-1]

Figure 112021067501219-pat00045
Figure 112021067501219-pat00045

[화학식 2-8-2][Formula 2-8-2]

Figure 112021067501219-pat00046
Figure 112021067501219-pat00046

[화학식 2-8-3][Formula 2-8-3]

Figure 112021067501219-pat00047
Figure 112021067501219-pat00047

[화학식 2-9-1][Formula 2-9-1]

Figure 112021067501219-pat00048
Figure 112021067501219-pat00048

[화학식 2-9-2][Formula 2-9-2]

Figure 112021067501219-pat00049
Figure 112021067501219-pat00049

[화학식 2-10-1][Formula 2-10-1]

Figure 112021067501219-pat00050
Figure 112021067501219-pat00050

[화학식 2-10-2][Formula 2-10-2]

Figure 112021067501219-pat00051
Figure 112021067501219-pat00051

상기 화학식 2-1-1 내지 화학식 2-10-2에서 In Formula 2-1-1 to Formula 2-10-2,

상기 R1 내지 R6은 각각 서로 독립적으로 수소; Wherein R 1 To R 6 They are each independently hydrogen;

치환 또는 비치환된 탄소수 1 내지 40개의 아릴기; a substituted or unsubstituted C 1 to C 40 aryl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아릴알킬기; a substituted or unsubstituted C 1 to C 40 arylalkyl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아릴아민기; a substituted or unsubstituted C 1 to C 40 arylamine group;

치환 또는 비치환된 탄소수 1 내지 30개의 아릴시안기; a substituted or unsubstituted C 1 to C 30 aryl cyan group;

치환 또는 비치환된 탄소수 1 내지 30개의 아릴플루오로기; a substituted or unsubstituted C1-C30 arylfluoro group;

치환 또는 비치환된 탄소수 1 내지 40개의 헤테로아릴기; a substituted or unsubstituted C 1 to C 40 heteroaryl group;

치환 또는 비치환된 탄소수 1 내지 40개의 헤테로아민아릴기; a substituted or unsubstituted C 1 to C 40 heteroamine aryl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아미노아릴기; a substituted or unsubstituted C1-C40 aminoaryl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아미노헤테로아릴기; a substituted or unsubstituted aminoheteroaryl group having 1 to 40 carbon atoms;

중에서 선택되고,is selected from

상기 Ar1은 The Ar 1 is

치환 또는 비치환된 탄소수 1 내지 40개의 알킬기; a substituted or unsubstituted C 1 to C 40 alkyl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아릴기; a substituted or unsubstituted C 1 to C 40 aryl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아릴알킬기; a substituted or unsubstituted C 1 to C 40 arylalkyl group;

치환 또는 비치환된 탄소수 1 내지 40개의 아릴아민기; a substituted or unsubstituted C 1 to C 40 arylamine group;

치환 또는 비치환된 탄소수 1 내지 40개의 헤테로아릴기; a substituted or unsubstituted C 1 to C 40 heteroaryl group;

치환 또는 비치환된 탄소수 1 내지 40개의 헤테로아민아릴기; a substituted or unsubstituted C 1 to C 40 heteroamine aryl group;

중에서 선택된다.is selected from

상기 화합물은 아래 화합물들 중 어느 하나인 것을 특징으로 한다.The compound is characterized in that it is any one of the following compounds.

Figure 112021067501219-pat00052
Figure 112021067501219-pat00052

Figure 112021067501219-pat00053
Figure 112021067501219-pat00053

Figure 112021067501219-pat00054
Figure 112021067501219-pat00054

Figure 112021067501219-pat00055
Figure 112021067501219-pat00055

Figure 112021067501219-pat00056
Figure 112021067501219-pat00056

Figure 112021067501219-pat00057
Figure 112021067501219-pat00057

Figure 112021067501219-pat00058
Figure 112021067501219-pat00058

Figure 112021067501219-pat00059
Figure 112021067501219-pat00059

Figure 112021067501219-pat00060
Figure 112021067501219-pat00060

Figure 112021067501219-pat00061
Figure 112021067501219-pat00061

Figure 112021067501219-pat00062
Figure 112021067501219-pat00062

Figure 112021067501219-pat00063
Figure 112021067501219-pat00063

Figure 112021067501219-pat00064
Figure 112021067501219-pat00064

Figure 112021067501219-pat00065
Figure 112021067501219-pat00065

Figure 112021067501219-pat00066
Figure 112021067501219-pat00066

Figure 112021067501219-pat00067
Figure 112021067501219-pat00067

Figure 112021067501219-pat00068
Figure 112021067501219-pat00068

본 발명의 일 측면에 따르면, 제1 전극, 제2 전극 및 이들 전극 사이에 배치된 1층 이상의 유기물 층을 포함하는 유기전자소자로서, 상기 유기물층 중 적어도 1층 이상이 상기 말로노나이트릴(malononitrile) 화합물을 포함하는 유기전자소자가 제공된다.According to an aspect of the present invention, an organic electronic device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the electrodes, wherein at least one of the organic material layers is the malononitrile (malononitrile). ) An organic electronic device comprising the compound is provided.

상기 말로노나이트릴(malononitrile) 화합물은 단일 물질 또는 서로 다른 물질의 혼합물의 형태로 상기 유기물층에 포함될 수 있다. The malononitrile compound may be included in the organic material layer in the form of a single material or a mixture of different materials.

상기 유기물층은 정공 주입층, 정공 수송층, 정공 주입 기능 및 정공 수송 기능을 동시에 갖는 기능층, 전자 저지층, 발광층, 정공 저지층, 전자 수송층, 전자 주입층 및 전자 수송 기능 및 전자 주입 기능을 동시에 갖는 기능층 중 적어도 하나를 포함할 수 있다. 상기 정공 주입층, 상기 정공 수송층 및 상기 정공 주입 기능 및 정공 수송 기능을 동시에 갖는 기능층 중 적어도 하나는, 통상의 정공 주입 물질, 정공 수송 물질 및 정공 주입 및 수송 기능을 동시에 하는 물질 외에, 전하-생성 물질을 더 포함할 수 있다.The organic material layer includes a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport function and an electron injection function. It may include at least one of the functional layers. At least one of the hole injection layer, the hole transport layer, and the functional layer having both the hole injection function and the hole transport function is, It may further include a product material.

