WO2020111586A1 - Novel compound and organic light-emitting device using same - Google Patents

Novel compound and organic light-emitting device using same Download PDF

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WO2020111586A1
WO2020111586A1 PCT/KR2019/015362 KR2019015362W WO2020111586A1 WO 2020111586 A1 WO2020111586 A1 WO 2020111586A1 KR 2019015362 W KR2019015362 W KR 2019015362W WO 2020111586 A1 WO2020111586 A1 WO 2020111586A1
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layer
substituted
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정민우
이동훈
장분재
홍완표
서상덕
이정하
한수진
박슬찬
황성현
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주식회사 엘지화학
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Priority claimed from KR1020190142730A external-priority patent/KR102341766B1/en
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Priority to CN201980060932.6A priority Critical patent/CN112739693B/en
Publication of WO2020111586A1 publication Critical patent/WO2020111586A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material.
  • the organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.
  • the organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode.
  • the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the present invention provides a compound represented by Formula 1:
  • X are each independently N or CH, provided that 2 or more of X are N,
  • Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • L is a single bond; Substituted or unsubstituted C 6-60 arylene; Or a substituted or unsubstituted C 5-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • E is a substituted or unsubstituted C 5-60 heteroaryl containing N or more
  • D is a substituent represented by any one of the following formulas 2-1 to 2-4,
  • A is a benzene ring fused with two adjacent pentagonal rings
  • Y 1 is O or S
  • Y 2 is O; S; NR 3 , or CR 4 R 5 ,
  • n is each independently an integer from 0 to 4,
  • R 1 is each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
  • R 2 to R 5 are each independently substituted or unsubstituted C 1-60 alkyl; Or substituted or unsubstituted C 6-60 aryl.
  • the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer provides an organic light emitting device including the compound represented by Chemical Formula 1.
  • the compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or life characteristics in the organic light emitting device.
  • the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • Figure 2 shows an example of an organic light emitting device consisting of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron transport layer (8) and a cathode (4) Did.
  • 3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (9), light emitting layer (7), hole blocking layer (10), electron transport layer (8) , It shows an example of an organic light-emitting device consisting of the electron injection layer 11 and the cathode (4).
  • the present invention provides a compound represented by Formula 1 above.
  • substituted or unsubstituted refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more
  • the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styrenyl group, styrenyl group, and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20.
  • the aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure.
  • the fluorenyl group When the fluorenyl group is substituted, It can be back. However, it is not limited thereto.
  • the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group,
  • an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above.
  • the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group.
  • heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group.
  • the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group.
  • the description of the aryl group described above may be applied, except that the arylene is a divalent group.
  • the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding.
  • the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.
  • E may be represented by any one of the following Chemical Formulas 3-1 to 3-5:
  • Z is each independently N or CH, provided that at least one of Z is N,
  • Ar 3 and Ar 4 are each independently substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • Ar 5 is substituted or unsubstituted C 6-60 aryl
  • Y 3 is O or S
  • n are each independently an integer from 0 to 4,
  • R 6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.
  • Z can all be N.
  • m can be each independently 0 or 1.
  • R 6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-20 aryl, more preferably hydrogen; heavy hydrogen; methyl; Or phenyl.
  • Ar 3 and Ar 4 may each independently be any one selected from the group consisting of:
  • Ar 3 and Ar 4 are each independently phenyl; Phenyl substituted with deuterium; It can be biphenyl or dibenzofuranyl.
  • Ar 5 may be substituted or unsubstituted C 6-20 aryl, and more preferably phenyl.
  • E can be selected from the group consisting of:
  • Ar 3 and Ar 4 are as defined above.
  • formula 2-4 may be represented by any one of the following formulas 4-1 to 4-4:
  • X can all be N.
  • Ar 1 and Ar 2 may each independently be any one selected from the group consisting of:
  • L can be a single bond, phenylene, biphenyldiyl, naphthalenediyl, dibenzofurandiyl, or dibenzothiophendiyl, more preferably single bond, phenylene, naphthalenediyl or dibenzothiophendi It can be one day.
  • n can be each independently 0, 1 or 2.
  • R 1 is each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-20 aryl, more preferably hydrogen; heavy hydrogen; Or phenyl.
  • R 2 to R 5 are each independently substituted or unsubstituted C 1-10 alkyl; Or it may be a substituted or unsubstituted C 6-20 aryl, more preferably methyl or phenyl.
