WO2014017844A1 - Organic light-emitting compound comprising acridine derivatives, and organic light-emitting device comprising same - Google Patents

Organic light-emitting compound comprising acridine derivatives, and organic light-emitting device comprising same Download PDF

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WO2014017844A1
WO2014017844A1 PCT/KR2013/006669 KR2013006669W WO2014017844A1 WO 2014017844 A1 WO2014017844 A1 WO 2014017844A1 KR 2013006669 W KR2013006669 W KR 2013006669W WO 2014017844 A1 WO2014017844 A1 WO 2014017844A1
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compound
light emitting
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organic light
formula
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Korean (ko)
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함호완
안현철
김동준
한정우
김근태
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주식회사 동진쎄미켐
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Priority claimed from KR1020130087572A external-priority patent/KR102169273B1/en
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Priority to CN201380038477.2A priority Critical patent/CN104471022B/en
Publication of WO2014017844A1 publication Critical patent/WO2014017844A1/en

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Definitions

  • the present invention relates to an organic light emitting compound comprising an acridine derivative and an organic light emitting device comprising the same.
  • an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices.
  • LCD liquid crystal display
  • the organic light emitting device has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode), and an organic material layer between the two electrodes.
  • the organic material layer may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (EIL) in addition to the light emitting layer (EML).
  • HIL hole injection layer
  • HTL hole transport layer
  • ETL electron transport layer
  • EIL electron injection layer
  • an electron injection layer and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to the light emission characteristics of the light emitting layer.
  • EBL electron blocking layer
  • HBL hole blocking layer
  • the light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to realize better natural colors according to light emission colors.
  • the light emitting layer (dopant) may be doped into the light emitting layer (host). The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to give high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
  • an object of the present invention is to provide a novel organic light emitting compound with improved color purity, luminous efficiency, luminance, power efficiency, heat resistance and the like.
  • Another object of the present invention is to provide an organic light emitting device including the compound, which exhibits low driving voltage, high luminous efficiency and luminous luminance, and is capable of long life.
  • the present invention provides an organic light emitting compound comprising an acridine derivative represented by the following formula (1):
  • X is substituted or unsubstituted C, O, P, S, Se or Si, and when X is O, the nitrogen atom of the acridine cannot be bonded at position 3 of the heteroaryl moiety;
  • R 1 to R 17 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-36 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Or a C 2-36 heteroaryl
  • X and R 1 to R 17 are the same as defined in Chemical Formula 1.
  • the present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer as a light emitting material.
  • the organic light emitting compound of the present invention is excellent in brightness, power efficiency, heat resistance, charge transport performance and charge injection performance by controlling the charge balance in the organic layer through the appropriate combination of the acridine derivative and the cyclic compound, the color purity and luminous efficiency Since it can be increased, it can be applied to one or more of the functional layer material of the organic light emitting device and the host or dopant of the light emitting layer. Therefore, the organic light emitting device including the compound of the present invention exhibits low driving voltage, high luminous luminance and luminous efficiency, and thus can maximize performance and improve lifespan in a full color organic panel.
  • FIG. 1 schematically shows a cross section of an OLED according to an embodiment of the invention
  • FIG. 2 shows a band diagram of an organic light emitting diode having a light emission principle due to an organic light emitting phenomenon.
  • the compound of the present invention represented by Formula 1 is characterized in that an acridine moiety and an aryl or heteroaryl moiety are directly connected to the nitrogen atom of the acridine:
  • X is substituted or unsubstituted C, O, P, S, Se or Si, and when X is O, the nitrogen atom of the acridine cannot be bonded at position 3 of the heteroaryl moiety;
  • R 1 to R 17 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-36 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Or a C 2-36 heteroaryl
  • R 1 to R 10 are each substituted with deuterium, they may be deuterated at least 20%, preferably at least 40%, and more preferably at least 50% of R 1 to R 10 .
  • aryl or heteroaryl moiety directly connected to the nitrogen atom of the acridine-based moiety in the compound is substituted with deuterium, it is preferably at least 50% deuterated.
  • substituents of X and R 1 to R 17 are each independently deuterium, halogen, nitrile group, nitro group, C 1-30 alkyl group, C 1-30 alkoxy group, C 3-30 cycloalkyl group, C 3-30 heterocycloalkyl group, C 6-30 aryl group, C 5-30 heteroaryl group, C 1-30 alkyloxy group, C 6-30 aryloxy group and C 6-30 arylamine It is preferably substituted with one or more substituents selected from the group consisting of groups, but is not limited thereto, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring.
  • the compound of formula 1 according to the present invention has an acridine-based moiety and an aryl- or heteroaryl-based moiety directly linked to the nitrogen atom of acridine so that the compound of the acridine derivative and the cyclic compound in the organic layer Adjust the charge balance.
  • the luminance, power efficiency, heat resistance, charge transport performance, and charge injection performance can be improved to increase color purity and luminous efficiency. Therefore, the present invention can be applied to one or more of the functional layer material of the organic light emitting device and the host or dopant of the light emitting layer. have.
  • the compound of the present invention when applied to an organic light emitting device, it is possible to improve characteristics such as driving voltage and luminous efficiency of the light emitting device.
  • the present invention provides a method for preparing Formula 1 comprising the step of reacting the following Formula 1-1 and Formula 1-2:
  • X and R 1 to R 17 are the same as defined in Chemical Formula 1.
  • the compound of Formula 1 according to the present invention may be prepared according to the method according to Scheme 1 below.
  • X is as defined in Formula 1, and each R corresponds to R 1 and R 2 of Formula 1-1, respectively.
  • the present invention provides an organic light emitting device comprising a compound represented by the formula (1) in the organic material layer as a light emitting material.
  • the compound of the present invention may be used alone or in combination with a known organic light emitting compound.
  • the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and the method of manufacturing the organic light emitting device is as follows.
  • the organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) between an anode and a cathode. It may contain one or more.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML emission layer
  • ETL electron transport layer
  • EIL electron injection layer
  • an anode is formed by depositing a material for an anode electrode having a high work function on the substrate.
  • the substrate may be a substrate used in a conventional organic light emitting device, it is particularly preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof.
  • the anode electrode material transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like may be used.
  • the anode electrode material may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.
  • the hole injection layer material may be formed on the anode electrode by a method such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), or the like. It is preferable to form by the vacuum evaporation method in that it is hard to generate
  • a method such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), or the like. It is preferable to form by the vacuum evaporation method in that it is hard to generate
  • the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It is preferable to select appropriately from a vacuum degree of 10 -8 to 10 -3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 mu m.
  • the hole injection layer material is not particularly limited, and TCTA (4,4 ′, 4 ′′ -tri (N-carbazolyl) tree, which is a phthalocyanine compound or starburst type amine derivative such as copper phthalocyanine disclosed in US Pat. No. 4,356,429.
  • the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, etc., but it is easy to obtain a uniform film quality and is difficult to generate pin holes. It is preferable to form by a vapor deposition method.
  • the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.
  • the hole transport layer material is not particularly limited, and may be arbitrarily selected and used from conventionally known materials used in the hole transport layer.
  • the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine ( ⁇ -NPD) Derivatives and the like can be used.
  • carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4
  • the light emitting layer material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but the vacuum deposition method is easy to obtain a uniform film quality and hard to generate pin holes. It is preferable to form by.
  • the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer.
  • the light emitting layer material may use the compound represented by Formula 1 of the present invention as a host or dopant.
  • a light emitting layer may be formed by using a phosphorescent or fluorescent dopant together.
  • the fluorescent dopant may be IDE102 or IDE105, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethyrylcrisne- which can be purchased from Idemitsu Co., Ltd.).
  • 6,12-diamine can be used as green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped).
  • the doping concentration of the dopant is not particularly limited, but the dopant is preferably doped at 0.01 to 15 parts by weight based on 100 parts by weight of the host.
  • the content of the dopant is less than 0.01 parts by weight, there is a problem in that the color development is not performed properly because the amount of the dopant is not sufficient, and if it exceeds 15 parts by weight, the efficiency is drastically reduced due to the concentration quenching phenomenon.
  • the hole suppression material HBL
  • HBL hole suppression material
  • the hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used.
  • an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited.
  • Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound e.g., BCP (vasocuproin) from UDC
  • BCP vasocuproin
  • An electron transport layer is formed on the light emitting layer formed as above, wherein the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is preferably formed by a vacuum deposition method.
  • the electron transport material as a function to transport a steady stream of electrons injected from the electron injecting electrode that kind is not particularly limited, for example, quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq 3 ), Or ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl) di-2,2'-bipyridine).
  • an electron injection layer (EIL) which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li 2 O, BaO, or the like. The substance of can be used.
  • the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.
  • an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is preferable to form by.
  • a cathode forming metal is formed on the electron injection layer by a method such as vacuum deposition or sputtering and used as a cathode.
  • the cathode forming metal may be a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. There is this.
  • a transmissive cathode using ITO or IZO may be used to obtain the front light emitting device.
  • the organic light emitting device of the present invention is not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device of the cathode structure, but also the structure of an organic light emitting device of various structures, 1 It is also possible to form a layer or two intermediate layers.
  • each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.
  • the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.
  • the organic light emitting compound of the present invention is excellent in brightness, power efficiency, heat resistance, charge transport performance and charge injection performance to increase the color purity and luminous efficiency, it is used as a light emitting material of the organic light emitting device is low driving voltage to the organic light emitting device And high luminous luminance and luminous efficiency, which can provide maximum performance and longer life in full color organic panels.
  • Compound 5 was obtained by the same method as the synthesis method of Compound 1, except that bromodibenzo [b, d] furan (247.09) and 4-bromodibenzo [b, d] furan were reacted with 1-bromodibenzo [b, d] furan. Got it.
  • Compound 10 was obtained by the same method as the synthesis method of compound 9, except that diphenylamine was reacted with 9H-carbazole.
  • Compound 13 was obtained by the same method as the synthesis method of compound 12, except that diphenylamine was reacted with 9H-carbazole.
  • An organic light emitting diode was manufactured in the same structure as in FIG. 1. Specifically, the glass substrate coated with a 1500 ⁇ m thick indium tin oxide (ITO) was washed with distilled water ultrasonic waves. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and the substrate is cleaned for 5 minutes using an oxygen plasma. Using an evaporator, 2-TNATA 600 ⁇ was formed as a hole injection layer and NPB 200 ⁇ was formed as a hole transport layer.
  • ITO indium tin oxide
  • the host material of Examples 1 to 20 synthesized in the above Example was doped with Ir (ppy) 3 7% to form 300 ⁇ .
  • TPBi 300 ⁇ was formed into an electron transport layer, followed by LiF 10 ⁇ and aluminum (Al) 1000 ⁇ , which were encapsulated in a glove box to produce an organic light emitting device.
  • a glass substrate coated with an indium tin oxide (ITO) 1500 ⁇ thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and the substrate is cleaned for 5 minutes using an oxygen plasma.
  • 2-TNATA 600 ⁇ was used as the hole injection layer, and 200 ⁇ of the compound synthesized in Examples 1 to 20 was formed into a hole transport layer using an evaporator.
  • mCP was doped with Ir (ppy) 3 7% to form 300 ⁇ .
  • TPBi 300 ⁇ was formed into an electron transport layer, followed by LiF 10 ⁇ and aluminum (Al) 1000 ⁇ .