본 명세서 중 "유기물층"은 유기전자소자 중 제1전극과 제2전극 사이에 개재된 모든 층을 가리키는 용어이다.In the present specification, the term "organic material layer" refers to all layers interposed between the first electrode and the second electrode among organic electronic devices.

예를 들어, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 인광 호스트, 형광 호스트, 인광 도판트 및 형광 도판트 중 하나 이상을 포함할 수 있다. For example, the organic material layer may include an emission layer, and the emission layer may include at least one of a phosphorescent host, a fluorescent host, a phosphorescent dopant, and a fluorescent dopant.

상기 발광층은 적색, 녹색 또는 청색 발광층일 수 있다. The light emitting layer may be a red, green or blue light emitting layer.

상기 전자 수송층에 상기 말로노나이트릴(malononitrile) 화합물이 포함되어 있으며, 고효율, 고휘도, 고색순도, 및 장수명을 갖는 유기전자소자를 제공할 수 있다.The electron transport layer contains the malononitrile compound, and it is possible to provide an organic electronic device having high efficiency, high brightness, high color purity, and a long lifespan.

또한, 상기 말로노나이트릴(malononitrile) 화합물은 상기 발광층, 정공 수송층 및 소자 성능향상의 구조 응용에 포함될 수 있다.In addition, the malononitrile (malononitrile) compound may be included in the light emitting layer, the hole transport layer and the structural application of improving device performance.

상기 유기전자소자는 상기 말로노나이트릴(malononitrile) 화합물을 이용하는 것을 제외하고는, 통상의 유기전자소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic electronic device may be manufactured by a typical organic electronic device manufacturing method and material, except for using the malononitrile compound.

본 발명의 일 측면에 따른 구체예로써, 상기 유기전자소자는 유기발광소자 (OLED), 유기태양전지 (OSC), 전자종이 (e-Paper), 유기감광체(OPC) 또는 유기트랜지스터 (OTFT)일 수 있다.As a specific example according to an aspect of the present invention, the organic electronic device may be an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoreceptor (OPC), or an organic transistor (OTFT). can

유기발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공전달층, 발광층, 정공저지층 및 전자전달층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착 시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기발광소자를 만들 수도 있다. 상기 유기물 층은 정공주입층, 정공전달층, 발광층, 정공저지층 및 전자전달층 등을 포함하는 다층 구조일 수도 있다. 또한, 상기 유기물 층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용매 공정(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.The organic light emitting device uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to deposit a metal or a conductive metal oxide or an alloy thereof on a substrate to form an anode. and forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer. In addition, the organic layer is formed using a variety of polymer materials using a solvent process rather than a vapor deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer using a smaller number of methods. It can be made in layers.

본 발명에 따른 유기발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다. 본 발명에 따른 화합물은 유기태양전지, 조명용 OLED, Flexible OLED, 유기감광체, 유기트랜지스터 등을 비롯한 유기전자소자에서도 유기발광소자에 적용되는 것과 유사한 원리로 작용할 수 있다. The organic light emitting diode according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used. The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, lighting OLEDs, flexible OLEDs, organic photoreceptors, organic transistors, and the like.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다. Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and thus the content of the present invention is not limited thereto.

또한, 본 발명의 각 실시예에서 제조방법이 구체적으로 개시되지 않은 화합물은 당업계에 통상적인 방법으로 제조하거나 또는 다른 실시예에 기재된 제조방법을 참고하여 제조함을 이해한다.In addition, it is understood that the compound for which the preparation method is not specifically disclosed in each embodiment of the present invention is prepared by a conventional method in the art or is prepared by referring to the preparation method described in other examples.

<중간체의 제조><Preparation of intermediate>

1-1 중간체 2-bromo-11H-benzo[b]fluoren-11-one의 제조 1-1 Preparation of intermediate 2-bromo-11H-benzo[b]fluoren-11-one

Figure 112021067501219-pat00069
Figure 112021067501219-pat00069

11H-benzo[b]fluoren-11-one (23.03g, 0.1 mol)과 Propylene carbonate (100 mL)에 녹인 후, N-bromo succinimide (17.8g, 0.1mol)을 넣고, 60℃에서 30분 동안 교반하였다. 반응을 실온으로 냉각시킨 후, 물 (1200 mL)희석하고 500 mL의 toluene으로 추출했으며, 유기물을 무수유산 마그네슘으로 건조시킨 후, 혼합물을 여과 농축하여 최종 화합물 (24.73g，80%）을 얻었다. MS [M+H]+ = 307After dissolving in 11H-benzo[b]fluoren-11-one (23.03g, 0.1 mol) and propylene carbonate (100 mL), N-bromo succinimide (17.8g, 0.1mol) was added, and stirred at 60℃ for 30 minutes. did After the reaction was cooled to room temperature, it was diluted with water (1200 mL), extracted with 500 mL of toluene, the organic material was dried over anhydrous magnesium lactate, and the mixture was concentrated by filtration to obtain the final compound (24.73 g, 80%). MS [M+H] + = 307

1-2 중간체 4,5,9,10-tetrabromoisochromeno[6,5,4-def]isochromene-1,3,6,8-tetraone의 제조1-2 Preparation of intermediate 4,5,9,10-tetrabromoisochromeno[6,5,4-def]isochromene-1,3,6,8-tetraone

Figure 112021067501219-pat00070
Figure 112021067501219-pat00070

isochromeno[6,5,4-def]isochromene-1,3,6,8-tetraone(26.82g, 0.1 mol)과 Propylene carbonate (200 mL)에 녹인 후, N-bromo succinimide (71.2g, 0.4mol)을 넣고, 60℃에서 30분 동안 교반하였다. 반응을 실온으로 냉각시킨 후, 물 (1200 mL)희석하고 500 mL의 toluene으로 추출했으며, 유기물을 무수유산 마그네슘으로 건조시킨 후, 혼합물을 여과 농축하여 최종 화합물 (35.03g，60%）을 얻었다. MS [M+H]+ = 580After dissolving in isochromeno[6,5,4-def]isochromene-1,3,6,8-tetraone (26.82g, 0.1 mol) and propylene carbonate (200 mL), N-bromo succinimide (71.2g, 0.4mol) was added and stirred at 60 °C for 30 minutes. The reaction was cooled to room temperature, diluted with water (1200 mL), extracted with 500 mL of toluene, the organic material was dried over anhydrous magnesium lactate, and the mixture was concentrated by filtration to obtain the final compound (35.03 g, 60%). MS [M+H] + = 580