  • the compound represented by Chemical Formula 1 may be selected from the group consisting of the following compounds:
  • the compound represented by the formula (1) may be prepared by the same method as in Scheme 1, for example.
  • the present invention provides an organic light emitting device comprising the compound represented by the formula (1).
  • the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and an organic light emitting device is provided. do.
  • the organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto, and may include fewer organic layers.
  • the organic material layer may include a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and transport, or an electron blocking layer, and the hole injection layer, a hole transport layer, and a layer or hole that simultaneously performs hole injection and transport
  • the layer may include a compound represented by Formula 1 above.
  • the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1.
  • the compound represented by Formula 1 may be used as a host material in the light emitting layer, and more specifically, the compound represented by Formula 1 may be used as a host used in the light emitting layer of the green organic light emitting device.
  • the organic material layer may include a hole blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously performs electron transport and electron injection, and the hole blocking layer, electron transport layer, electron injection layer, or electron transport and electron
  • the simultaneous injection layer may include a compound represented by Chemical Formula 1 above.
  • the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 to 3.
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • the compound represented by Chemical Formula 1 may be included in the light emitting layer.
  • Figure 2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 Did.
  • the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.
  • the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer.
  • the organic light-emitting device according to the present invention can be made of materials and methods known in the art, except that at least one layer of the organic material layer contains the compound represented by Chemical Formula 1.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
  • PVD physical vapor deposition
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon.
  • an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth.
  • the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
  • the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof;
  • a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
  • the hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer.
  • a compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred.
  • the high occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer.
  • hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances.
  • Organic anthraquinone and polyaniline and polythiophene-based conductive polymers are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light-emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • the electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility, prevent excessive movement of electrons, and increase the probability of hole-electron bonding, thereby increasing the efficiency of the organic light emitting device. It serves to improve.
  • the electron blocking layer includes an electron blocking material, and a material having a stable structure in which electrons do not flow out of the light emitting layer is suitable as the electron blocking material.
  • an arylamine-based organic material or the like may be used, but is not limited thereto.
  • a material capable of emitting light in the visible region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively is preferably a material having good quantum efficiency for fluorescence or phosphorescence.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
  • the light emitting layer may include a host material and a dopant material.
  • the host material may be a condensed aromatic ring derivative or a heterocyclic compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the dopant material examples include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound.
  • a compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like but are not limited thereto.
  • examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.
  • the hole blocking layer is formed on the light emitting layer, and specifically, the hole blocking layer is provided in contact with the light emitting layer, thereby preventing excessive movement of holes and increasing the probability of hole-electron bonding, thereby improving the efficiency of the organic light emitting device Do it.
  • the hole blocking layer includes a hole blocking material, and as the hole blocking material, a material having a stable structure in which holes may not flow out of the light emitting layer is suitable. Examples of the hole blocking material include azine derivatives including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; Compounds in which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer.
  • the electron transport material a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material, as used according to the prior art.
  • suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.
  • the electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, and bis(8-hydroxyquinolinato) manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
  • the organic light emitting device may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
  • the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • A1-1 (20 g, 55.3 mmol) and bis(pinacolato)diboron (21.8 g, 55.3 mmol) were added to 400 ml of Diox, stirred and refluxed. After this, potassium triphosphate (35.2 g, 165.8 mmol) was introduced and sufficiently stirred, and then palladium dibenzylidene acetone palladium (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. After 7 hours of reaction, after cooling to room temperature, the organic layer was filtered to remove salt, and then the filtered organic layer was distilled.
  • A1-2 (30 g, 66.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (17.7 g, 66.2 mmol) were added to 600 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (27.4 g, 198.5 mmol) was dissolved in 27 ml of water, stirred thoroughly, and then tetrakistriphenyl-phosphino palladium (2.3 g, 2 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated and the organic layer was distilled.
  • B1-2 (30 g, 58.9 mmol) and bis(pinacolato)diboron (23.3 g, 58.9mmol) were added to Diox 600ml, stirred and refluxed. After this, potassium triphosphate (37.5 g, 176.8 mmol) was introduced and sufficiently stirred, and then palladium dibenzylidene acetone palladium (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and then the filtered organic layer was distilled.
  • A1 (15 g, 26.9 mmol) and 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (7.6 g, 26.9 mmol) were placed in 300 ml of dimethylformamide, stirred and refluxed. . After that, sodium tibutoxide (7.7 g, 80.6 mmol) was added and heated and stirred. After the reaction for 3 hours, the resulting solid was filtered after being cooled to room temperature.