  • the organic light emitting device was manufactured by encapsulating the device in a glove box.
  • An organic light emitting diode was manufactured according to the same method as the hole transport layer and the light emitting layer host, except for using NPB and mCP.
  • Example 21 ITO / 2-TNATA / NPB / Compound 1: Ir (ppy) 3 (7%) / TPBi / LiF / Al 38.5 17.7 18
  • Example 22 ITO / 2-TNATA / NPB / Compound 2: Ir (ppy) 3 (7%) / TPBi / LiF / Al 39.2 17.9 18.3
  • Example 23 ITO / 2-TNATA / NPB / Compound 3: Ir (ppy) 3 (7%) / TPBi / LiF / Al 40 19 19.2
  • Example 24 ITO / 2-TNATA / NPB / Compound 4: Ir (ppy) 3 (7%) / TPBi / LiF / Al 41 19.3 20
  • Example 25 ITO / 2-TNATA / NPB / Compound 5: Ir (ppy) 3 (7%) / TPBi / LiF / Al 38.2 17.8 16.9
  • Example 26 ITO / 2-TNATA / NPB / Compound 1: Ir (
  • the organic light emitting compound of the present invention is excellent in brightness, power efficiency, heat resistance, charge transport performance and charge injection performance by controlling the charge balance in the organic layer through the appropriate combination of the acridine derivative and the cyclic compound, the color purity and luminous efficiency Since it can be increased, it can be applied to one or more of the functional layer material of the organic light emitting device and the host or dopant of the light emitting layer. Therefore, the organic light emitting device including the compound of the present invention exhibits low driving voltage, high luminous luminance and luminous efficiency, and thus can maximize performance and improve lifespan in a full color organic panel.

Abstract

The organic light-emitting compound comprising acridine derivatives according to the present invention adjusts the charge balance in an organic material layer by means of comprising an appropriate balance between the acridine derivatives and a cyclic compound, thereby achieving excellent luminance, power efficiency, heat resistance, charge transport performance, and charge injection performance to thus increase color purity and luminous efficiency. Therefore, the organic light-emitting compound of the present invention can be used as a light-emitting material for an organic light-emitting device in order to exhibit low driving voltage and high luminance and luminous efficiency for an organic light-emitting device, thus enabling the maximized performance and improved lifespan of a full-color organic panel.

Description

아크리딘 유도체를 포함하는 유기발광 화합물 및 이를 포함하는 유기발광소자An organic light emitting compound comprising an acridine derivative and an organic light emitting device comprising the same
본 발명은 아크리딘 유도체를 포함하는 유기발광 화합물 및 이를 포함하는 유기발광소자에 관한 것이다.The present invention relates to an organic light emitting compound comprising an acridine derivative and an organic light emitting device comprising the same.
최근, 자체 발광형으로 저전압 구동이 가능한 유기발광소자는, 평판 표시소자의 주류인 액정디스플레이(LCD, liquid crystal display)에 비해, 시야각, 대조비 등이 우수하고 백라이트가 불필요하여 경량 및 박형이 가능하며 소비전력 측면에서도 유리하고 색 재현 범위가 넓어, 차세대 표시소자로서 주목을 받고 있다.Recently, an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices. In terms of power consumption and wide color reproduction range, it is attracting attention as a next-generation display device.
일반적으로, 유기발광소자는 음극(전자주입전극)과 양극(정공주입전극), 및 상기 두 전극 사이에 유기물층을 포함하는 구조를 갖는다. 이때, 유기물층은 발광층(EML, light emitting layer) 이외에, 정공주입층(HIL, hole injection layer), 정공수송층(HTL, hole transport layer), 전자수송층(ETL, electron transport layer) 또는 전자주입층(EIL, electron injection layer)을 포함할 수 있으며, 발광층의 발광특성상 전자차단층(EBL, electron blocking layer) 또는 정공차단층(HBL, hole blocking layer)을 추가로 포함할 수 있다.In general, the organic light emitting device has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode), and an organic material layer between the two electrodes. In this case, the organic material layer may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (EIL) in addition to the light emitting layer (EML). , an electron injection layer, and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to the light emission characteristics of the light emitting layer.
이러한 구조의 유기발광소자에 전기장이 가해지면, 양극으로부터 정공이 주입되고, 음극으로부터 전자가 주입되어, 정공과 전자는 각각 정공수송층과 전자수송층을 거쳐 발광층에서 재조합(recombination)하게 되어 발광여기자(엑시톤, exitons)를 형성한다. 형성된 발광여기자는 바닥상태(ground states)로 전이하면서 빛을 방출한다.When an electric field is applied to the organic light emitting device having such a structure, holes are injected from the anode, electrons are injected from the cathode, and holes and electrons are recombined in the light emitting layer through the hole transport layer and the electron transport layer, respectively, thereby emitting light excitons (excitons). , exitons). The formed light exciton emits light as it transitions to ground states.
발광물질은 발광색에 따라 청색, 녹색, 적색 발광물질과 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광물질로 구분될 수 있다. 또한, 발광상태의 효율과 안정성을 증가시키기 위하여, 발광 색소(도펀트)를 발광층(호스트)에 도핑하기도 한다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도펀트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도펀트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도펀트의 파장대로 이동하므로, 이용하는 도펀트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.The light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to realize better natural colors according to light emission colors. Further, in order to increase the efficiency and stability of the light emitting state, the light emitting layer (dopant) may be doped into the light emitting layer (host). The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to give high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
현재까지 유기발광소자의 발광층에 사용되는 발광물질로서 다양한 화합물들이 알려져 있으나, 이제까지 알려진 발광물질을 이용한 유기발광소자의 경우 높은 구동전압, 낮은 효율 및 짧은 수명으로 인해 실용화하는 데에 많은 어려움이 있었다. 따라서 우수한 발광특성을 갖는 물질을 이용하여 저전압 구동, 고휘도 및 장수명을 갖는 유기발광소자를 개발하려는 노력이 지속되어 왔다.To date, various compounds are known as light emitting materials used in the light emitting layer of the organic light emitting device, but the organic light emitting device using the known light emitting materials has had many difficulties in practical use due to high driving voltage, low efficiency and short lifespan. Therefore, efforts have been made to develop organic light emitting diodes having low voltage driving, high brightness and long life using materials having excellent light emitting characteristics.
상기와 같은 문제점을 해결하기 위해, 본 발명은 색순도, 발광효율, 휘도, 전력효율, 내열성 등이 향상된 신규한 유기발광 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a novel organic light emitting compound with improved color purity, luminous efficiency, luminance, power efficiency, heat resistance and the like.
본 발명은 또한 상기 화합물을 포함하여 낮은 구동전압과 높은 발광효율 및 발광휘도를 나타내며 장수명 구현이 가능한 유기발광소자를 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an organic light emitting device including the compound, which exhibits low driving voltage, high luminous efficiency and luminous luminance, and is capable of long life.
상기 목적을 달성하기 위해 본 발명은 하기 화학식 1로 표시되는 아크리딘 유도체를 포함하는 유기발광 화합물을 제공한다:In order to achieve the above object, the present invention provides an organic light emitting compound comprising an acridine derivative represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2013006669-appb-I000001
Figure PCTKR2013006669-appb-I000001
상기 식에서,Where
X는 치환 또는 비치환된 C, O, P, S, Se 또는 Si이고, X가 O일 경우 아크리딘의 질소 원자는 헤테로아릴계 모이어티의 3번 위치에는 결합될 수 없고;X is substituted or unsubstituted C, O, P, S, Se or Si, and when X is O, the nitrogen atom of the acridine cannot be bonded at position 3 of the heteroaryl moiety;
R1 내지 R17은 각각 독립적으로, 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-36의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-36의 헤테로아릴기이고, 선택적으로, 상기 R1 내지 R17 중 인접한 기가 서로 결합하여 포화 또는 불포화 탄소 고리를 형성할 수 있다.R 1 to R 17 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-36 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Or a C 2-36 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group, and optionally, adjacent groups of R 1 to R 17 may combine with each other to form a saturated or unsaturated carbon ring. Can be.
또한 하기 화학식 1-1과 화학식 1-2를 반응시키는 단계를 포함하는 특징으로 하는 화학식 1의 제조방법을 제공한다:Also provided is a method for preparing Formula 1, comprising the step of reacting Formula 1-1 with Formula 1-2:
[화학식 1-1][Formula 1-1]
Figure PCTKR2013006669-appb-I000002
Figure PCTKR2013006669-appb-I000002
[화학식 1-2][Formula 1-2]
Figure PCTKR2013006669-appb-I000003
Figure PCTKR2013006669-appb-I000003
상기에서 X 및 R1 내지 R17은 화학식 1에서 정의한 바와 같다.X and R 1 to R 17 are the same as defined in Chemical Formula 1.
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 발광물질로서 유기물층에 포함하는 유기발광소자를 제공한다.The present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer as a light emitting material.
본 발명의 유기발광 화합물은 아크리딘 유도체와 고리화합물의 적절한 조화를 통해 유기물층 내에서의 전하균형을 조절함으로써, 휘도, 전력효율, 내열성, 전하수송 성능 및 전하주입 성능이 우수하여 색순도 및 발광효율을 증가시킬 수 있으므로, 유기발광소자의 기능층 재료 및 발광층의 호스트나 도판트 중 하나 이상에 적용할 수 있다. 따라서, 본 발명의 화합물을 포함하는 유기발광소자는 낮은 구동전압과 높은 발광휘도 및 발광효율을 나타내며, 이에 따라 풀 칼라 유기 패널에서 성능 극대화 및 수명 향상을 제공할 수 있다.The organic light emitting compound of the present invention is excellent in brightness, power efficiency, heat resistance, charge transport performance and charge injection performance by controlling the charge balance in the organic layer through the appropriate combination of the acridine derivative and the cyclic compound, the color purity and luminous efficiency Since it can be increased, it can be applied to one or more of the functional layer material of the organic light emitting device and the host or dopant of the light emitting layer. Therefore, the organic light emitting device including the compound of the present invention exhibits low driving voltage, high luminous luminance and luminous efficiency, and thus can maximize performance and improve lifespan in a full color organic panel.
도 1은 본 발명의 일 실시예에 따른 OLED의 단면을 개략적으로 도시한 것이며, 1 schematically shows a cross section of an OLED according to an embodiment of the invention,
도 2는 유기발광현상에 의한 발광원리를 갖는 유기전계발광 다이오드의 밴드 다이어그램을 나타낸 것이다.2 shows a band diagram of an organic light emitting diode having a light emission principle due to an organic light emitting phenomenon.