2-1 중간체 2-(2-bromo-11H-benzo[b]fluoren-11-ylidene)malononitrile의 제조2-1 Preparation of intermediate 2-(2-bromo-11H-benzo[b]fluoren-11-ylidene)malononitrile

Figure 112021067501219-pat00071
Figure 112021067501219-pat00071

500ml 둥근 바닥 플라스크에 화합물2-bromo-11H-benzo[b]fluoren-11-one (4.641g, 15.0mmol), 말로노나이트릴(malononitrile)(30.0mmol) 및 디 클로로메테인 용매를 넣고 아르곤 조건 하에서 30분간 교반 한다. 0℃로 냉각하여 10분간 교반 후 사염화티타늄 (TiCl4)(3.28ml, 30m mol)을 천천히 넣어준 후 피리딘(7.40ml, 9.2mmol)을 넣고 0℃에서 상온으로 천천히 온도를 올려 상온에서 2시간 교반시킨다. 이후 디클로로메탄/염화암모늄 수용액(CH2Cl2/aq.NH4Cl)으로 추출한 후에 유기물층을 무수황산마그네슘으로 건조시키고 유기층을 모아 감압하에서 증류하여 컬럼크로마토그래피를 이용하여 최종 화합물 （2.14g, 수율 40%)을 얻었다. MS [M+H]+ 357Compound 2-bromo-11H-benzo[b]fluoren-11-one (4.641g, 15.0mmol), malononitrile (30.0mmol) and dichloromethane solvent were placed in a 500ml round bottom flask under argon conditions. under stirring for 30 minutes. After cooling to 0°C and stirring for 10 minutes, titanium tetrachloride (TiCl 4 ) (3.28ml, 30mmol) was slowly added, pyridine (7.40ml, 9.2mmol) was added, and the temperature was slowly raised from 0°C to room temperature for 2 hours at room temperature. agitate. After extraction with dichloromethane/ammonium chloride aqueous solution (CH 2 Cl 2 /aq.NH 4 Cl), the organic layer was dried over anhydrous magnesium sulfate, the organic layers were collected, distilled under reduced pressure, and column chromatography was used to obtain the final compound (2.14 g, yield). 40%) was obtained. MS [M+H] + 357

2-2 중간체 2,2'-(3-chlorocyclohexa-3,5-diene-1,2-diylidene)dimalononitrile의 제조2-2 Preparation of intermediate 2,2'-(3-chlorocyclohexa-3,5-diene-1,2-diylidene)dimalononitrile

Figure 112021067501219-pat00072
Figure 112021067501219-pat00072

500ml 둥근 바닥 플라스크에 화합물isoindoline-1,3-dione(2.21g, 15.0mmol), 말로노나이트릴(malononitrile)(60.0mmol) 및 디 클로로메테인 용매를 넣고 아르곤 조건 하에서 30분간 교반 한다. 0℃로 냉각하여 10분간 교반 후 사염화티타늄 (TiCl4)(6.56ml, 60m mol)을 천천히 넣어준 후 피리딘(7.40ml, 9.2mmol)을 넣고 0℃에서 상온으로 천천히 온도를 올려 상온에서 2시간 교반시킨다. 이후 디클로로메탄/염화암모늄 수용액(CH2Cl2/aq.NH4Cl)으로 추출한 후에 유기물층을 무수황산마그네슘으로 건조시키고 유기층을 모아 감압하에서 증류하여 컬럼크로마토그래피를 이용하여 최종 화합물 (1.64g, 수율 45.0%)을 얻는다. MS [M+H]+ = 238Put the compound isoindoline-1,3-dione (2.21g, 15.0mmol), malononitrile (60.0mmol) and dichloromethane solvent in a 500ml round bottom flask, and stir for 30 minutes under argon conditions. After cooling to 0℃ and stirring for 10 minutes, titanium tetrachloride (TiCl 4 ) (6.56ml, 60mmol) was slowly added, pyridine (7.40ml, 9.2mmol) was added, and the temperature was slowly raised from 0℃ to room temperature for 2 hours at room temperature. agitate. After extraction with dichloromethane/ammonium chloride aqueous solution (CH 2 Cl 2 /aq.NH 4 Cl), the organic layer was dried over anhydrous magnesium sulfate, the organic layers were collected, distilled under reduced pressure, and the final compound (1.64 g, yield) by column chromatography 45.0%) is obtained. MS [M+H] + = 238

3-1 중간체(11-(dicyanomethylene)-11H-benzo[b]fluoren-2-yl)boronic acid의 제조Preparation of 3-1 intermediate (11-(dicyanomethylene)-11H-benzo[b]fluoren-2-yl)boronic acid

Figure 112021067501219-pat00073
Figure 112021067501219-pat00073

질소 보호 하에 3 구 플라스크에 THF (500mL)을 반응 용기에 넣고 2-(2-bromo-11H-benzo[b]fluoren-11-ylidene)malononitrile (30.61g, 85.7mmol), 질소 및 -78℃ 조건하에서 30분 동안 교반한다. butyl lithium （1.25 M/72mL）을 넣고, 1h 교반 후, Triisopropyl borate (17.03g, 90mmol)를 넣고, 낮은 온도에서 1h 교반하고, 점차 실온으로 회복한다. 2M 염산을 넣어 PH를 4-5로 조절한 다음 반응을 정지시킨다. 유기상을 취하고 무수황산마그네슘으로 건조시킨다. 건조된 혼합물을 여과하고 감압 농축한 후 실리카겔 크로마토 그래피 컬럼 또는 증류법으로 정제하여 최종 화합물 (16.56g, 수율 60%)을 얻었다. MS [M+H]+ 322THF (500mL) was placed in a reaction vessel in a three-neck flask under nitrogen protection, and 2-(2-bromo-11H-benzo[b]fluoren-11-ylidene)malononitrile (30.61g, 85.7mmol), nitrogen and -78℃ conditions under stirring for 30 minutes. butyl lithium (1.25 M/72mL) was added, and after stirring for 1 h, triisopropyl borate (17.03 g, 90 mmol) was added, stirred at low temperature for 1 h, and gradually returned to room temperature. Add 2M hydrochloric acid to adjust the PH to 4-5, and then stop the reaction. The organic phase is taken and dried over anhydrous magnesium sulfate. The dried mixture was filtered, concentrated under reduced pressure, and purified by silica gel chromatography column or distillation to obtain the final compound (16.56 g, yield 60%). MS [M+H] + 322