  • B1 (20 g, 33.3 mmol) and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (12.9 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran and stirred and refluxed. Did. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer and water layer were separated, and then the organic layer was distilled.
  • B1 (20 g, 33.3 mmol) and 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (12.9 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran and stirred and refluxed. Did. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated and the organic layer was distilled.
  • B1 (20 g, 33.3 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (9.3 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer and water layer were separated, and then the organic layer was distilled.
  • B1 (20 g, 33.3 mmol) and 2-chlorobenzo[d]thiazole (5.6 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and then the organic layer was distilled.
  • ITO Indium Tin Oxide
  • distilled water filtered secondarily by a filter of Millipore Co.
  • ultrasonic cleaning was repeated twice with distilled water for 10 minutes.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner.
  • the substrate was transferred to a vacuum evaporator.
  • the following HT-A compound and the following PD compound were thermally vacuum-deposited to a thickness of 100 ⁇ at a weight ratio of 95:5, and then the following HT-A compound was deposited to a thickness of 1150 ⁇ to form a hole transport layer. Formed.
  • the following HT-B compound was thermally vacuum-deposited to a thickness of 450 MPa to form an electron blocking layer.
  • Compound 1 and the following GD compound prepared above were vacuum-deposited at a weight ratio of 85:15 to a thickness of 400 Pa to form a light emitting layer.
  • a hole blocking layer was formed by vacuum-depositing the following ET-A compound to a thickness of 50 MPa.
  • the following ET-B compound and the following Liq compound were thermally vacuum-deposited to a thickness of 250 ⁇ at a weight ratio of 2:1, and then vacuum-deposited LiF and magnesium at a thickness of 30 ⁇ at a weight ratio of 1:1.
  • To form an electron transport and injection layer On the electron injection layer, magnesium and silver were deposited to a thickness of 160 4 in a weight ratio of 1:4 to form a cathode, thereby manufacturing an organic light emitting device.
  • the deposition rate of the organic material was maintained at 0.4 to 0.7 ⁇ /sec
  • the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 ⁇ /sec for silver and magnesium, and 2 ⁇ /sec for silver and magnesium.
  • An organic light emitting device was manufactured by maintaining 10 ⁇ 7 ⁇ 5 ⁇ 10 ⁇ 6 torr.
  • An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 below was used instead of Compound 1.
  • T95 Voltage, efficiency, and lifetime
  • the monocyclic nitrogen-containing heterocycle that serves as an electron acceptor in the molecule is linked to each other at a para position, so that the stability of the molecule is high, and it is advantageous for both hole and electron transport.
  • substrate 2 anode

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Abstract

The present invention provides a novel compound and an organic light-emitting device using same.

Description

신규한 화합물 및 이를 이용한 유기 발광 소자Novel compound and organic light emitting device using same
관련 출원(들)과의 상호 인용Cross-citation with relevant application(s)
본 출원은 2018년 11월 27일자 한국 특허 출원 제10-2018-0148563호 및 2019년 11월 8일자 한국 특허 출원 제10-2019-0142730호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0148563 dated November 27, 2018 and Korean Patent Application No. 10-2019-0142730 dated November 8, 2019. All content disclosed in the literature is incorporated as part of this specification.
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to a novel compound and an organic light emitting device comprising the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다.In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물층을 포함하는 구조를 가진다. 상기 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다.The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.