* 도면의 주요부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
10 : 기판10: substrate
11 : 양극11: anode
12 : 정공주입층12: hole injection layer
13 : 정공전달층13: hole transport layer
14 : 발광층14: light emitting layer
15 : 전자전달층15: electron transport layer
16: 음극16: cathode
하기 화학식 1로 표시되는 본 발명의 화합물은 아크리딘계 모이어티(moiety)와 아릴계 또는 헤테로아릴계 모이어티가 아크리딘의 질소 원자에 직접 연결되는 것을 특징으로 한다:The compound of the present invention represented by Formula 1 is characterized in that an acridine moiety and an aryl or heteroaryl moiety are directly connected to the nitrogen atom of the acridine:
[화학식 1][Formula 1]
Figure PCTKR2013006669-appb-I000004
Figure PCTKR2013006669-appb-I000004
상기 식에서,Where
X는 치환 또는 비치환된 C, O, P, S, Se 또는 Si이고, X가 O일 경우 아크리딘의 질소 원자는 헤테로아릴계 모이어티의 3번 위치에는 결합될 수 없고;X is substituted or unsubstituted C, O, P, S, Se or Si, and when X is O, the nitrogen atom of the acridine cannot be bonded at position 3 of the heteroaryl moiety;
R1 내지 R17은 각각 독립적으로, 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-36의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-36의 헤테로아릴기이고, 선택적으로, 상기 R1 내지 R17 중 인접한 기가 서로 결합하여 포화 또는 불포화 탄소 고리를 형성할 수 있다. R 1 to R 17 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-36 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Or a C 2-36 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group, and optionally, adjacent groups of R 1 to R 17 may combine with each other to form a saturated or unsaturated carbon ring. Can be.
상기 R1 내지 R10는 각각 중수소로 치환되는 경우에는, R1 내지 R10 중 적어도 20%, 바람직하게는 적어도 40%, 더욱 바람직하게는 적어도 50%로 중수소화 될 수 있다.When R 1 to R 10 are each substituted with deuterium, they may be deuterated at least 20%, preferably at least 40%, and more preferably at least 50% of R 1 to R 10 .
또한, 상기 화합물에서 아크리딘계 모이어티(moiety)의 질소 원자에 직접 연결된 아릴계 또는 헤테로아릴계 모이어티가 중수소로 치환되는 경우에는, 적어도 50% 중수소화 되는 것이 바람직하다.In addition, when the aryl or heteroaryl moiety directly connected to the nitrogen atom of the acridine-based moiety in the compound is substituted with deuterium, it is preferably at least 50% deuterated.
또한, 상기 X 및 R1 내지 R17의 치환기는 각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, C1-30의 알킬기, C1-30의 알콕시기, C3-30의 시클로알킬기, C3-30의 헤테로시클로알킬기, C6-30의 아릴기, C5-30의 헤테로아릴기, C1-30의 알킬옥시기, C6-30의 아릴옥시기 및 C6-30의 아릴아민기로 이루어진 군에서 선택되는 하나 이상의 치환기로 치환되는 것이 바람직하나, 이에 한정되지는 않으며, 인접한 기가 서로 결합하여 포화 또는 불포화 탄소 고리를 형성할 수 있다.In addition, the substituents of X and R 1 to R 17 are each independently deuterium, halogen, nitrile group, nitro group, C 1-30 alkyl group, C 1-30 alkoxy group, C 3-30 cycloalkyl group, C 3-30 heterocycloalkyl group, C 6-30 aryl group, C 5-30 heteroaryl group, C 1-30 alkyloxy group, C 6-30 aryloxy group and C 6-30 arylamine It is preferably substituted with one or more substituents selected from the group consisting of groups, but is not limited thereto, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring.
본 발명에 있어서, 상기 화학식 1로 표시되는 화합물의 바람직한 예는 다음과 같다:In the present invention, preferred examples of the compound represented by Formula 1 are as follows:
Figure PCTKR2013006669-appb-I000005
Figure PCTKR2013006669-appb-I000005
Figure PCTKR2013006669-appb-I000006
Figure PCTKR2013006669-appb-I000006
Figure PCTKR2013006669-appb-I000007
Figure PCTKR2013006669-appb-I000007
Figure PCTKR2013006669-appb-I000008
Figure PCTKR2013006669-appb-I000008
Figure PCTKR2013006669-appb-I000009
Figure PCTKR2013006669-appb-I000009
Figure PCTKR2013006669-appb-I000010
Figure PCTKR2013006669-appb-I000010
Figure PCTKR2013006669-appb-I000011
Figure PCTKR2013006669-appb-I000011
Figure PCTKR2013006669-appb-I000012
Figure PCTKR2013006669-appb-I000012
Figure PCTKR2013006669-appb-I000013
Figure PCTKR2013006669-appb-I000013
Figure PCTKR2013006669-appb-I000014
Figure PCTKR2013006669-appb-I000014
Figure PCTKR2013006669-appb-I000015
Figure PCTKR2013006669-appb-I000015
Figure PCTKR2013006669-appb-I000016
Figure PCTKR2013006669-appb-I000016
Figure PCTKR2013006669-appb-I000017
Figure PCTKR2013006669-appb-I000017
Figure PCTKR2013006669-appb-I000018
Figure PCTKR2013006669-appb-I000018
Figure PCTKR2013006669-appb-I000019
Figure PCTKR2013006669-appb-I000019
Figure PCTKR2013006669-appb-I000020
Figure PCTKR2013006669-appb-I000020
Figure PCTKR2013006669-appb-I000021
Figure PCTKR2013006669-appb-I000021
Figure PCTKR2013006669-appb-I000022
Figure PCTKR2013006669-appb-I000022
Figure PCTKR2013006669-appb-I000023
Figure PCTKR2013006669-appb-I000023
Figure PCTKR2013006669-appb-I000024
Figure PCTKR2013006669-appb-I000024
Figure PCTKR2013006669-appb-I000025
Figure PCTKR2013006669-appb-I000025
Figure PCTKR2013006669-appb-I000026
Figure PCTKR2013006669-appb-I000026
Figure PCTKR2013006669-appb-I000027
Figure PCTKR2013006669-appb-I000028
Figure PCTKR2013006669-appb-I000027
Figure PCTKR2013006669-appb-I000028
Figure PCTKR2013006669-appb-I000029
Figure PCTKR2013006669-appb-I000029
Figure PCTKR2013006669-appb-I000030
Figure PCTKR2013006669-appb-I000030
Figure PCTKR2013006669-appb-I000031
Figure PCTKR2013006669-appb-I000032
Figure PCTKR2013006669-appb-I000031
Figure PCTKR2013006669-appb-I000032
Figure PCTKR2013006669-appb-I000033
Figure PCTKR2013006669-appb-I000034
Figure PCTKR2013006669-appb-I000033
Figure PCTKR2013006669-appb-I000034
Figure PCTKR2013006669-appb-I000035
Figure PCTKR2013006669-appb-I000035
Figure PCTKR2013006669-appb-I000036
Figure PCTKR2013006669-appb-I000036
Figure PCTKR2013006669-appb-I000037
Figure PCTKR2013006669-appb-I000037
Figure PCTKR2013006669-appb-I000038
Figure PCTKR2013006669-appb-I000038
Figure PCTKR2013006669-appb-I000039
Figure PCTKR2013006669-appb-I000039
Figure PCTKR2013006669-appb-I000040
Figure PCTKR2013006669-appb-I000040
Figure PCTKR2013006669-appb-I000041
Figure PCTKR2013006669-appb-I000041
Figure PCTKR2013006669-appb-I000042
Figure PCTKR2013006669-appb-I000042
Figure PCTKR2013006669-appb-I000043
Figure PCTKR2013006669-appb-I000043
Figure PCTKR2013006669-appb-I000044
Figure PCTKR2013006669-appb-I000044
Figure PCTKR2013006669-appb-I000045
Figure PCTKR2013006669-appb-I000045
Figure PCTKR2013006669-appb-I000046
Figure PCTKR2013006669-appb-I000046
Figure PCTKR2013006669-appb-I000047
Figure PCTKR2013006669-appb-I000047
Figure PCTKR2013006669-appb-I000048
Figure PCTKR2013006669-appb-I000048
Figure PCTKR2013006669-appb-I000049
Figure PCTKR2013006669-appb-I000049
Figure PCTKR2013006669-appb-I000050
Figure PCTKR2013006669-appb-I000050
Figure PCTKR2013006669-appb-I000051
Figure PCTKR2013006669-appb-I000051
Figure PCTKR2013006669-appb-I000052
Figure PCTKR2013006669-appb-I000052
Figure PCTKR2013006669-appb-I000053
Figure PCTKR2013006669-appb-I000053
Figure PCTKR2013006669-appb-I000054
Figure PCTKR2013006669-appb-I000054
Figure PCTKR2013006669-appb-I000055
Figure PCTKR2013006669-appb-I000055
Figure PCTKR2013006669-appb-I000056
Figure PCTKR2013006669-appb-I000056
본 발명에 따른 화학식 1의 화합물은 아크리딘계 모이어티와 아릴계 또는 헤테로아릴계 모이어티가 아크리딘의 질소 원자에 직접 연결되어 아크리딘 유도체와 고리화합물의 적절한 조화를 통해 유기물층 내에서의 전하균형을 조절한다. 이로 인해 휘도, 전력효율, 내열성, 전하수송 성능 및 전하주입 성능이 우수하여 색순도 및 발광효율을 증가시킬 수 있으므로, 유기발광소자의 기능층 재료 및 발광층의 호스트나 도판트 중 하나 이상에 적용할 수 있다. The compound of formula 1 according to the present invention has an acridine-based moiety and an aryl- or heteroaryl-based moiety directly linked to the nitrogen atom of acridine so that the compound of the acridine derivative and the cyclic compound in the organic layer Adjust the charge balance. As a result, the luminance, power efficiency, heat resistance, charge transport performance, and charge injection performance can be improved to increase color purity and luminous efficiency. Therefore, the present invention can be applied to one or more of the functional layer material of the organic light emitting device and the host or dopant of the light emitting layer. have.
따라서, 본 발명의 화합물을 유기발광소자에 적용하면, 발광소자의 구동전압 및 발광 효율 등의 특성을 향상 시킬 수 있다.Therefore, when the compound of the present invention is applied to an organic light emitting device, it is possible to improve characteristics such as driving voltage and luminous efficiency of the light emitting device.
또한 본 발명은 하기 화학식 1-1과 화학식 1-2를 반응시키는 단계를 포함하는 특징으로 하는 화학식 1의 제조방법을 제공한다:In another aspect, the present invention provides a method for preparing Formula 1 comprising the step of reacting the following Formula 1-1 and Formula 1-2:
[화학식 1-1][Formula 1-1]
Figure PCTKR2013006669-appb-I000057
Figure PCTKR2013006669-appb-I000057
[화학식 1-2][Formula 1-2]
Figure PCTKR2013006669-appb-I000058
Figure PCTKR2013006669-appb-I000058
상기에서 X 및 R1 내지 R17은 화학식 1에서 정의한 바와 같다.X and R 1 to R 17 are the same as defined in Chemical Formula 1.
구체적인 일예로 본 발명에 따른 화학식 1의 화합물은 하기 반응식 1에 따른 방법에 따라 제조될 수 있다.As a specific example, the compound of Formula 1 according to the present invention may be prepared according to the method according to Scheme 1 below.
[반응식 1]Scheme 1
Figure PCTKR2013006669-appb-I000059
Figure PCTKR2013006669-appb-I000059
상기 반응식 1에서 X는 화학식 1에서 정의한 바와 같으며, 각각의 R은 각각 화학식 1-1의 R1 및 R2에 대응된다.In Scheme 1, X is as defined in Formula 1, and each R corresponds to R 1 and R 2 of Formula 1-1, respectively.
또한, 본 발명은 발광물질로서 상기 화학식 1로 표시되는 화합물을 유기물층에 포함하는 유기발광소자를 제공한다. 이때, 본 발명의 화합물은 단독으로 사용되거나 공지의 유기발광 화합물과 함께 사용될 수 있다.In addition, the present invention provides an organic light emitting device comprising a compound represented by the formula (1) in the organic material layer as a light emitting material. In this case, the compound of the present invention may be used alone or in combination with a known organic light emitting compound.