3-2 중간체 (5,6-bis(dicyanomethylene)cyclohexa-1,3-dien-1-yl)boronic acid의 제조Preparation of 3-2 intermediate (5,6-bis(dicyanomethylene)cyclohexa-1,3-dien-1-yl)boronic acid

Figure 112021067501219-pat00074
Figure 112021067501219-pat00074

질소 보호 하에 3 구 플라스크에 THF (500mL)을 반응 용기에 넣고 3-chlorocyclohexa-3,5-diene-1,2-dione (21.52g, 85.7mmol), 질소 및 -78℃ 조건하에서 30분 동안 교반한다. butyl lithium （1.25 M/72mL）을 넣고, 1h 교반 후, Triisopropyl borate (17.03g, 90mmol)를 넣고, 낮은 온도에서 1h 교반하고, 점차 실온으로 회복한다. 2M 염산을 넣어 PH를 4-5로 조절한 다음 반응을 정지시킨다. 유기상을 취하고 무수황산마그네슘으로 건조시킨다. 건조 된 혼합물을 여과하고 감압 농축 한 후 실리카겔 크로마토 그래피 컬럼 또는 증류법으로 정제하여 최종 화합물 (14.32g, 수율 : 70 %)를 얻었다. MS [M+H]+ = 248THF (500mL) was placed in a reaction vessel in a three-necked flask under nitrogen protection, and stirred for 30 minutes under the conditions of 3-chlorocyclohexa-3,5-diene-1,2-dione (21.52g, 85.7mmol), nitrogen and -78°C. do. butyl lithium (1.25 M/72mL) was added, and after stirring for 1 h, triisopropyl borate (17.03 g, 90 mmol) was added, stirred at low temperature for 1 h, and gradually returned to room temperature. Add 2M hydrochloric acid to adjust the PH to 4-5, and then stop the reaction. The organic phase is taken and dried over anhydrous magnesium sulfate. The dried mixture was filtered, concentrated under reduced pressure, and purified by silica gel chromatography column or distillation to obtain the final compound (14.32 g, yield: 70%). MS [M+H] + = 248

4-1 2,2'-(4'-(10-phenylanthracen-9-yl)-[1,1'-biphenyl]-2,3-diylidene)dimalononitri le의 제조4-1 Preparation of 2,2'-(4'-(10-phenylanthracen-9-yl)-[1,1'-biphenyl]-2,3-diylidene)dimalononitri le

Figure 112021067501219-pat00075
Figure 112021067501219-pat00075

질소조건하에서 (5,6-bis(dicyanomethylene)cyclohexa-1,3-dien-1-yl)boronic acid9.92g，40mmol), 9-(4-bromophenyl)-10-phenylanthracene（16.32g ，160mmol）, 테트라하이드로퓨란 400mL 및 물 200mL를 혼합하고 60℃로 가열하였다. 포타슘카보네이트 480mmol 및 테트라키스트라이페닐포스핀팔라듐(0.2mmol)을 첨가 하여 리플럭스 상태로 6시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 유기층을 추출한 후, 클로로 포름과 헥산으로 2회 재결정을 실시하여, 최종 화합물 (11.31g,54 %)을 얻었다. MS [M+H]+ = 532(5,6-bis(dicyanomethylene)cyclohexa-1,3-dien-1-yl)boronic acid9.92g, 40mmol), 9-(4-bromophenyl)-10-phenylanthracene (16.32g, 160mmol) under nitrogen condition, 400 mL of tetrahydrofuran and 200 mL of water were mixed and heated to 60°C. 480 mmol of potassium carbonate and tetrakistriphenylphosphine palladium (0.2 mmol) were added, and the mixture was stirred under reflux for 6 hours. After the reaction, the organic layer was extracted from the reaction solution returned to room temperature, and recrystallized twice with chloroform and hexane to obtain the final compound (11.31 g, 54 %). MS [M+H] + = 532

4-2 중간체 2,2'-(3-(bis(4-isopropylphenyl)amino)cyclohexa-3,5-diene-1,2-diylidene) dimalononitrile의 제조4-2 Preparation of intermediate 2,2'-(3-(bis(4-isopropylphenyl)amino)cyclohexa-3,5-diene-1,2-diylidene) dimalononitrile

Figure 112021067501219-pat00076
Figure 112021067501219-pat00076

질소조건하에서 중간체 2,2'-(3-chlorocyclohexa-3,5-diene-1,2-diylidene)dimalo nonitrile (3.39g, 10mmol), bis(4-isopropylphenyl)amine(2.53g, 10mmol), Sodium tert-butoxide (1.3g, 13.5mmol), Tris (dibenzylideneacetone) dipalladium (0.046g, 0.05mmol), tri-tert-butylphosphine (0.021g, 0.1mmol) 및 탈수 톨루엔 (50ml)을 80℃에서 2h 동안 반응시켰다. 냉각 후 물 (500ml)을 가하고 혼합물을 여과하고, 여액을 톨루엔으로 추출하고, 유기상을 무수 황산 마그네슘으로 건조시켰다. 감압 농축하고, 생성된 생성물을 컬럼 정제한 후, 톨루엔으로 재결정 및 여과 건조하여 최종 화합물（3.50g, 75%)을 얻었다. MS [M+H]+ = 455Intermediate 2,2'-(3-chlorocyclohexa-3,5-diene-1,2-diylidene)dimalo nonitrile (3.39g, 10mmol), bis(4-isopropylphenyl)amine (2.53g, 10mmol), Sodium under nitrogen condition tert-butoxide (1.3g, 13.5mmol), Tris (dibenzylideneacetone) dipalladium (0.046g, 0.05mmol), tri-tert-butylphosphine (0.021g, 0.1mmol) and dehydrated toluene (50ml) were reacted at 80°C for 2h . After cooling, water (500 ml) was added, the mixture was filtered, the filtrate was extracted with toluene, and the organic phase was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting product was purified by column, recrystallized with toluene and filtered and dried to obtain the final compound (3.50 g, 75%). MS [M+H] + = 455

<화합물의 제조><Preparation of compound>

* 화합물 a-1 내지 a-40의 제조* Preparation of compounds a-1 to a-40

상기 1-1과 1-2 및 당량 조절방법을 이용하여 하기 [표 1]의 화합물을 얻었다:The compounds of [Table 1] below were obtained by using the 1-1 and 1-2 and the equivalent control method:

Figure 112021067501219-pat00077
Figure 112021067501219-pat00077

Figure 112021067501219-pat00078
Figure 112021067501219-pat00078

Figure 112021067501219-pat00079
Figure 112021067501219-pat00079

Figure 112021067501219-pat00080
Figure 112021067501219-pat00080

Figure 112021067501219-pat00081
Figure 112021067501219-pat00081

Figure 112021067501219-pat00082
Figure 112021067501219-pat00082

Figure 112021067501219-pat00083
Figure 112021067501219-pat00083

* 화합물 a-1-1 내지 a-1-5의 제조* Preparation of compounds a-1-1 to a-1-5

상기 4-1 및 당량 조절방법을 이용하여 하기 [표 2]의 화합물을 얻었다:The compounds of Table 2 below were obtained by using 4-1 and the method for equivalence control:

Figure 112021067501219-pat00084
Figure 112021067501219-pat00084

* 화합물 b-1 내지 b-35의 제조* Preparation of compounds b-1 to b-35

상기 3-1과 3-2 및 당량 조절방법을 이용하여 하기 [표 3]의 화합물을 얻었다:The compounds of Table 3 below were obtained by using the above 3-1 and 3-2 and the equivalence control method:

Figure 112021067501219-pat00085
Figure 112021067501219-pat00085

Figure 112021067501219-pat00086
Figure 112021067501219-pat00086

Figure 112021067501219-pat00087
Figure 112021067501219-pat00087

Figure 112021067501219-pat00088
Figure 112021067501219-pat00088

Figure 112021067501219-pat00089
Figure 112021067501219-pat00089

Figure 112021067501219-pat00090
Figure 112021067501219-pat00090

* 실시예 A-1 내지 A-114의 제조* Preparation of Examples A-1 to A-114

상기 표 1 내지 3의 화합물 및 당량 조절방법을 이용하여 하기 [표 4]의 화합물을 얻었다:The compounds of Table 4 below were obtained by using the compounds of Tables 1 to 3 and the method for controlling the equivalent weight:

Figure 112021067501219-pat00091
Figure 112021067501219-pat00091

Figure 112021067501219-pat00092
Figure 112021067501219-pat00092

Figure 112021067501219-pat00093
Figure 112021067501219-pat00093

Figure 112021067501219-pat00094
Figure 112021067501219-pat00094

Figure 112021067501219-pat00095
Figure 112021067501219-pat00095

Figure 112021067501219-pat00096
Figure 112021067501219-pat00096

Figure 112021067501219-pat00097
Figure 112021067501219-pat00097

Figure 112021067501219-pat00098
Figure 112021067501219-pat00098

Figure 112021067501219-pat00099
Figure 112021067501219-pat00099

Figure 112021067501219-pat00100
Figure 112021067501219-pat00100

Figure 112021067501219-pat00101
Figure 112021067501219-pat00101

Figure 112021067501219-pat00102
Figure 112021067501219-pat00102

Figure 112021067501219-pat00103
Figure 112021067501219-pat00103

Figure 112021067501219-pat00104
Figure 112021067501219-pat00104

Figure 112021067501219-pat00105
Figure 112021067501219-pat00105

Figure 112021067501219-pat00106
Figure 112021067501219-pat00106

Figure 112021067501219-pat00107
Figure 112021067501219-pat00107

Figure 112021067501219-pat00108
1
Figure 112021067501219-pat00109
Figure 112021067501219-pat00108
One
Figure 112021067501219-pat00109

* 실시예 B-1 내지 B-125의 제조* Preparation of Examples B-1 to B-125

상기 표 1 내지 3의 화합물 및 당량 조절방법을 이용하여 하기 [표 5]의 화합물을 얻었다:The compounds of Table 5 below were obtained by using the compounds of Tables 1 to 3 and the method for controlling the equivalent weight:

Figure 112021067501219-pat00110
Figure 112021067501219-pat00110

Figure 112021067501219-pat00111
Figure 112021067501219-pat00111

Figure 112021067501219-pat00112
Figure 112021067501219-pat00112

Figure 112021067501219-pat00113
Figure 112021067501219-pat00113

Figure 112021067501219-pat00114
Figure 112021067501219-pat00114

Figure 112021067501219-pat00115
Figure 112021067501219-pat00115

Figure 112021067501219-pat00116
Figure 112021067501219-pat00116

Figure 112021067501219-pat00117
Figure 112021067501219-pat00117

Figure 112021067501219-pat00118
Figure 112021067501219-pat00118

Figure 112021067501219-pat00119
Figure 112021067501219-pat00119

Figure 112021067501219-pat00120
Figure 112021067501219-pat00120

Figure 112021067501219-pat00121
Figure 112021067501219-pat00121

Figure 112021067501219-pat00122
Figure 112021067501219-pat00122

Figure 112021067501219-pat00123
Figure 112021067501219-pat00123

Figure 112021067501219-pat00124
Figure 112021067501219-pat00124

Figure 112021067501219-pat00125
Figure 112021067501219-pat00125

Figure 112021067501219-pat00126
Figure 112021067501219-pat00126

Figure 112021067501219-pat00127
Figure 112021067501219-pat00127

Figure 112021067501219-pat00128
Figure 112021067501219-pat00128

Figure 112021067501219-pat00129
Figure 112021067501219-pat00129

Figure 112021067501219-pat00130
Figure 112021067501219-pat00130

Figure 112021067501219-pat00131
Figure 112021067501219-pat00131

<실험예><Experimental example>

ITO가 1500Å의 두께로 박막 코팅된 유리 기판을 피셔사의 세제를 녹인 2차 증류수에 넣고 초음파로 30분간 세척하였다. ITO를 30 분간 세척한 후 증류수로 2 회 반복하여 초음파 세척을 10 분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척하고 건조시킨 후, 플라즈마 세정기로 이송시켜, 산소 플라즈마를 이용하여 상기 기판을 5 분간 세정한 후 진공 증착기로 기판을 이송시켰다.A glass substrate coated with a thin film of ITO to a thickness of 1500 Å was placed in distilled water in which Fisher's detergent was dissolved and washed with ultrasonic waves for 30 minutes. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic cleaning with a solvent of isopropyl alcohol, acetone, and methanol was used, dried, transferred to a plasma cleaner, and the substrate was cleaned using oxygen plasma for 5 minutes, followed by transferring the substrate to a vacuum evaporator.