[선행기술문헌][Advanced technical literature]
[특허문헌][Patent Document]
(특허문헌 0001) 한국특허 공개번호 제10-2000-0051826호(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to a novel compound and an organic light emitting device comprising the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by Formula 1:
[화학식 1][Formula 1]
Figure PCTKR2019015362-appb-I000001
Figure PCTKR2019015362-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
X는 각각 독립적으로 N 또는 CH이고, 단 X 중 2 이상은 N이고,X are each independently N or CH, provided that 2 or more of X are N,
Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
L은 단일결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 치환 또는 비치환된 C5-60 헤테로아릴렌이고,L is a single bond; Substituted or unsubstituted C 6-60 arylene; Or a substituted or unsubstituted C 5-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
E는 N을 1 이상 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,E is a substituted or unsubstituted C 5-60 heteroaryl containing N or more,
D는 하기 화학식 2-1 내지 2-4 중 어느 하나로 표시되는 치환기이고,D is a substituent represented by any one of the following formulas 2-1 to 2-4,
[화학식 2-1][Formula 2-1]
Figure PCTKR2019015362-appb-I000002
Figure PCTKR2019015362-appb-I000002
[화학식 2-2][Formula 2-2]
Figure PCTKR2019015362-appb-I000003
Figure PCTKR2019015362-appb-I000003
[화학식 2-3][Formula 2-3]
Figure PCTKR2019015362-appb-I000004
Figure PCTKR2019015362-appb-I000004
[화학식 2-4][Formula 2-4]
Figure PCTKR2019015362-appb-I000005
Figure PCTKR2019015362-appb-I000005
상기 화학식 2-1 내지 2-4에서,In Chemical Formulas 2-1 to 2-4,
A는 인접한 두 개의 오각 고리와 융합된 벤젠 고리이고,A is a benzene ring fused with two adjacent pentagonal rings,
Y1은 O 또는 S이고,Y 1 is O or S,
Y2는 O; S; NR3, 또는 CR4R5이고,Y 2 is O; S; NR 3 , or CR 4 R 5 ,
n은 각각 독립적으로 0 내지 4의 정수이고,n is each independently an integer from 0 to 4,
R1은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,R 1 is each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
R2 내지 R5는 각각 독립적으로 치환 또는 비치환된 C1-60 알킬; 또는 치환 또는 비치환된 C6-60 아릴이다.R 2 to R 5 are each independently substituted or unsubstituted C 1-60 alkyl; Or substituted or unsubstituted C 6-60 aryl.
또한, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer provides an organic light emitting device including the compound represented by Chemical Formula 1.
상술한 화학식 1로 표시되는 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있으며, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 상술한 화학식 1로 표시되는 화합물은 정공주입, 정공수송, 정공주입 및 수송, 발광, 전자수송, 또는 전자주입 재료로 사용될 수 있다.The compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or life characteristics in the organic light emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.
도 1은 기판(1), 양극(2), 발광층(3), 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(7), 전자수송층(8) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.Figure 2 shows an example of an organic light emitting device consisting of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron transport layer (8) and a cathode (4) Did.
도 3은 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(9), 발광층(7), 정공차단층(10), 전자수송층(8), 전자주입층(11) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (9), light emitting layer (7), hole blocking layer (10), electron transport layer (8) , It shows an example of an organic light-emitting device consisting of the electron injection layer 11 and the cathode (4).
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, it will be described in more detail in order to help the understanding of the present invention.
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by Formula 1 above.
본 명세서에서,
Figure PCTKR2019015362-appb-I000006
,
Figure PCTKR2019015362-appb-I000007
또는
Figure PCTKR2019015362-appb-I000008
는 다른 치환기에 연결되는 결합을 의미한다.In this specification,
Figure PCTKR2019015362-appb-I000006
,
Figure PCTKR2019015362-appb-I000007
or
Figure PCTKR2019015362-appb-I000008
Means a linkage to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 사이클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴포스핀기; 또는 N, O 및 S 원자 중 1개 이상을 포함하는 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In this specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2019015362-appb-I000009
Figure PCTKR2019015362-appb-I000009
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 25의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2019015362-appb-I000010
Figure PCTKR2019015362-appb-I000010
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In this specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2019015362-appb-I000011
Figure PCTKR2019015362-appb-I000011
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다.In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸,사이클로헥틸메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styrenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2019015362-appb-I000012
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,
Figure PCTKR2019015362-appb-I000012
It can be back. However, it is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 이종 원소로 O, N, Si 및 S 중 1개 이상을 포함하는 헤테로고리기로서, 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 헤테로고리기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 피리미딜기, 트리아진기, 트리아졸기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, but are not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기 중의 아릴기는 전술한 아릴기의 예시와 같다. 본 명세서에 있어서, 아르알킬기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기의 예시와 같다. 본 명세서에 있어서, 헤테로아릴아민 중 헤테로아릴은 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 아르알케닐기 중 알케닐기는 전술한 알케닐기의 예시와 같다. 본 명세서에 있어서, 아릴렌은 2가기인 것을 제외하고는 전술한 아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로아릴렌은 2가기인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 탄화수소 고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 아릴기 또는 사이클로알킬기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group. In the present specification, heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In this specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.