또한 본 발명의 유기발광소자는 상기 화학식 1로 표시되는 화합물을 포함하는 1층 이상의 유기물층을 포함하는 바, 상기 유기발광소자의 제조방법을 설명하면 다음과 같다.In addition, the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and the method of manufacturing the organic light emitting device is as follows.
상기 유기발광소자는 애노드(anode)와 캐소드(cathod) 사이에 정공주입층(HIL), 정공수송층(HTL), 발광층(EML), 전자수송층(ETL), 전자주입층(EIL) 등의 유기물층을 1 개 이상 포함할 수 있다.The organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) between an anode and a cathode. It may contain one or more.
먼저, 기판 상부에 높은 일함수를 갖는 애노드 전극용 물질을 증착시켜 애노드를 형성한다. 이때, 상기 기판은 통상의 유기발광소자에서 사용되는 기판을 사용할 수 있으며, 특히 기계적 강도, 열적 안정성, 투명성, 표면평활성, 취급용이성, 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판을 사용하는 것이 좋다. 또한, 애노드 전극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등을 사용할 수 있다. 상기 애노드 전극용 물질은 통상의 애노드 형성방법에 의해 증착할 수 있으며, 구체적으로 증착법 또는 스퍼터링법에 의해 증착할 수 있다.First, an anode is formed by depositing a material for an anode electrode having a high work function on the substrate. In this case, the substrate may be a substrate used in a conventional organic light emitting device, it is particularly preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof. In addition, as the anode electrode material, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like may be used. The anode electrode material may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.
그 다음, 상기 애노드 전극 상부에 정공주입층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB(Langmuir-Blodgett)법 등과 같은 방법에 의해 형성할 수 있지만, 균일한 막질을 얻기 쉽고, 또한 핀정공이 발생하기 어렵다는 등의 점에서 진공증착법에 의해 형성하는 것이 바람직하다. 상기 진공증착법에 의해 정공주입층을 형성하는 경우 그 증착조건은 정공주입층의 재료로서 사용하는 화합물, 목적하는 정공주입층의 구조 및 열적특성 등에 따라 다르지만, 일반적으로 50-500 ℃의 증착온도, 10-8 내지 10-3 torr의 진공도, 0.01 내지 100 Å/sec의 증착속도, 10 Å 내지 5 ㎛의 층 두께 범위에서 적절히 선택하는 것이 바람직하다.Subsequently, the hole injection layer material may be formed on the anode electrode by a method such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), or the like. It is preferable to form by the vacuum evaporation method in that it is hard to generate | occur | produce. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It is preferable to select appropriately from a vacuum degree of 10 -8 to 10 -3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 mu m.
상기 정공주입층 물질은 특별히 제한되지 않으며, 미국특허 제4,356,429호에 개시된 구리 프탈로시아닌 등의 프탈로시아닌 화합물 또는 스타버스트형 아민 유도체류인 TCTA(4,4',4"-트리(N-카바졸릴)트리페닐아민), m-MTDATA(4,4',4"-트리스(3-메틸페닐아미노)트리페닐아민), m-MTDAPB(4,4',4"-트리스(3-메틸페닐아미노)페녹시벤젠), HI-406(N1,N1'-(비페닐-4,4'-디일)비스(N1-(나프탈렌-1-일)-N4,N4-디페닐벤젠-1,4-디아민) 등을 정공주입층 물질로 사용할 수 있다.The hole injection layer material is not particularly limited, and TCTA (4,4 ′, 4 ″ -tri (N-carbazolyl) tree, which is a phthalocyanine compound or starburst type amine derivative such as copper phthalocyanine disclosed in US Pat. No. 4,356,429. Phenylamine), m-MTDATA (4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine), m-MTDAPB (4,4', 4" -tris (3-methylphenylamino) phenoxybenzene ), HI-406 (N 1 , N 1 '- ( biphenyl-4,4'-diyl) bis (N 1 - (naphthalen-1-yl) -N 4, N 4 - benzene-1,4-diphenyl -Diamine) and the like can be used as the hole injection layer material.
다음으로 상기 정공주입층 상부에 정공수송층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있지만, 균일한 막질을 얻기 쉽고, 핀정공이 발생하기 어렵다는 점에서 진공증착법에 의해 형성하는 것이 바람직하다. 상기 진공증착법에 의해 정공수송층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다.Next, the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, etc., but it is easy to obtain a uniform film quality and is difficult to generate pin holes. It is preferable to form by a vapor deposition method. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.
또한, 상기 정공수송층 물질은 특별히 제한되지는 않으며, 정공수송층에 사용되고 있는 통상의 공지 물질 중에서 임의로 선택하여 사용할 수 있다. 구체적으로, 상기 정공수송층 물질은 N-페닐카바졸, 폴리비닐카바졸 등의 카바졸 유도체, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), N.N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상의 아민 유도체 등이 사용될 수 있다.In addition, the hole transport layer material is not particularly limited, and may be arbitrarily selected and used from conventionally known materials used in the hole transport layer. Specifically, the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) Derivatives and the like can be used.
그 후, 상기 정공수송층 상부에 발광층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있지만, 균일한 막질을 얻기 쉽고, 핀정공이 발생하기 어렵다는 점에서 진공증착법에 의해 형성하는 것이 바람직하다. 상기 진공증착법에 의해 발광층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다. 또한, 상기 발광층 재료는 본 발명의 화학식 1로 표시되는 화합물을 호스트 또는 도펀트로 사용할 수 있다.Thereafter, the light emitting layer material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but the vacuum deposition method is easy to obtain a uniform film quality and hard to generate pin holes. It is preferable to form by. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer. In addition, the light emitting layer material may use the compound represented by Formula 1 of the present invention as a host or dopant.
상기 화학식 1로 표시되는 화합물을 발광 호스트로 사용하는 경우, 인광 또는 형광 도펀트를 함께 사용하여 발광층을 형성할 수 있다. 이때, 형광 도펀트로는 이데미츠사(Idemitsu사)에서 구입 가능한 IDE102 또는 IDE105, 또는 BD142(N6,N12-비스(3,4-디메틸페닐)-N6,N12-디메시틸크리센-6,12-디아민)를 사용할 수 있으며, 인광 도펀트로는 녹색 인광 도펀트 Ir(ppy)3(트리스(2-페닐피리딘) 이리듐), 청색 인광 도펀트인 F2Irpic(이리듐(Ⅲ) 비스[4,6-다이플루오로페닐)-피리디나토-N,C2'] 피콜린산염), UDC사의 적색 인광 도펀트 RD61 등이 공동 진공증착(도핑)될 수 있다. 도펀트의 도핑농도는 특별히 제한되지 않으나, 호스트 100 중량부 대비 도펀트가 0.01 내지 15 중량부로 도핑되는 것이 바람직하다. 만약 도펀트의 함량이 0.01 중량부 미만일 경우에는 도펀트량이 충분치 못하여 발색이 제대로 이루어지지 않는다는 문제점이 있으며, 15 중량부를 초과할 경우에는 농도 소광 현상으로 인해 효율이 급격히 감소된다는 문제점이 있다.When the compound represented by Chemical Formula 1 is used as a light emitting host, a light emitting layer may be formed by using a phosphorescent or fluorescent dopant together. In this case, the fluorescent dopant may be IDE102 or IDE105, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethyrylcrisne- which can be purchased from Idemitsu Co., Ltd.). 6,12-diamine) can be used as green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped). The doping concentration of the dopant is not particularly limited, but the dopant is preferably doped at 0.01 to 15 parts by weight based on 100 parts by weight of the host. If the content of the dopant is less than 0.01 parts by weight, there is a problem in that the color development is not performed properly because the amount of the dopant is not sufficient, and if it exceeds 15 parts by weight, the efficiency is drastically reduced due to the concentration quenching phenomenon.
또한, 발광층에 인광 도펀트와 함께 사용할 경우에는 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지하기 위하여 정공억제재료(HBL)를 추가로 진공증착법 또는 스핀코팅법에 의해 적층시키는 것이 바람직하다. 이때 사용할 수 있는 정공억제물질은 특별히 제한되지는 않으나, 정공억제재료로 사용되고 있는 공지의 것에서 임의의 것을 선택해서 이용할 수 있다. 예를 들면, 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, 또는 일본특개평 11-329734(A1)에 기재되어 있는 정공억제재료 등을 들 수 있으며, 대표적으로 Balq(비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄 비페녹사이드), 페난트롤린(phenanthrolines)계 화합물(예: UDC사 BCP(바쏘쿠프로인)) 등을 사용할 수 있다.In addition, when using the phosphorescent dopant in the light emitting layer, it is preferable to further laminate the hole suppression material (HBL) by vacuum deposition or spin coating to prevent the triplet excitons or holes from diffusing into the electron transport layer. The hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited. Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound (e.g., BCP (vasocuproin) from UDC) can be used.
상기와 같이 형성된 발광층 상부에는 전자수송층이 형성되는데, 이때 상기 전자수송층은 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 바람직하다.An electron transport layer is formed on the light emitting layer formed as above, wherein the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is preferably formed by a vacuum deposition method.
상기 전자수송층 재료는 전자주입전극으로부터 주입된 전자를 안정하게 수송하는 기능을 하는 것으로서 그 종류가 특별히 제한되지는 않으며, 예를 들어 퀴놀린 유도체, 특히 트리스(8-퀴놀리놀라토)알루미늄(Alq3), 또는 ET4(6,6'-(3,4-디메시틸-1,1-디메틸-1H-실올-2,5-디일)디-2,2'-비피리딘)을 사용할 수 있다. 또한, 전자수송층 상부에 캐소드로부터 전자의 주입을 용이하게 하는 기능을 가지는 물질인 전자주입층(EIL)이 적층될 수 있으며, 전자주입층 물질로는 LiF, NaCl, CsF, Li2O, BaO 등의 물질을 이용할 수 있다.The electron transport material as a function to transport a steady stream of electrons injected from the electron injecting electrode that kind is not particularly limited, for example, quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq 3 ), Or ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl) di-2,2'-bipyridine). In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li 2 O, BaO, or the like. The substance of can be used.
또한, 상기 전자수송층의 증착조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다.In addition, although the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.
그 뒤, 상기 전자수송층 상부에 전자주입층 물질을 형성할 수 있으며, 이때 상기 전자수송층은 통상의 전자주입층 물질을 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 바람직하다.Subsequently, an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is preferable to form by.
마지막으로 전자주입층 상부에 캐소드 형성용 금속을 진공증착법이나 스퍼터링법 등의 방법에 의해 형성하고 캐소드로 사용한다. 여기서 캐소드 형성용 금속으로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물, 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 있다. 또한, 전면 발광소자를 얻기 위하여 ITO, IZO를 사용한 투과형 캐소드를 사용할 수도 있다.Finally, a cathode forming metal is formed on the electron injection layer by a method such as vacuum deposition or sputtering and used as a cathode. The cathode forming metal may be a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. There is this. In addition, a transmissive cathode using ITO or IZO may be used to obtain the front light emitting device.