이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine)를 500Å 진공증착 후, 정공전달층으로 a-NPD (N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-ciphenyl)-4,4'-diamine) 300Å 진공 증착한 후, 청색 물질의 경우 청색 호스트로 AND (9,10-Di(2-naphthyl)anthracene)에 도판트 DPAP-DPPA (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyren-1-amine) 5%를 도핑하였으며, 적색의 경우 RH-01 (9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-cicarcazole)에 RD-01 (5,6,11,12-tetraphenyltetracene) 5%를 도핑하여 300Å의 두께로 진공 증착하였다. 그리고 정공저지층 및 정공전달층으로 TPBi 2,2',2''-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) 물질을 400Å의 두께로 진공 증착 하였으며, 순차적으로 LiF 5Å과 Al(알루미늄) 2000Å 증착하여 음극을 형성하였다. After vacuum deposition of 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) as a hole injection layer on the prepared ITO transparent electrode in 500Å, a-NPD (N, After vacuum deposition of N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-ciphenyl)-4,4'-diamine) 300 Å, in the case of blue material, AND (9, 10-Di(2-naphthyl)anthracene) was doped with 5% of the dopant DPAP-DPPA (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyren-1-amine), and in the case of red, RH-01 Doping RD-01 (5,6,11,12-tetraphenyltetracene) 5% to (9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-cicarcazole) and vacuum deposition to a thickness of 300 Å, and TPBi 2,2',2''-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) as a hole blocking layer and a hole transport layer The material was vacuum-deposited to a thickness of 400 Å, and LiF 5 Å and Al (aluminum) 2000 Å were sequentially deposited to form a cathode.

상기 내용에서 실시예를 이용한 비교실험은 하기와 같다.Comparative experiments using Examples in the above contents are as follows.

1) AND과 DPAP-DPPA 청색 발광에서 HIL (2-TNATA) 비교 실험은 표 61) HIL (2-TNATA) comparison experiments in AND and DPAP-DPPA blue light emission are shown in Table 6

2) AND과 DPAP-DPPA 청색 발광에서 ETL (TPBi) 비교실험은 표 72) ETL (TPBi) comparison experiments in AND and DPAP-DPPA blue light emission are shown in Table 7

3) RH01과 RD01적색 발광에서 도판트 (RD-01) 비교 실험은 표 83) Comparative experiment of dopant (RD-01) in RH01 and RD01 red emission is shown in Table 8

상기 발명으로 기재된 실시예의 일부 물질의 성능을 비교하였다.The performance of some materials of the examples described above with the invention was compared.

상기의 과정에서 유기물의 증착속도는 1 Å/sec를 유지하였고, LiF는 0.2 Å/sec, 알루미늄은 3~7Å/sec의 증착속도를 유지하였다.In the above process, the deposition rate of the organic material was maintained at 1 Å/sec, the deposition rate of 0.2 Å/sec for LiF and 3-7 Å/sec for aluminum was maintained.

Figure 112021067501219-pat00132
Figure 112021067501219-pat00132

상기에서 제조된 유기 발광 소자에 대한 전기적 발광특성을 하기에 나타내었다.The electroluminescence characteristics of the organic light emitting device prepared above are shown below.

청색 발광에서 AND 호스트와 DPAP-DPPA 상태에서 2-TNATA와 실시예의 정공주입층 (HIL) 성능 비교하여 아래 표 6에 나타내었다.Table 6 below compares the hole injection layer (HIL) performance of 2-TNATA and Examples in the AND host and DPAP-DPPA states in blue light emission.

Figure 112021067501219-pat00133
Figure 112021067501219-pat00133

청색 발광에서 AND 호스트와 DPAP-DPPA 상태에서 TPBi와 실시예의 전자전달층 (ETL) 성능 비교하여 아래 표 7에 나타내었다.Table 7 below shows the comparison of the electron transport layer (ETL) performance of TPBi and Examples in the AND host and DPAP-DPPA states in blue light emission.

Figure 112021067501219-pat00134
Figure 112021067501219-pat00134

적색 발광의 RH-01/RD-01 상태에서 RD-01와 실시예의 성능 비교하여 아래 표 8에 나타내었다.The performance of RD-01 and Example in the RH-01/RD-01 state of red emission was compared and shown in Table 8 below.

Figure 112021067501219-pat00135
Figure 112021067501219-pat00135

Figure 112021067501219-pat00136
Figure 112021067501219-pat00136

상기 표 6 내지 표 8의 결과로부터, 본 발명에 따른 말로노나이트릴(malononitrile) 화합물은 정공주입의 HIL과 전자전달의 ETL 및 적색 발광의 Dopant에서 성능 향상 결과를 얻었으며, 청색 발광의 HIL과 ETL 응용성 및 소자의 수명 특성이 향상됨을 확인할 수 있었다.From the results of Tables 6 to 8, the malononitrile compound according to the present invention obtained performance improvement results in HIL of hole injection, ETL of electron transport, and Dopant of red emission, and HIL of blue emission and It was confirmed that ETL applicability and device lifetime characteristics were improved.

본 발명의 말로노나이트릴(malononitrile) 화합물을 이용한 유기발광소자는 발광 효율과 수명이 우수한 향상을 얻을 수 있었다. 이 때문에, 실용성이 높은 OLED로서 산업적으로 유용하다. The organic light emitting device using the malononitrile compound of the present invention was able to obtain excellent improvements in luminous efficiency and lifespan. For this reason, it is industrially useful as OLED with high practicality.

본 발명의 유기발광소자는 평면 패널 디스플레이, 평면 발광체, 조명용 면발광 OLED의 발광체, flexible 발광체, 복사기, 프린터, LCD 백라이트 또는 계량기류 등의 광원, 디스플레이판, 표식등 등에 적합하게 이용할 수 있다.The organic light emitting device of the present invention can be suitably used for a light source such as a flat panel display, a flat light emitting body, a surface light emitting OLED for lighting, a flexible light emitting body, a copier, a printer, a light source such as an LCD backlight or meter, a display plate, a marker, and the like.