바람직하게는, 상기 E는 하기 화학식 3-1 내지 3-5 중 어느 하나로 표시될 수 있다:Preferably, E may be represented by any one of the following Chemical Formulas 3-1 to 3-5:
[화학식 3-1][Formula 3-1]
Figure PCTKR2019015362-appb-I000013
Figure PCTKR2019015362-appb-I000013
[화학식 3-2][Formula 3-2]
Figure PCTKR2019015362-appb-I000014
Figure PCTKR2019015362-appb-I000014
[화학식 3-3][Formula 3-3]
Figure PCTKR2019015362-appb-I000015
Figure PCTKR2019015362-appb-I000015
[화학식 3-4][Formula 3-4]
Figure PCTKR2019015362-appb-I000016
Figure PCTKR2019015362-appb-I000016
[화학식 3-5][Formula 3-5]
Figure PCTKR2019015362-appb-I000017
Figure PCTKR2019015362-appb-I000017
상기 화학식 3-1 내지 3-5에서,In Chemical Formulas 3-1 to 3-5,
Z는 각각 독립적으로 N 또는 CH이고, 단 Z 중 1 이상은 N이고,Z is each independently N or CH, provided that at least one of Z is N,
Ar3 및 Ar4는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,Ar 3 and Ar 4 are each independently substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
Ar5는 치환 또는 비치환된 C6-60 아릴이고,Ar 5 is substituted or unsubstituted C 6-60 aryl,
Y3은 O 또는 S이고,Y 3 is O or S,
m은 각각 독립적으로 0 내지 4의 정수이고,m are each independently an integer from 0 to 4,
R6은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이다.R 6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.
바람직하게는, Z는 모두 N일 수 있다.Preferably, Z can all be N.
바람직하게는, m은 각각 독립적으로 0 또는 1일 수 있다.Preferably, m can be each independently 0 or 1.
바람직하게는, R6은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 또는 치환 또는 비치환된 C6-20 아릴일 수 있으며, 보다 바람직하게는 수소; 중수소; 메틸; 또는 페닐일 수 있다.Preferably, R 6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-20 aryl, more preferably hydrogen; heavy hydrogen; methyl; Or phenyl.
바람직하게는, 상기 Ar3 및 Ar4는 각각 독립적으로 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다:Preferably, Ar 3 and Ar 4 may each independently be any one selected from the group consisting of:
Figure PCTKR2019015362-appb-I000018
Figure PCTKR2019015362-appb-I000018
보다 바람직하게는, 상기 Ar3 및 Ar4는 각각 독립적으로 페닐; 중수소로 치환된 페닐; 비페닐 또는 디벤조퓨라닐일 수 있다.More preferably, Ar 3 and Ar 4 are each independently phenyl; Phenyl substituted with deuterium; It can be biphenyl or dibenzofuranyl.
바람직하게는, Ar5는 치환 또는 비치환된 C6-20 아릴일 수 있으며, 보다 바람직하게는 페닐일 수 있다.Preferably, Ar 5 may be substituted or unsubstituted C 6-20 aryl, and more preferably phenyl.
예를 들면, 상기 E는 하기로 구성되는 군으로부터 선택될 수 있다:For example, E can be selected from the group consisting of:
Figure PCTKR2019015362-appb-I000019
Figure PCTKR2019015362-appb-I000019
상기에서,In the above,
Ar3 및 Ar4는 앞서 정의한 바와 같다.Ar 3 and Ar 4 are as defined above.
바람직하게는, 상기 화학식 2-4는 하기 화학식 4-1 내지 4-4 중 어느 하나로 표시될 수 있다:Preferably, the formula 2-4 may be represented by any one of the following formulas 4-1 to 4-4:
[화학식 4-1][Formula 4-1]
Figure PCTKR2019015362-appb-I000020
Figure PCTKR2019015362-appb-I000020
[화학식 4-2][Formula 4-2]
Figure PCTKR2019015362-appb-I000021
Figure PCTKR2019015362-appb-I000021
[화학식 4-3][Formula 4-3]
Figure PCTKR2019015362-appb-I000022
Figure PCTKR2019015362-appb-I000022
[화학식 4-4][Formula 4-4]
Figure PCTKR2019015362-appb-I000023
Figure PCTKR2019015362-appb-I000023
바람직하게는, X는 모두 N일 수 있다.Preferably, X can all be N.