본 발명의 유기발광소자는 애노드, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 캐소드 구조의 유기발광소자 뿐만 아니라, 다양한 구조의 유기발광소자의 구조가 가능하며, 필요에 따라 1층 또는 2층의 중간층을 더 형성하는 것도 가능하다.The organic light emitting device of the present invention is not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device of the cathode structure, but also the structure of an organic light emitting device of various structures, 1 It is also possible to form a layer or two intermediate layers.
상기와 같이 본 발명에 따라 형성되는 각 유기물층의 두께는 요구되는 정도에 따라 조절할 수 있으며, 바람직하게는 10 내지 1,000 ㎚이며, 더욱 바람직하게는 20 내지 150 ㎚인 것이 좋다.As described above, the thickness of each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.
또한 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 유기물층의 두께를 분자 단위로 조절할 수 있기 때문에 표면이 균일하며, 형태안정성이 뛰어난 장점이 있다.In addition, the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.
본 발명의 유기발광 화합물은 휘도, 전력효율, 내열성, 전하수송 성능 및 전하주입 성능이 우수하여 색순도 및 발광효율을 증가시킬 수 있으므로, 유기발광소자의 발광물질로 사용되어 유기발광소자에 낮은 구동전압과 높은 발광휘도 및 발광효율을 나타내며, 이에 따라 풀 칼라 유기 패널에서 성능 극대화 및 수명 향상을 제공할 수 있다.The organic light emitting compound of the present invention is excellent in brightness, power efficiency, heat resistance, charge transport performance and charge injection performance to increase the color purity and luminous efficiency, it is used as a light emitting material of the organic light emitting device is low driving voltage to the organic light emitting device And high luminous luminance and luminous efficiency, which can provide maximum performance and longer life in full color organic panels.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예 1: 화합물 1의 합성]Example 1: Synthesis of Compound 1
Figure PCTKR2013006669-appb-I000060
Figure PCTKR2013006669-appb-I000060
9,9-dimethyl-9,10-dihydroacridine 5 g, 4-bromodibenzo[b,d]furan 7.1 g, t-BuONa 3.5 g, Pd2(dba)3 0.9 g, (t-Bu)3P 1.2 ml를 톨루엔 100 ml에 녹인 후 환류 교반하였다. 반응이 종결되면 증류수와 EA로 추출한 후 컬럼정제하여 화합물 1을 얻었다. (수율 61%)9,9-dimethyl-9,10-dihydroacridine 5 g, 4-bromodibenzo [b, d] furan 7.1 g, t-BuONa 3.5 g, Pd 2 (dba) 3 0.9 g, (t-Bu) 3 P 1.2 ml It was dissolved in 100 ml of toluene and stirred under reflux. When the reaction was terminated, extracted with distilled water and EA and purified by column to obtain Compound 1. (Yield 61%)
m/z: 375.16 (100.0%), 376.17 (29.5%), 377.17 (4.4%)m / z: 375.16 (100.0%), 376.17 (29.5%), 377.17 (4.4%)
[실시예 2: 화합물 2의 합성]Example 2: Synthesis of Compound 2
Figure PCTKR2013006669-appb-I000061
Figure PCTKR2013006669-appb-I000061
2-bromo-N-phenylaniline 10 g을 THF 100 ml에 녹인 후 반응 온도를 -78 ℃로 낮추고 BuLi 2.5 M을 20 ml 천천히 적가하고 1시간 동안 교반하였다. Benzophenone 11 g을 THF 100 ml에 녹인 후 천천히 적가한 후 실온으로 온도를 높이고 12시간 교반하였다. 반응이 종결된 후 증류수와 MC로 추출하고 무수황산마그네슘으로 물을 제거한 후 감압여과하여 얻은 고체를 더 이상의 정제 없이 Acetic acid 100 ml에 녹인 후 황산 7 ml를 적가하고 환류교반하였다. 반응이 종결된 후 증류수와 MC로 추출하고 생성된 고체를 컬럼 정제하여 I2 7.1 g을 얻었다. (수율 53%)After dissolving 10 g of 2-bromo-N-phenylaniline in 100 ml of THF, the reaction temperature was lowered to -78 ° C and BuLi 2.5 M was slowly added dropwise to 20 ml and stirred for 1 hour. 11 g of benzophenone was dissolved in 100 ml of THF, and slowly added dropwise thereto, and then the temperature was raised to room temperature and stirred for 12 hours. After completion of the reaction, the mixture was extracted with distilled water and MC, water was removed with anhydrous magnesium sulfate, and the solid obtained by filtration under reduced pressure was dissolved in 100 ml of Acetic acid without further purification, and 7 ml of sulfuric acid was added dropwise and stirred under reflux. After completion of the reaction, the mixture was extracted with distilled water and MC, and the resulting solid was purified by column to obtain 7.1 g of I 2 . (Yield 53%)
상기 단계의 I2 7g, 4-bromodibenzo[b,d]furan 6.5 g, t-BuONa 3 g, Pd2(dba)3 0.7 g, (t-Bu)3P 1 ml를 톨루엔 150 ml에 녹인 후 환류 교반하였다. 반응이 종결되면 증류수와 EA로 추출한 후 컬럼정제하여 화합물을 얻었다. (수율 67%)After dissolving 7 g of I 2 , 6.5 g of 4-bromodibenzo [b, d] furan, 3 g of t-BuONa, 0.7 g of Pd 2 (dba) 3 and 1 ml of (t-Bu) 3 P in 150 ml of toluene It was stirred at reflux. When the reaction was terminated, the mixture was extracted with distilled water and EA and purified by column to obtain a compound. (Yield 67%)
m/z: 499.19 (100.0%), 500.20 (40.3%), 501.20 (8.1%), 502.20 (1.1%)m / z: 499.19 (100.0%), 500.20 (40.3%), 501.20 (8.1%), 502.20 (1.1%)
[실시예 3: 화합물 3의 합성]Example 3: Synthesis of Compound 3
Benzophenone을 9H-fluoren-9-one으로 반응한 것을 제외하고는 화합물 2의 합성방법과 동일한 방법으로 하기 화합물 3을 얻었다.The following Compound 3 was obtained by the same method as the synthesis method of Compound 2, except that Benzophenone was reacted with 9H-fluoren-9-one.
m/z: 497.18 (100.0%), 498.18 (40.3%), 499.18 (8.1%), 500.19 (1.1%)m / z: 497.18 (100.0%), 498.18 (40.3%), 499.18 (8.1%), 500.19 (1.1%)
Figure PCTKR2013006669-appb-I000062
Figure PCTKR2013006669-appb-I000062
[실시예 4: 화합물 4의 합성]Example 4: Synthesis of Compound 4
Benzophenone을 di(pyridin-3-yl)methanone으로 반응한 것을 제외하고는 화합물 2의 합성방법과 동일한 방법으로 하기 화합물 4를 얻었다.Compound 4 was obtained in the same manner as in the synthesis of compound 2, except that benzophenone was reacted with di (pyridin-3-yl) methanone.
m/z: 501.18 (100.0%), 502.19 (38.2%), 503.19 (7.3%), 502.18 (1.1%)m / z: 501.18 (100.0%), 502.19 (38.2%), 503.19 (7.3%), 502.18 (1.1%)
Figure PCTKR2013006669-appb-I000063
Figure PCTKR2013006669-appb-I000063
[실시예 5: 화합물 5의 합성]Example 5: Synthesis of Compound 5
bromodibenzo[b,d]furan(247.09), 4-bromodibenzo[b,d]furan을 1-bromodibenzo[b,d]furan으로 반응한 것을 제외하고는 화합물 1의 합성방법과 동일한 방법으로 하기 화합물 5를 얻었다.Compound 5 was obtained by the same method as the synthesis method of Compound 1, except that bromodibenzo [b, d] furan (247.09) and 4-bromodibenzo [b, d] furan were reacted with 1-bromodibenzo [b, d] furan. Got it.
m/z: 375.16 (100.0%), 376.17 (29.5%), 377.17 (4.4%)m / z: 375.16 (100.0%), 376.17 (29.5%), 377.17 (4.4%)
[실시예 6: 화합물 6의 합성]Example 6: Synthesis of Compound 6
4-bromodibenzo[b,d]furan을 1-bromodibenzo[b,d]furan으로 반응한 것을 제외하고는 화합물 2의 합성방법과 동일한 방법으로 하기 화합물 6을 얻었다.Compound 6 was obtained by the same method as the synthesis method of compound 2, except that 4-bromodibenzo [b, d] furan was reacted with 1-bromodibenzo [b, d] furan.
m/z: 499.19 (100.0%), 500.20 (40.3%), 501.20 (8.1%), 502.20 (1.1%)m / z: 499.19 (100.0%), 500.20 (40.3%), 501.20 (8.1%), 502.20 (1.1%)
Figure PCTKR2013006669-appb-I000065
Figure PCTKR2013006669-appb-I000065
[실시예 7: 화합물 7의 합성]Example 7: Synthesis of Compound 7
4-4-bromodibenzo[b,d]furan을 1-bromodibenzo[b,d]furan으로 반응한 것을 제외하고는 화합물 3의 합성방법과 동일한 방법으로 하기 화합물 7을 얻었다.The following compound 7 was obtained by the same method as the synthesis method of compound 3, except that 4-4-bromodibenzo [b, d] furan was reacted with 1-bromodibenzo [b, d] furan.
m/z: 497.18 (100.0%), 498.18 (40.3%), 499.18 (8.1%), 500.19 (1.1%)m / z: 497.18 (100.0%), 498.18 (40.3%), 499.18 (8.1%), 500.19 (1.1%)
Figure PCTKR2013006669-appb-I000066
Figure PCTKR2013006669-appb-I000066
[실시예 8: 화합물 8의 합성]Example 8: Synthesis of Compound 8
4-4-bromodibenzo[b,d]furan을 1-bromodibenzo[b,d]furan으로 반응한 것을 제외하고는 화합물 4의 합성방법과 동일한 방법으로 하기 화합물 8을 얻었다.The following compound 8 was obtained by the same method as the synthesis method of compound 4, except that 4-4-bromodibenzo [b, d] furan was reacted with 1-bromodibenzo [b, d] furan.