Claims (6)

하기 화학식 1-1로 표시되는 말로노나이트릴(malononitrile) 화합물:
[화학식 1-1]
Figure 112022030684795-pat00137

상기 R1 내지 R4은 각각 서로 독립적으로 수소;
치환 또는 비치환된 탄소수 1 내지 40개의 알킬기;
치환 또는 비치환된 탄소수 2 내지 40개의 알킬알콕시기;
치환 또는 비치환된 탄소수 6 내지 40개의 아릴기;
치환 또는 비치환된 탄소수 7 내지 40개의 아릴알킬기;
치환 또는 비치환된 탄소수 6 내지 40개의 아릴아민기;
치환 또는 비치환된 탄소수 6 내지 30개의 시아노아릴기;
치환 또는 비치환된 탄소수 6 내지 30개의 플루오로아릴기;
치환 또는 비치환된 탄소수 11 내지 40개의 헤테로아릴기;
치환 또는 비치환된 탄소수 6 내지 40개의 아미노아릴기;
치환 또는 비치환된 탄소수 5 내지 40개의 아미노헤테로아릴기;
중에서 선택된다.A malononitrile compound represented by the following formula 1-1:
[Formula 1-1]
Figure 112022030684795-pat00137

Wherein R 1 To R 4 They are each independently hydrogen;
a substituted or unsubstituted C 1 to C 40 alkyl group;
a substituted or unsubstituted C2-C40 alkylalkoxy group;
a substituted or unsubstituted C 6 to C 40 aryl group;
a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms;
a substituted or unsubstituted C 6 to C 40 arylamine group;
a substituted or unsubstituted cyanoaryl group having 6 to 30 carbon atoms;
a substituted or unsubstituted C6-C30 fluoroaryl group;
a substituted or unsubstituted C11 to C40 heteroaryl group;
a substituted or unsubstituted C6-C40 aminoaryl group;
a substituted or unsubstituted aminoheteroaryl group having 5 to 40 carbon atoms;
is selected from 제1항에 있어서,
상기 화학식 1-1의 구체적 구조는 하기 화학식 2-1-1 내지 2-1-2 중 어느 하나로 표시되는 것을 특징으로 하는 말로노나이트릴(malononitrile) 화합물:
[화학식 2-1-1]
Figure 112022030684795-pat00147

[화학식 2-1-2]
Figure 112022030684795-pat00148

상기 화학식 2-1-1 내지 화학식 2-1-2에서
상기 R1 내지 R2은 각각 서로 독립적으로 수소;
치환 또는 비치환된 탄소수 1 내지 40개의 아릴기;
치환 또는 비치환된 탄소수 1 내지 40개의 아릴알킬기;
치환 또는 비치환된 탄소수 1 내지 40개의 아릴아민기;
치환 또는 비치환된 탄소수 1 내지 30개의 시아노아릴기;
치환 또는 비치환된 탄소수 1 내지 30개의 플루오로아릴기;
치환 또는 비치환된 탄소수 1 내지 40개의 헤테로아릴기;
치환 또는 비치환된 탄소수 1 내지 40개의 헤테로아민아릴기;
치환 또는 비치환된 탄소수 1 내지 40개의 아미노아릴기;
치환 또는 비치환된 탄소수 1 내지 40개의 아미노헤테로아릴기;
중에서 선택된다.The method of claim 1,
The specific structure of Formula 1-1 is a malononitrile compound, characterized in that it is represented by any one of the following Formulas 2-1-1 to 2-1-2:
[Formula 2-1-1]
Figure 112022030684795-pat00147

[Formula 2-1-2]
Figure 112022030684795-pat00148

In Formulas 2-1-1 to 2-1-2,
Wherein R 1 To R 2 They are each independently hydrogen;
a substituted or unsubstituted C 1 to C 40 aryl group;
a substituted or unsubstituted C 1 to C 40 arylalkyl group;
a substituted or unsubstituted C 1 to C 40 arylamine group;
a substituted or unsubstituted C 1 to C 30 cyanoaryl group;
a substituted or unsubstituted C 1 to C 30 fluoroaryl group;
a substituted or unsubstituted C 1 to C 40 heteroaryl group;
a substituted or unsubstituted C 1 to C 40 heteroamine aryl group;
a substituted or unsubstituted C 1 to C 40 aminoaryl group;
a substituted or unsubstituted aminoheteroaryl group having 1 to 40 carbon atoms;
is selected from 제1항 또는 제2항에 있어서,
상기 화합물은 아래 화합물들 중 어느 하나인 것을 특징으로 하는 화합물:
Figure 112022030684795-pat00178

Figure 112022030684795-pat00179

Figure 112022030684795-pat00187

Figure 112022030684795-pat00186

Figure 112022030684795-pat00188
3. The method of claim 1 or 2,
A compound characterized in that the compound is any one of the following compounds:
Figure 112022030684795-pat00178

Figure 112022030684795-pat00179

Figure 112022030684795-pat00187

Figure 112022030684795-pat00186

Figure 112022030684795-pat00188
 제 1전극, 제 2전극 및 이들 전극 사이에 배치된 1층 이상의 유기물 층을 포함하는 유기전자소자로서,
상기 유기물층 중 적어도 1층 이상이 제 1 항의 말로노나이트릴(malononitrile) 화합물을 포함하는 유기전자소자. An organic electronic device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the electrodes, the organic electronic device comprising:
At least one layer of the organic layer contains the malononitrile compound of claim 1 Organic electronic device including. 제 4 항에 있어서,
상기 유기물층은 정공 주입층, 정공 수송층, 정공 주입 기능 및 정공 수송 기능을 동시에 갖는 기능층, 전자 저지층, 발광층, 정공 저지층, 전자 수송층, 전자 주입층, 및 전자 수송 기능 및 전자 주입 기능을 동시에 갖는 기능층 중 적어도 하나를 포함하는 유기전자소자.5. The method of claim 4,
The organic material layer is a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function at the same time An organic electronic device comprising at least one of the functional layers having. 제 5 항에 있어서,
상기 유기전자소자가 유기발광소자 (OLED), 유기태양전지 (OSC), 전자종이 (e-Paper), 유기감광체(OPC) 또는 유기트랜지스터 (OTFT)인 유기전자소자.6. The method of claim 5,
The organic electronic device is an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoreceptor (OPC) or an organic transistor (OTFT).
KR1020210075918A 2021-06-11 2021-06-11 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device KR102401913B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020210075918A KR102401913B1 (en) 2021-06-11 2021-06-11 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035270A KR20220167743A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035274A KR102573956B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035271A KR20220167744A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035272A KR20220167745A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035273A KR102624591B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020210075918A KR102401913B1 (en) 2021-06-11 2021-06-11 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Related Child Applications (5)