바람직하게는, Ar1 및 Ar2는 각각 독립적으로 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다:Preferably, Ar 1 and Ar 2 may each independently be any one selected from the group consisting of:
Figure PCTKR2019015362-appb-I000024
Figure PCTKR2019015362-appb-I000024
바람직하게는, L은 단일결합, 페닐렌, 비페닐디일, 나프탈렌디일, 디벤조퓨란디일, 또는 디벤조티오펜디일일 수 있으며, 보다 바람직하게는 단일결합, 페닐렌, 나프탈렌디일 또는 디벤조티오펜디일일 수 있다.Preferably, L can be a single bond, phenylene, biphenyldiyl, naphthalenediyl, dibenzofurandiyl, or dibenzothiophendiyl, more preferably single bond, phenylene, naphthalenediyl or dibenzothiophendi It can be one day.
바람직하게는, n은 각각 독립적으로 0, 1 또는 2일 수 있다.Preferably, n can be each independently 0, 1 or 2.
바람직하게는, R1은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 또는 치환 또는 비치환된 C6-20 아릴일 수 있으며, 보다 바람직하게는 수소; 중수소; 또는 페닐일 수 있다.Preferably, R 1 is each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-20 aryl, more preferably hydrogen; heavy hydrogen; Or phenyl.
바람직하게는, R2 내지 R5는 각각 독립적으로 치환 또는 비치환된 C1-10 알킬; 또는 치환 또는 비치환된 C6-20 아릴일 수 있으며, 보다 바람직하게는 메틸 또는 페닐일 수 있다.Preferably, R 2 to R 5 are each independently substituted or unsubstituted C 1-10 alkyl; Or it may be a substituted or unsubstituted C 6-20 aryl, more preferably methyl or phenyl.
예를 들어, 상기 화학식 1로 표시되는 화합물은, 하기 화합물로 구성되는 군으로부터 선택될 수 있다:For example, the compound represented by Chemical Formula 1 may be selected from the group consisting of the following compounds:
Figure PCTKR2019015362-appb-I000025
Figure PCTKR2019015362-appb-I000025
Figure PCTKR2019015362-appb-I000026
Figure PCTKR2019015362-appb-I000026
Figure PCTKR2019015362-appb-I000027
Figure PCTKR2019015362-appb-I000027
Figure PCTKR2019015362-appb-I000028
Figure PCTKR2019015362-appb-I000028
Figure PCTKR2019015362-appb-I000029
Figure PCTKR2019015362-appb-I000029
Figure PCTKR2019015362-appb-I000030
Figure PCTKR2019015362-appb-I000030
Figure PCTKR2019015362-appb-I000031
Figure PCTKR2019015362-appb-I000031
Figure PCTKR2019015362-appb-I000032
Figure PCTKR2019015362-appb-I000032
Figure PCTKR2019015362-appb-I000033
Figure PCTKR2019015362-appb-I000033
Figure PCTKR2019015362-appb-I000034
Figure PCTKR2019015362-appb-I000034
Figure PCTKR2019015362-appb-I000035
Figure PCTKR2019015362-appb-I000035
Figure PCTKR2019015362-appb-I000036
Figure PCTKR2019015362-appb-I000036
Figure PCTKR2019015362-appb-I000037
Figure PCTKR2019015362-appb-I000037
Figure PCTKR2019015362-appb-I000038
Figure PCTKR2019015362-appb-I000038
Figure PCTKR2019015362-appb-I000039
Figure PCTKR2019015362-appb-I000039
한편, 상기 화학식 1로 표시되는 화합물은 일례로 하기 반응식 1과 같은 제조 방법으로 제조할 수 있다.On the other hand, the compound represented by the formula (1) may be prepared by the same method as in Scheme 1, for example.
[반응식 1][Scheme 1]
Figure PCTKR2019015362-appb-I000040
Figure PCTKR2019015362-appb-I000040
상기 반응식 1에서, 치환기에 대한 정의는 앞서 설명한 바와 같고, 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.In Reaction Scheme 1, the definition of the substituent is as described above, and the production method may be more specifically defined in the Production Example to be described later.
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다. 일례로, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물 층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and an organic light emitting device is provided. do.
본 발명의 유기 발광 소자의 유기물 층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물 층으로서 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include fewer organic layers.
또한, 상기 유기물 층은 정공주입층, 정공수송층, 정공 주입과 수송을 동시에 하는 층 또는 전자차단층을 포함할 수 있고, 상기 정공주입층, 정공수송층, 정공 주입과 수송을 동시에 하는 층 또는 전자차단층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer may include a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and transport, or an electron blocking layer, and the hole injection layer, a hole transport layer, and a layer or hole that simultaneously performs hole injection and transport The layer may include a compound represented by Formula 1 above.