m/z: 501.18 (100.0%), 502.19 (38.2%), 503.19 (7.3%), 502.18 (1.1%)m / z: 501.18 (100.0%), 502.19 (38.2%), 503.19 (7.3%), 502.18 (1.1%)
Figure PCTKR2013006669-appb-I000067
Figure PCTKR2013006669-appb-I000067
[실시예 9: 화합물 9의 합성]Example 9: Synthesis of Compound 9
Figure PCTKR2013006669-appb-I000068
Figure PCTKR2013006669-appb-I000068
2-bromo-N-phenylaniline 10 g을 THF 100 ml에 녹인 후 반응 온도를 -78 ℃로 낮추고 BuLi 2.5 M을 20 ml 천천히 적가하고 1시간 동안 교반하였다. bis(4-chlorophenyl)methanone 15.2 g을 THF 150 ml에 녹인 후 천천히 적가한 후 실온으로 온도를 높이고 12시간 교반하였다. 반응이 종결된 후 증류수와 MC로 추출하고 무수황산마그네슘으로 물을 제거한 후 감압여과하여 얻은 고체를 더 이상의 정제 없이 Acetic acid 150 ml에 녹인 후 황산 10 ml를 적가하고 환류 교반하였다. 반응이 종결된 후 증류수와 MC로 추출하고 생성된 고체를 컬럼 정제하여 I3 10 g을 얻었다. (수율 62%)After dissolving 10 g of 2-bromo-N-phenylaniline in 100 ml of THF, the reaction temperature was lowered to -78 ° C and BuLi 2.5 M was slowly added dropwise to 20 ml and stirred for 1 hour. 15.2 g of bis (4-chlorophenyl) methanone was dissolved in 150 ml of THF, and slowly added dropwise thereto, the temperature was raised to room temperature, and stirred for 12 hours. After completion of the reaction, the mixture was extracted with distilled water and MC, water was removed with anhydrous magnesium sulfate, and the solid obtained by filtration under reduced pressure was dissolved in 150 ml of Acetic acid without further purification, and 10 ml of sulfuric acid was added dropwise and stirred under reflux. After completion of the reaction, the mixture was extracted with distilled water and MC and the resulting solid was purified by column to obtain I 3 10 g. (Yield 62%)
상기 단계의 I3 9 g, 4-bromodibenzo[b,d]furan 6.65 g, t-BuONa 3.2 g, Pd2(dba)3 0.8 g, (t-Bu)3P 1.1 ml를 톨루엔 200 ml에 녹인 후 환류 교반하였다. 반응이 종결되면 증류수와 EA로 추출한 후 컬럼정제하여 I3-1 11 g을 얻었다. (수율 59%)9 g of I 3 in this step, 6.65 g of 4-bromodibenzo [b, d] furan, 3.2 g of t-BuONa, 0.8 g of Pd 2 (dba) 3 , and 1.1 ml of (t-Bu) 3 P were dissolved in 200 ml of toluene. After stirring under reflux. After completion of the reaction, the mixture was extracted with distilled water and EA and purified by column to obtain 11 g of I 3-1 . (Yield 59%)
상기 단계의 I3-1 10 g, diphenylamine 6.85 g, t-BuONa 2.5 g, Pd2(dba)3 0.6 g, (t-Bu)3P 1.6 ml를 톨루엔 200 ml에 녹인 후 환류 교반하였다. 반응이 종결되면 증류수와 EA로 추출한 후 컬럼정제하여 화합물 9 8 g을 얻었다. (수율 55%)10 g of I 3-1 , 6.85 g of diphenylamine, 2.5 g of t-BuONa, 0.6 g of Pd 2 (dba) 3 and 1.6 ml of (t-Bu) 3 P were dissolved in 200 ml of toluene, followed by stirring under reflux. When the reaction was terminated, extracted with distilled water and EA and purified by column to give the compound 9 8 g. (Yield 55%)
m/z: 833.34 (100.0%), 834.34 (67.1%), 835.35 (21.8%), 836.35 (4.8%)m / z: 833.34 (100.0%), 834.34 (67.1%), 835.35 (21.8%), 836.35 (4.8%)
[실시예 10: 화합물 10의 합성]Example 10 Synthesis of Compound 10
diphenylamine을 9H-carbazole로 반응한 것을 제외하고는 화합물 9의 합성방법과 동일한 방법으로 하기 화합물 10을 얻었다. Compound 10 was obtained by the same method as the synthesis method of compound 9, except that diphenylamine was reacted with 9H-carbazole.
m/z: 829.31 (100.0%), 830.31 (67.1%), 831.32 (21.7%), 832.32 (4.8%)m / z: 829.31 (100.0%), 830.31 (67.1%), 831.32 (21.7%), 832.32 (4.8%)
Figure PCTKR2013006669-appb-I000069
Figure PCTKR2013006669-appb-I000069
[실시예 11: 화합물 11의 합성]Example 11: Synthesis of Compound 11
bis(4-chlorophenyl)methanone을 2,7-dichloro-9H-fluoren-9-one으로 반응한 것을 제외하고는 화합물 9의 합성방법과 동일한 방법으로 하기 화합물 11을 얻었다. Compound 11 was obtained in the same manner as in the synthesis of Compound 9, except that bis (4-chlorophenyl) methanone was reacted with 2,7-dichloro-9H-fluoren-9-one.
m/z: 831.32 (100.0%), 832.33 (66.5%), 833.33 (22.7%), 834.34 (4.7%), 832.32 (1.1%)m / z: 831.32 (100.0%), 832.33 (66.5%), 833.33 (22.7%), 834.34 (4.7%), 832.32 (1.1%)
Figure PCTKR2013006669-appb-I000070
Figure PCTKR2013006669-appb-I000070
[실시예 12: 화합물 12의 합성]Example 12 Synthesis of Compound 12
4-4-bromodibenzo[b,d]furan을 1-bromodibenzo[b,d]furan으로 반응한 것을 제외하고는 화합물 9의 합성방법과 동일한 방법으로 하기 화합물 12을 얻었다.The following compound 12 was obtained by the same method as the synthesis method of compound 9, except that 4-4-bromodibenzo [b, d] furan was reacted with 1-bromodibenzo [b, d] furan.
m/z: 833.34 (100.0%), 834.34 (67.1%), 835.35 (21.8%), 836.35 (4.8%)m / z: 833.34 (100.0%), 834.34 (67.1%), 835.35 (21.8%), 836.35 (4.8%)
Figure PCTKR2013006669-appb-I000071
Figure PCTKR2013006669-appb-I000071
[실시예 13: 화합물 13의 합성]Example 13: Synthesis of Compound 13
diphenylamine을 9H-carbazole로 반응한 것을 제외하고는 화합물 12의 합성방법과 동일한 방법으로 하기 화합물 13을 얻었다. Compound 13 was obtained by the same method as the synthesis method of compound 12, except that diphenylamine was reacted with 9H-carbazole.
m/z: 829.31 (100.0%), 830.31 (67.1%), 831.32 (21.7%), 832.32 (4.8%)m / z: 829.31 (100.0%), 830.31 (67.1%), 831.32 (21.7%), 832.32 (4.8%)
Figure PCTKR2013006669-appb-I000072
Figure PCTKR2013006669-appb-I000072
[실시예 14: 화합물 14의 합성]Example 14 Synthesis of Compound 14
4-4-bromodibenzo[b,d]furan을 1-bromodibenzo[b,d]furan으로 반응한 것을 제외하고는 화합물 11의 합성방법과 동일한 방법으로 하기 화합물 14를 얻었다. Compound 14 was obtained in the same manner as in the synthesis of Compound 11, except that 4-4-bromodibenzo [b, d] furan was reacted with 1-bromodibenzo [b, d] furan.
m/z: 831.32 (100.0%), 832.33 (66.5%), 833.33 (22.7%), 834.34 (4.7%), 832.32 (1.1%)m / z: 831.32 (100.0%), 832.33 (66.5%), 833.33 (22.7%), 834.34 (4.7%), 832.32 (1.1%)
Figure PCTKR2013006669-appb-I000073
Figure PCTKR2013006669-appb-I000073
[실시예 15: 화합물 15의 합성]Example 15 Synthesis of Compound 15
Figure PCTKR2013006669-appb-I000074
Figure PCTKR2013006669-appb-I000074
9,9-dimethyl-9,10-dihydroacridine 5 g, 4-bromodibenzo[b,d]thiophene 6.9 g, t-BuONa 3.5 g, Pd2(dba)3 0.9g, (t-Bu)3P 1.2 ml를 톨루엔 100 ml에 녹인후 환류 교반하였다. 반응이 종결되면 증류수와 EA로 추출한 후 컬럼정제하여 화합물 15를 얻었다. (수율 61%)9,9-dimethyl-9,10-dihydroacridine 5 g, 4-bromodibenzo [b, d] thiophene 6.9 g, t-BuONa 3.5 g, Pd 2 (dba) 3 0.9 g, (t-Bu) 3 P 1.2 ml Was dissolved in 100 ml of toluene and stirred under reflux. When the reaction was terminated, the mixture was extracted with distilled water and EA and purified by column to obtain Compound 15. (Yield 61%)
m/z: 391.14 (100.0%), 392.14 (30.4%), 393.14 (4.9%), 393.15 (4.2%), 394.14 (1.3%)m / z: 391.14 (100.0%), 392.14 (30.4%), 393.14 (4.9%), 393.15 (4.2%), 394.14 (1.3%)
[실시예 16: 화합물 16의 합성]Example 16: Synthesis of Compound 16
4-4-bromodibenzo[b,d]furan을 4-bromodibenzo[b,d]thiophene으로 반응한 것을 제외하고는 화합물 2의 합성방법과 동일한 방법으로 하기 화합물 16을 얻었다.The following compound 16 was obtained by the same method as the synthesis method of compound 2, except that 4-4-bromodibenzo [b, d] furan was reacted with 4-bromodibenzo [b, d] thiophene.
m/z: 515.17 (100.0%), 516.17 (41.2%), 517.18 (7.9%), 517.17 (5.0%), 518.17 (1.9%), 518.18m / z: 515.17 (100.0%), 516.17 (41.2%), 517.18 (7.9%), 517.17 (5.0%), 518.17 (1.9%), 518.18
Figure PCTKR2013006669-appb-I000075
Figure PCTKR2013006669-appb-I000075
[실시예 17: 화합물 17의 합성]Example 17 Synthesis of Compound 17
4-4-bromodibenzo[b,d]furan을 4-bromodibenzo[b,d]thiophene으로 반응한 것을 제외하고는 화합물 3의 합성방법과 동일한 방법으로 하기 화합물 17을 얻었다.The following compound 17 was obtained by the same method as the synthesis method of compound 3, except that 4-4-bromodibenzo [b, d] furan was reacted with 4-bromodibenzo [b, d] thiophene.
m/z: 513.16 (100.0%), 514.16 (40.3%), 515.16 (8.4%), 515.15 (4.5%), 516.15 (1.8%), 514.15 (1.2%), 516.17 (1.0%)m / z: 513.16 (100.0%), 514.16 (40.3%), 515.16 (8.4%), 515.15 (4.5%), 516.15 (1.8%), 514.15 (1.2%), 516.17 (1.0%)
Figure PCTKR2013006669-appb-I000076
Figure PCTKR2013006669-appb-I000076
[실시예 18: 화합물 18의 합성]Example 18 Synthesis of Compound 18
4-4-bromodibenzo[b,d]furan을 2-bromo-9,9-dimethyl-9H-fluorene으로 반응한 것을 제외하고는 화합물 4의 합성방법과 동일한 방법으로 하기 화합물 18을 얻었다.The following compound 18 was obtained by the same method as the synthesis method of compound 4, except that 4-4-bromodibenzo [b, d] furan was reacted with 2-bromo-9,9-dimethyl-9H-fluorene.
Figure PCTKR2013006669-appb-I000077
Figure PCTKR2013006669-appb-I000077
[실시예 19: 화합물 19의 합성]Example 19 Synthesis of Compound 19
4-4-bromodibenzo[b,d]furan을 2-bromo-9,9-dimethyl-9H-fluorene으로 반응한 것을 제외하고는 화합물 2의 합성방법과 동일한 방법으로 하기 화합물 19를 얻었다.The following compound 19 was obtained by the same method as the synthesis method of compound 2, except that 4-4-bromodibenzo [b, d] furan was reacted with 2-bromo-9,9-dimethyl-9H-fluorene.
m/z: 525.25 (100.0%), 526.25 (43.6%), 527.25 (9.3%), 528.26 (1.3%)m / z: 525.25 (100.0%), 526.25 (43.6%), 527.25 (9.3%), 528.26 (1.3%)
Figure PCTKR2013006669-appb-I000078
Figure PCTKR2013006669-appb-I000078
[실시예 20: 화합물 20의 합성]Example 20 Synthesis of Compound 20
4-4-bromodibenzo[b,d]furan을 2-bromo-9,9-dimethyl-9H-fluorene으로 반응한 것을 제외하고는 화합물 4의 합성방법과 동일한 방법으로 하기 화합물 20을 얻었다.The following compound 20 was obtained by the same method as the synthesis method of compound 4, except that 4-4-bromodibenzo [b, d] furan was reacted with 2-bromo-9,9-dimethyl-9H-fluorene.