Application Number Title Priority Date Filing Date
KR1020220035271A Division KR20220167744A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035272A Division KR20220167745A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035273A Division KR102624591B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035274A Division KR102573956B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035270A Division KR20220167743A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Publications (1)

Publication Number Publication Date
KR102401913B1 true KR102401913B1 (en) 2022-05-25

Family

ID=81797321

Family Applications (6)

Application Number Title Priority Date Filing Date
KR1020210075918A KR102401913B1 (en) 2021-06-11 2021-06-11 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035270A KR20220167743A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035273A KR102624591B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035274A KR102573956B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035271A KR20220167744A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035272A KR20220167745A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Family Applications After (5)

Application Number Title Priority Date Filing Date
KR1020220035270A KR20220167743A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035273A KR102624591B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035274A KR102573956B1 (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035271A KR20220167744A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR1020220035272A KR20220167745A (en) 2021-06-11 2022-03-22 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Country Status (1)

Country Link
KR (6) KR102401913B1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100101795A (en) * 2009-03-10 2010-09-20 한국전자통신연구원 Ambipolar thiophene compounds and field effect transistor having the same
KR20200066250A (en) * 2018-11-30 2020-06-09 주식회사 엘지화학 Optical laminate
KR20200119046A (en) * 2019-04-09 2020-10-19 주식회사 엘지화학 Heterocyclic compound and organic electronic device comprising the same
CN112876382A (en) * 2019-11-29 2021-06-01 广州华睿光电材料有限公司 Organic compounds, mixtures, compositions and uses thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10161394A (en) * 1996-11-26 1998-06-19 Fuji Xerox Co Ltd Electrostatic charge imparting member for electrostatic charge image development, electrostatic charge image development and image forming method
JP3652088B2 (en) * 1997-11-21 2005-05-25 三井化学株式会社 Novel organic fluorescent materials and their uses
DE10039232A1 (en) * 2000-08-11 2002-02-21 Basf Ag Liquid crystalline perylene-3,4: 9,10-tetracarboxylic acid diimides
JP2006086497A (en) * 2004-08-19 2006-03-30 Fuji Xerox Co Ltd Organic electroluminescent element
CN112745333B (en) * 2019-10-30 2022-12-20 北京夏禾科技有限公司 Organic Electroluminescent Materials and Devices
KR102283490B1 (en) * 2021-01-07 2021-08-03 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR102323603B1 (en) * 2021-03-16 2021-11-10 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100101795A (en) * 2009-03-10 2010-09-20 한국전자통신연구원 Ambipolar thiophene compounds and field effect transistor having the same
KR20200066250A (en) * 2018-11-30 2020-06-09 주식회사 엘지화학 Optical laminate
KR20200119046A (en) * 2019-04-09 2020-10-19 주식회사 엘지화학 Heterocyclic compound and organic electronic device comprising the same
CN112876382A (en) * 2019-11-29 2021-06-01 广州华睿光电材料有限公司 Organic compounds, mixtures, compositions and uses thereof

Also Published As

Publication number Publication date
KR20220167198A (en) 2022-12-20
KR20220167744A (en) 2022-12-21
KR102573956B1 (en) 2023-09-01
KR20220167743A (en) 2022-12-21
KR20220167745A (en) 2022-12-21
KR102624591B1 (en) 2024-01-16
KR20220167746A (en) 2022-12-21

Similar Documents

Publication Publication Date Title
TWI388647B (en) Novel compound and organic light-emitting device using same
CN101426760B (en) Novel anthracene derivatives, method for preparation thereof, and organic electronic device using the same
WO2011025282A2 (en) Novel organic compound and organic light-emitting device using same
KR20130121597A (en) Using triphenylamine as hole transporting mateial and organic electroluminescent device using the same
CN115210893A (en) Organic light emitting element with high efficiency and long lifetime
KR101334204B1 (en) A New Pyrene Compounds, Method of Producing the Same and Organic Electroluminescent Device Comprising the Same
CN111116628A (en) Organic compound and organic electroluminescent device using same
KR20130121516A (en) Using new alylamine as hole transporting mateial and organic electroluminescent device using the same
KR102323603B1 (en) Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR102283490B1 (en) Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR101375542B1 (en) Hole transport material containing thiophene derivative and organic light emitting device using same
KR20130051321A (en) Novel tetiary aryl amine and organic electroluminescent device using the same
KR102201028B1 (en) Compound for organic light emitting diode, organic light emitting diode having the same, and display apparatus having organic light emitting diode
KR100887870B1 (en) Novel anthracene derivatives, preparation method thereof and organic electronic device using same
KR101327301B1 (en) Amine derivative as hole transporting material and organic electroluminescent device using the same
KR20120128386A (en) Organic compounds for organic electro luminescente device and organic electro luminescent device using same
WO2021103728A1 (en) Organic compound and organic electroluminescent device using same
WO2024078287A1 (en) Organic compound, organic electroluminescent device, and electronic apparatus
KR102118688B1 (en) Compound for organic light emitting diode, organic light emitting diode having the same, and display apparatus having organic light emitting diode
KR102401913B1 (en) Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR102175379B1 (en) Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
KR100509122B1 (en) Luminescent spiro compound and organic light-emitting device comprising the same
KR102118875B1 (en) Compound for organic light emitting diode, organic light emitting diode having the same, and display apparatus having organic light emitting diode
KR100754474B1 (en) Anthracene-based organic light emitting compound and organic light emitting diode comprising same
KR102209237B1 (en) Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Legal Events

Date Code Title Description
PA0109 Patent application

Patent event code: PA01091R01D

Comment text: Patent Application

Patent event date: 20210611

PA0201 Request for examination
PA0302 Request for accelerated examination

Patent event date: 20210611

Patent event code: PA03022R01D

Comment text: Request for Accelerated Examination

PE0902 Notice of grounds for rejection

Comment text: Notification of reason for refusal

Patent event date: 20211126

Patent event code: PE09021S01D

PA0107 Divisional application

Comment text: Divisional Application of Patent

Patent event date: 20220322

Patent event code: PA01071R01D

E701 Decision to grant or registration of patent right
PE0701 Decision of registration

Patent event code: PE07011S01D

Comment text: Decision to Grant Registration

Patent event date: 20220428

GRNT Written decision to grant
PR0701 Registration of establishment

Comment text: Registration of Establishment

Patent event date: 20220520

Patent event code: PR07011E01D

PR1002 Payment of registration fee

Payment date: 20220520

End annual number: 3

Start annual number: 1

PG1601 Publication of registration