또한, 상기 유기물 층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 이때, 상기 화학식 1로 표시되는 화합물은 발광층에서 호스트 물질로 사용될 수 있으며, 더욱 구체적으로, 상기 화학식 1로 표시되는 화합물은 녹색 유기 발광 소자의 발광층에 사용되는 호스트로 사용될 수 있다.In addition, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1. At this time, the compound represented by Formula 1 may be used as a host material in the light emitting layer, and more specifically, the compound represented by Formula 1 may be used as a host used in the light emitting layer of the green organic light emitting device.
또한, 상기 유기물 층은 정공차단층, 전자수송층, 전자주입층, 또는 전자수송 및 전자주입을 동시에 하는 층을 포함할 수 있고, 상기 정공차단층, 전자수송층, 전자주입층, 또는 전자수송 및 전자주입을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer may include a hole blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously performs electron transport and electron injection, and the hole blocking layer, electron transport layer, electron injection layer, or electron transport and electron The simultaneous injection layer may include a compound represented by Chemical Formula 1 above.
또한, 본 발명에 따른 유기 발광 소자는, 기판 상에 양극, 1층 이상의 유기물 층 및 음극이 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. 또한, 본 발명에 따른 유기 발광 소자는 기판 상에 음극, 1층 이상의 유기물 층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. 예컨대, 본 발명의 일실시예에 따른 유기 발광 소자의 구조는 도 1 내지 3에 예시되어 있다.Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 to 3.
도 1은 기판(1), 양극(2), 발광층(3), 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 발광층에 포함될 수 있다.1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(7), 전자수송층(8) 및 음극(4)로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공주입층, 정공수송층, 발광층 및 전자수송층 중 1층 이상에 포함될 수 있다.Figure 2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 Did. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.
도 3은 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(9), 발광층(7), 정공차단층(10), 전자수송층(8), 전자주입층(11) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공주입층, 정공수송층, 전자차단층, 발광층, 정공차단층, 전자수송층, 전자주입층 중 1층 이상에 포함될 수 있다.3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (9), light emitting layer (7), hole blocking layer (10), electron transport layer (8) , It shows an example of an organic light-emitting device consisting of the electron injection layer 11 and the cathode (4). In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer.
본 발명에 따른 유기 발광 소자는, 상기 유기물 층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. 또한, 상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다.The organic light-emitting device according to the present invention can be made of materials and methods known in the art, except that at least one layer of the organic material layer contains the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 발명에 따른 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다.For example, the organic light emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물 층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다.In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
일례로, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이거나, 또는 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다.In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.
상기 양극 물질로는 통상 유기물 층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
상기 정공주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물 층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정 되는 것은 아니다.The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer. A compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred. It is preferred that the high occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. , Organic anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다.The hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light-emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
상기 전자차단층은 상기 정공수송층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 정공 이동도를 조절하고, 전자의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 한다. 상기 전자차단층은 전자 차단 물질을 포함하고, 이러한 전자 차단 물질로는 발광층에서 전자가 흘러나오지 않을 수 있는 안정된 구조를 갖는 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility, prevent excessive movement of electrons, and increase the probability of hole-electron bonding, thereby increasing the efficiency of the organic light emitting device. It serves to improve. The electron blocking layer includes an electron blocking material, and a material having a stable structure in which electrons do not flow out of the light emitting layer is suitable as the electron blocking material. As a specific example, an arylamine-based organic material or the like may be used, but is not limited thereto.
상기 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다.As the light-emitting material, a material capable of emitting light in the visible region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다.The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.
상기 정공차단층은 상기 발광층 상에 형성되어, 구체적으로 상기 정공차단층은 발광층에 접하여 구비되어, 정공의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 한다. 상기 정공차단층은 정공 차단 물질을 포함하고, 이러한 정공 차단 물질로는 발광층에서 정공이 흘러나오지 않을 수 있는 안정된 구조를 갖는 물질이 적합하다. 상기 정공 차단 물질로는 트리아진을 포함한 아진류 유도체; 트리아졸 유도체; 옥사디아졸 유도체; 페난트롤린 유도체; 포스핀옥사이드 유도체 등의 전자흡인기가 도입된 화합물을 사용할 수 있으나, 이에 한정되는 것은 아니다.The hole blocking layer is formed on the light emitting layer, and specifically, the hole blocking layer is provided in contact with the light emitting layer, thereby preventing excessive movement of holes and increasing the probability of hole-electron bonding, thereby improving the efficiency of the organic light emitting device Do it. The hole blocking layer includes a hole blocking material, and as the hole blocking material, a material having a stable structure in which holes may not flow out of the light emitting layer is suitable. Examples of the hole blocking material include azine derivatives including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; Compounds in which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.