Figure PCTKR2013006669-appb-I000079
Figure PCTKR2013006669-appb-I000079
호스트를 이용한 유기발광소자의 제조Fabrication of Organic Light Emitting Diode Using Host
도 1과 같은 구조로 유기발광소자를 제조하였다. 구체적으로 인듐틴옥사이드(ITO)가 1500 Å 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층으로 2-TNATA 600 Å, 정공전달층으로 NPB 200 Å를 제막하였다.An organic light emitting diode was manufactured in the same structure as in FIG. 1. Specifically, the glass substrate coated with a 1500 μm thick indium tin oxide (ITO) was washed with distilled water ultrasonic waves. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and the substrate is cleaned for 5 minutes using an oxygen plasma. Using an evaporator, 2-TNATA 600 으로 was formed as a hole injection layer and NPB 200 전 was formed as a hole transport layer.
다음으로 상기 실시예에서 합성한 실시예 1 내지 20의 호스트 물질을 Ir(ppy)3 7%로 도핑하여 300 Å 제막하였다. 다음으로 전자전달층으로 TPBi 300 Å 제막한 후 LiF 10 Å, 알루미늄(Al) 1000 Å 제막하고, 이 소자를 글로브 박스에서 밀봉(Encapsulation)함으로써 유기발광소자를 제작하였다.Next, the host material of Examples 1 to 20 synthesized in the above Example was doped with Ir (ppy) 3 7% to form 300 Å. Next, TPBi 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 Å, which were encapsulated in a glove box to produce an organic light emitting device.
정공수송층을 이용한 유기발광소자의 제조Fabrication of Organic Light Emitting Diode Using Hole Transport Layer
인듐틴옥사이드(ITO)가 1500 Å 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송 시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층으로 2-TNATA 600 Å, 정공전달층으로 상기 실시예 1 내지 20에서 합성한 화합물 200 Å를 제막하였다. 다음으로 mCP를 Ir(ppy)3 7%로 도핑하여 300 Å 제막하였다. 다음으로 전자전달층으로 TPBi 300 Å 제막한후 LiF 10 Å, 알루미늄(Al) 1000 Å 제막하고, 이 소자를 글로브 박스에서 밀봉(Encapsulation)함으로써 유기발광소자를 제작하였다.A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and the substrate is cleaned for 5 minutes using an oxygen plasma. 2-TNATA 600 Å was used as the hole injection layer, and 200 화합물 of the compound synthesized in Examples 1 to 20 was formed into a hole transport layer using an evaporator. Next, mCP was doped with Ir (ppy) 3 7% to form 300 Å. Next, TPBi 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막. The organic light emitting device was manufactured by encapsulating the device in a glove box.
비교예 : 정공수송층을 이용한 유기발광소자의 제조Comparative Example: Fabrication of Organic Light Emitting Diode Using Hole Transport Layer
상기 실시예의 정공수송층과 발광층 호스트를 NPB와 mCP를 사용한 것을 제외하고는 동일한 방법으로 유기발광소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as the hole transport layer and the light emitting layer host, except for using NPB and mCP.
유기발광소자의 성능평가Performance Evaluation of Organic Light Emitting Diode
키슬리 2400 소스 메져먼트 유닛(Kiethley 2400 source measurement unit) 으로 전압을 인가하여 전자 및 정공을 주입하고 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 실시예 및 비교예의 유기발광소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건하에 측정하여 평가하였으며, 그 결과를 표 1에 나타내었다.Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 1.
표 1
소자구성 1000nit
LE(cd/A) EQE(%) PE(lm/w)
실시예21 ITO / 2-TNATA / NPB /화합물1:Ir(ppy)3(7%) / TPBi / LiF / Al 38.5 17.7 18
실시예22 ITO / 2-TNATA / NPB /화합물2:Ir(ppy)3(7%) / TPBi / LiF / Al 39.2 17.9 18.3
실시예23 ITO / 2-TNATA / NPB / 화합물3:Ir(ppy)3(7%) / TPBi / LiF / Al 40 19 19.2
실시예24 ITO / 2-TNATA / NPB / 화합물4:Ir(ppy)3(7%) / TPBi / LiF / Al 41 19.3 20
실시예25 ITO / 2-TNATA / NPB / 화합물5:Ir(ppy)3(7%) / TPBi / LiF / Al 38.2 17.8 16.9
실시예26 ITO / 2-TNATA / NPB / 화합물6:Ir(ppy)3(7%) / TPBi / LiF / Al 39.1 18 17.9
실시예27 ITO / 2-TNATA / NPB / 화합물7:Ir(ppy)3(7%) / TPBi / LiF / Al 39.3 18.2 17.5
실시예28 ITO / 2-TNATA / NPB / 화합물8:Ir(ppy)3(7%) / TPBi / LiF / Al 40.9 18.9 19
실시예29 ITO / 2-TNATA / NPB / 화합물10:Ir(ppy)3(7%) / TPBi / LiF / Al 41.1 19.5 20.2
실시예30 ITO / 2-TNATA / 화합물9 /mCP:Ir(ppy)3(7%) / TPBi / LiF / Al 39.9 19.1 18.7
실시예31 ITO / 2-TNATA / 화합물10 /mCP:Ir(ppy)3(7%) / TPBi / LiF / Al 40.6 18.8 19.5
실시예32 ITO / 2-TNATA / 화합물11 /mCP:Ir(ppy)3(7%) / TPBi / LiF / Al 40.9 18.9 19.8
비교예 ITO / 2-TNATA / NPB /mCP:Ir(ppy)3(7%) / TPBi / LiF / Al 38 16.6 15.2
Table 1
Device composition 1000nit
LE (cd / A) EQE (%) PE (lm / w)
Example 21 ITO / 2-TNATA / NPB / Compound 1: Ir (ppy) 3 (7%) / TPBi / LiF / Al 38.5 17.7 18
Example 22 ITO / 2-TNATA / NPB / Compound 2: Ir (ppy) 3 (7%) / TPBi / LiF / Al 39.2 17.9 18.3
Example 23 ITO / 2-TNATA / NPB / Compound 3: Ir (ppy) 3 (7%) / TPBi / LiF / Al 40 19 19.2
Example 24 ITO / 2-TNATA / NPB / Compound 4: Ir (ppy) 3 (7%) / TPBi / LiF / Al 41 19.3 20
Example 25 ITO / 2-TNATA / NPB / Compound 5: Ir (ppy) 3 (7%) / TPBi / LiF / Al 38.2 17.8 16.9
Example 26 ITO / 2-TNATA / NPB / Compound 6: Ir (ppy) 3 (7%) / TPBi / LiF / Al 39.1 18 17.9
Example 27 ITO / 2-TNATA / NPB / Compound 7: Ir (ppy) 3 (7%) / TPBi / LiF / Al 39.3 18.2 17.5
Example 28 ITO / 2-TNATA / NPB / Compound 8: Ir (ppy) 3 (7%) / TPBi / LiF / Al 40.9 18.9 19
Example 29 ITO / 2-TNATA / NPB / Compound 10: Ir (ppy) 3 (7%) / TPBi / LiF / Al 41.1 19.5 20.2
Example 30 ITO / 2-TNATA / Compound 9 / mCP: Ir (ppy) 3 (7%) / TPBi / LiF / Al 39.9 19.1 18.7
Example 31 ITO / 2-TNATA / Compound 10 / mCP: Ir (ppy) 3 (7%) / TPBi / LiF / Al 40.6 18.8 19.5
Example 32 ITO / 2-TNATA / Compound 11 / mCP: Ir (ppy) 3 (7%) / TPBi / LiF / Al 40.9 18.9 19.8
Comparative example ITO / 2-TNATA / NPB / mCP: Ir (ppy) 3 (7%) / TPBi / LiF / Al 38 16.6 15.2
상기 표 1에 나타나는 바와 같이 본 발명에 따른 실시예 1 내지 11에서 합성한 화합물을 사용한 실시예 21 내지 32의 유기발광소자는 비교예에 비하여 휘도, 효율 및 전류밀도가 모두 우수함을 확인할 수 있다.As shown in Table 1, it can be seen that the organic light emitting diodes of Examples 21 to 32 using the compounds synthesized in Examples 1 to 11 according to the present invention are superior in brightness, efficiency, and current density as compared with the comparative examples.
본 발명의 유기발광 화합물은 아크리딘 유도체와 고리화합물의 적절한 조화를 통해 유기물층 내에서의 전하균형을 조절함으로써, 휘도, 전력효율, 내열성, 전하수송 성능 및 전하주입 성능이 우수하여 색순도 및 발광효율을 증가시킬 수 있으므로, 유기발광소자의 기능층 재료 및 발광층의 호스트나 도판트 중 하나 이상에 적용할 수 있다. 따라서, 본 발명의 화합물을 포함하는 유기발광소자는 낮은 구동전압과 높은 발광휘도 및 발광효율을 나타내며, 이에 따라 풀 칼라 유기 패널에서 성능 극대화 및 수명 향상을 제공할 수 있다.The organic light emitting compound of the present invention is excellent in brightness, power efficiency, heat resistance, charge transport performance and charge injection performance by controlling the charge balance in the organic layer through the appropriate combination of the acridine derivative and the cyclic compound, the color purity and luminous efficiency Since it can be increased, it can be applied to one or more of the functional layer material of the organic light emitting device and the host or dopant of the light emitting layer. Therefore, the organic light emitting device including the compound of the present invention exhibits low driving voltage, high luminous luminance and luminous efficiency, and thus can maximize performance and improve lifespan in a full color organic panel.

Claims (11)

  1. 하기 화학식 1로 표시되는, 아크리딘 유도체를 포함하는 유기발광 화합물 :An organic light emitting compound including an acridine derivative represented by Formula 1 below:
    [화학식 1][Formula 1]
    Figure PCTKR2013006669-appb-I000080
    Figure PCTKR2013006669-appb-I000080
    상기 식에서,Where
    X는 치환 또는 비치환된 C, O, P, S, Se 또는 Si이고, X가 O일 경우 아크리딘의 질소 원자는 헤테로아릴계 모이어티의 3번 위치에는 결합될 수 없고;X is substituted or unsubstituted C, O, P, S, Se or Si, and when X is O, the nitrogen atom of the acridine cannot be bonded at position 3 of the heteroaryl moiety;
    R1 내지 R17은 각각 독립적으로, 수소; 중수소; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-36의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환된 치환되거나 치환되지 않은 C2-36의 헤테로아릴기이고, 선택적으로, 상기 R1 내지 R17 중 인접한 기가 서로 결합하여 포화 또는 불포화 탄소 고리를 형성할 수 있다.R 1 to R 17 are each independently hydrogen; heavy hydrogen; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 6-36 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; Or a substituted or unsubstituted C 2-36 heteroaryl group substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group, and optionally, adjacent groups of R 1 to R 17 combine with each other to form a saturated or unsaturated carbon ring. Can be formed.
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1의 화합물이 중수소로 치환되는 경우, 적어도 20%로 중수소화 되는 것을 특징으로 하는 유기발광 화합물.When the compound of Formula 1 is substituted with deuterium, the organic light emitting compound, characterized in that deuterated at least 20%.
  3. 제1항에 있어서,The method of claim 1,
    상기 아크리딘계 모이어티(moiety)의 질소 원자에 직접 연결된 아릴계 또는 헤테로아릴계 모이어티가 중수소로 치환되는 경우에는, 적어도 50% 중수소화 되는 것을 특징으로 하는 유기발광 화합물.When the aryl or heteroaryl moiety directly connected to the nitrogen atom of the acridine-based moiety is substituted with deuterium, at least 50% deuterated.
  4. 제1항에 있어서,The method of claim 1,
    하기 화학식들 중 어느 하나로 표시되는 것을 특징으로 하는 유기발광 화합물:An organic light emitting compound, characterized in that represented by any one of the following formula:
    Figure PCTKR2013006669-appb-I000081
    Figure PCTKR2013006669-appb-I000081
    Figure PCTKR2013006669-appb-I000082
    Figure PCTKR2013006669-appb-I000082
    Figure PCTKR2013006669-appb-I000083
    Figure PCTKR2013006669-appb-I000083
    Figure PCTKR2013006669-appb-I000084
    Figure PCTKR2013006669-appb-I000084
    Figure PCTKR2013006669-appb-I000085
    Figure PCTKR2013006669-appb-I000085
    Figure PCTKR2013006669-appb-I000086
    Figure PCTKR2013006669-appb-I000086
    Figure PCTKR2013006669-appb-I000087
    Figure PCTKR2013006669-appb-I000087
    Figure PCTKR2013006669-appb-I000088
    Figure PCTKR2013006669-appb-I000088
    Figure PCTKR2013006669-appb-I000089
    Figure PCTKR2013006669-appb-I000089
    Figure PCTKR2013006669-appb-I000090
    Figure PCTKR2013006669-appb-I000090
    Figure PCTKR2013006669-appb-I000091
    Figure PCTKR2013006669-appb-I000091
    Figure PCTKR2013006669-appb-I000092
    Figure PCTKR2013006669-appb-I000092
    Figure PCTKR2013006669-appb-I000093
    Figure PCTKR2013006669-appb-I000093
    Figure PCTKR2013006669-appb-I000094
    Figure PCTKR2013006669-appb-I000094
    Figure PCTKR2013006669-appb-I000095
    Figure PCTKR2013006669-appb-I000095
    Figure PCTKR2013006669-appb-I000096
    Figure PCTKR2013006669-appb-I000096
    Figure PCTKR2013006669-appb-I000097
    Figure PCTKR2013006669-appb-I000097
    Figure PCTKR2013006669-appb-I000098
    Figure PCTKR2013006669-appb-I000098
    Figure PCTKR2013006669-appb-I000099
    Figure PCTKR2013006669-appb-I000099
    Figure PCTKR2013006669-appb-I000100
    Figure PCTKR2013006669-appb-I000100
    Figure PCTKR2013006669-appb-I000101
    Figure PCTKR2013006669-appb-I000101
    Figure PCTKR2013006669-appb-I000102
    Figure PCTKR2013006669-appb-I000102
    Figure PCTKR2013006669-appb-I000103
    Figure PCTKR2013006669-appb-I000104
    Figure PCTKR2013006669-appb-I000103
    Figure PCTKR2013006669-appb-I000104
    Figure PCTKR2013006669-appb-I000105
    Figure PCTKR2013006669-appb-I000105
    Figure PCTKR2013006669-appb-I000106
    Figure PCTKR2013006669-appb-I000106
    Figure PCTKR2013006669-appb-I000107
    Figure PCTKR2013006669-appb-I000108
    Figure PCTKR2013006669-appb-I000107
    Figure PCTKR2013006669-appb-I000108
    Figure PCTKR2013006669-appb-I000109
    Figure PCTKR2013006669-appb-I000110
    Figure PCTKR2013006669-appb-I000109
    Figure PCTKR2013006669-appb-I000110
    Figure PCTKR2013006669-appb-I000111
    Figure PCTKR2013006669-appb-I000111
    Figure PCTKR2013006669-appb-I000112
    Figure PCTKR2013006669-appb-I000112
    Figure PCTKR2013006669-appb-I000113
    Figure PCTKR2013006669-appb-I000113
    Figure PCTKR2013006669-appb-I000114
    Figure PCTKR2013006669-appb-I000114
    Figure PCTKR2013006669-appb-I000115
    Figure PCTKR2013006669-appb-I000115
    Figure PCTKR2013006669-appb-I000116
    Figure PCTKR2013006669-appb-I000116
    Figure PCTKR2013006669-appb-I000117
    Figure PCTKR2013006669-appb-I000117
    Figure PCTKR2013006669-appb-I000118
    Figure PCTKR2013006669-appb-I000118
    Figure PCTKR2013006669-appb-I000119
    Figure PCTKR2013006669-appb-I000119
    Figure PCTKR2013006669-appb-I000120
    Figure PCTKR2013006669-appb-I000120
    Figure PCTKR2013006669-appb-I000121
    Figure PCTKR2013006669-appb-I000121
    Figure PCTKR2013006669-appb-I000122
    Figure PCTKR2013006669-appb-I000122
    Figure PCTKR2013006669-appb-I000123
    Figure PCTKR2013006669-appb-I000123
    Figure PCTKR2013006669-appb-I000124
    Figure PCTKR2013006669-appb-I000124
    Figure PCTKR2013006669-appb-I000125
    Figure PCTKR2013006669-appb-I000125
    Figure PCTKR2013006669-appb-I000126
    Figure PCTKR2013006669-appb-I000126
    Figure PCTKR2013006669-appb-I000127
    Figure PCTKR2013006669-appb-I000127
    Figure PCTKR2013006669-appb-I000128
    Figure PCTKR2013006669-appb-I000128
    Figure PCTKR2013006669-appb-I000129
    Figure PCTKR2013006669-appb-I000129
    Figure PCTKR2013006669-appb-I000130
    Figure PCTKR2013006669-appb-I000130
    Figure PCTKR2013006669-appb-I000131
    Figure PCTKR2013006669-appb-I000131
    Figure PCTKR2013006669-appb-I000132
    Figure PCTKR2013006669-appb-I000132
  5. 하기 화학식 1-1과 화학식 1-2를 반응시키는 단계를 포함하는 특징으로 하는 화학식 1의 제조방법:A method of preparing Formula 1, comprising reacting Formula 1-1 with Formula 1-2:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2013006669-appb-I000133
    Figure PCTKR2013006669-appb-I000133
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2013006669-appb-I000134
    Figure PCTKR2013006669-appb-I000134
    상기에서 X 및 R1 내지 R17은 화학식 1에서 정의한 바와 같다.X and R 1 to R 17 are the same as defined in Chemical Formula 1.
  6. 제1항에 있어서,The method of claim 1,
    상기 제조방법은 하기 반응식 1로 표시되는 것 중 어느 하나인 것을 특징으로 하는 화학식 1의 제조방법:The preparation method is a manufacturing method of Formula 1, characterized in that any one of the following Reaction Scheme 1:
    [반응식 1]Scheme 1
    Figure PCTKR2013006669-appb-I000135
    Figure PCTKR2013006669-appb-I000135
    상기 반응식 1에서 X는 화학식 1에서 정의한 바와 같으며, 각각의 R은 각각 화학식 1-1의 R1 및 R2에 대응된다.In Scheme 1, X is as defined in Formula 1, and each R corresponds to R 1 and R 2 of Formula 1-1, respectively.
  7. 애노드(anode), 캐소드(cathode) 및 두 전극 사이에 제1항의 화합물을 함유하는 1층 이상의 유기물층을 포함하는 유기발광소자.An organic light emitting device comprising an anode, a cathode and at least one organic layer containing the compound of claim 1 between two electrodes.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 유기물층이 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군에서 선택되는 하나 이상인 것을 특징으로 하는 유기발광소자.And the organic material layer is at least one selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  9. 제8항에 있어서,The method of claim 8,
    상기 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층이 각각 10 내지 1,000 ㎚의 두께를 갖는 것을 특징으로 하는 유기발광소자.And the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer each have a thickness of 10 to 1,000 nm.
  10. 제7항에 있어서,The method of claim 7, wherein
    상기 유기물층이 제1항의 화합물을 발광 호스트 또는 도펀트로서 함유하는 것을 특징으로 하는 유기발광소자.An organic light emitting device, characterized in that the organic layer contains the compound of claim 1 as a light emitting host or dopant.
  11. 제10항에 있어서,The method of claim 10,
    상기 도펀트가 호스트 100 중량부 대비 0.01 내지 15 중량부의 양으로 첨가되는 것을 특징으로 하는 유기발광소자.The organic light emitting device, characterized in that the dopant is added in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the host.
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* Cited by examiner, † Cited by third party
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WO2016111196A1 (en) * 2015-01-08 2016-07-14 国立大学法人九州大学 Compound, mixture, light-emitting layer, organic light-emitting element, and assist dopant
JP2016130231A (en) * 2015-01-08 2016-07-21 国立大学法人九州大学 Compound, mixture, light-emitting layer, organic light-emitting element, and assist dopant
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US9960372B2 (en) 2014-11-27 2018-05-01 Samsung Display Co., Ltd. Monoamine derivative and organic electroluminescent device including the same
JP2016130231A (en) * 2015-01-08 2016-07-21 国立大学法人九州大学 Compound, mixture, light-emitting layer, organic light-emitting element, and assist dopant
WO2016111196A1 (en) * 2015-01-08 2016-07-14 国立大学法人九州大学 Compound, mixture, light-emitting layer, organic light-emitting element, and assist dopant
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CN106220645A (en) * 2016-04-25 2016-12-14 中节能万润股份有限公司 Compound based on monosubstituted-9-fluorenone and application thereof
US11440925B2 (en) 2016-11-08 2022-09-13 Merck Patent Gmbh Compounds for electronic devices
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WO2018159663A1 (en) * 2017-02-28 2018-09-07 国立大学法人九州大学 Light-emitting material, organic light-emitting element and compound
CN108976212A (en) * 2017-06-02 2018-12-11 北京鼎材科技有限公司 Fluorene derivative and its application in luminous organic material
JP2021506822A (en) * 2017-12-15 2021-02-22 メルク パテント ゲーエムベーハー Substituted aromatic amines for use in organic electroluminescent devices
US11925113B2 (en) 2018-04-24 2024-03-05 Lg Chem, Ltd. Heterocyclic compound and organic light emitting device comprising the same
DE102021213722A1 (en) 2021-12-02 2023-06-07 Continental Reifen Deutschland Gmbh Connection, rubber mixture containing the connection, vehicle tire which has the rubber mixture in at least one component, method for producing the connection and use of the connection as anti-aging agent and/or antioxidant and/or colorant
WO2023098953A1 (en) 2021-12-02 2023-06-08 Continental Reifen Deutschland Gmbh Compound, rubber blend containing the compound, vehicle tire comprising the rubber blend in at least one component, process for producing the compound, and use of the compound as an ageing protectant and/or antioxidant and/or dye

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