상기 전자수송층은 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material, as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 있으나, 이에 한정되지 않는다.The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, and bis(8-hydroxyquinolinato) manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
상기 화학식 1로 표시되는 화합물 및 이를 포함하는 유기 발광 소자의 제조는 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.The preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the invention, and the scope of the invention is not limited by them.
제조예 1: 화합물 A1의 제조Preparation Example 1 Preparation of Compound A1
Figure PCTKR2019015362-appb-I000041
Figure PCTKR2019015362-appb-I000041
1) 화합물 A1-1의 제조1) Preparation of Compound A1-1
질소 분위기에서 (4-chloro-2-fluorophenyl)boronic acid(20 g, 114.7 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(30.7 g, 114.7mmol)를 테트라하이드로 퓨란 400ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(47.6 g, 344.1mmol)를 물48 ml에 녹여 투입하고 충분히 교반한 후 테트라키스트리페닐-포스피노팔라듐(4 g, 3.4mmol)을 투입하였다. 3시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 830 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 흰색의 고체 화합물 A1-1(30.7g, 74%, MS: [M+H]+ = 362.8)을 제조하였다.(4-chloro-2-fluorophenyl)boronic acid (20 g, 114.7 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (30.7 g, 114.7 mmol) tetrahydrofuran in a nitrogen atmosphere It was put in 400 ml, stirred and refluxed. Thereafter, potassium carbonate (47.6 g, 344.1 mmol) was dissolved in 48 ml of water, stirred thoroughly, and then tetrakistriphenyl-phosphino palladium (4 g, 3.4 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and then the organic layer was distilled. This was again dissolved in 830 mL of 20 times chloroform, washed twice with water, and the organic layer was separated, and anhydrous magnesium sulfate was added, stirred, and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound A1-1 (30.7 g, 74%, MS: [M+H] + =362.8) by recrystallization of chloroform and ethyl acetate.
2) 화합물 A1-2의 제조2) Preparation of Compound A1-2
질소 분위기에서 A1-1(20 g, 55.3 mmol)와 비스(피나콜라토)디보론(21.8 g, 55.3mmol)를 Diox 400ml에 넣고 교반 및 환류하였다. 이 후 제3인산칼륨(35.2 g, 165.8mmol)를투입하고 충분히 교반한 후 팔라듐디벤질리덴아세톤팔라듐(1 g, 1.7mmol) 및 트리시클로헥실포스핀 (0.9 g, 3.3mmol) 을 투입하였다. 7시간 반응 후 상온으로 식인 후 유기층을 필터처리하여 염을 제거 한 후 걸러진 유기층을 증류하였다. 이를 다시 클로로포름 10 배 251 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에탄올재결정을 통해 흰색의 고체 화합물 A1-2(13g, 52%, MS: [M+H]+ = 454.3)을 제조하였다.In a nitrogen atmosphere, A1-1 (20 g, 55.3 mmol) and bis(pinacolato)diboron (21.8 g, 55.3 mmol) were added to 400 ml of Diox, stirred and refluxed. After this, potassium triphosphate (35.2 g, 165.8 mmol) was introduced and sufficiently stirred, and then palladium dibenzylidene acetone palladium (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. After 7 hours of reaction, after cooling to room temperature, the organic layer was filtered to remove salt, and then the filtered organic layer was distilled. This was again dissolved in 251 mL of 10 times chloroform, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound A1-2 (13 g, 52%, MS: [M+H] + = 454.3) through chloroform and ethanol recrystallization.
3) 화합물 A1의 제조3) Preparation of Compound A1
질소 분위기에서 A1-2(30 g, 66.2 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(17.7 g, 66.2mmol)를 테트라하이드로 퓨란 600ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(27.4 g, 198.5mmol)를 물27 ml에 녹여 투입하고 충분히 교반한 후 테트라키스트리페닐-포스피노팔라듐(2.3 g, 2mmol)을 투입하였다. 2시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 779 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 노란색의 고체 화합물 2-(4-chloro-2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine(20.3g, 52%, MS: [M+H]+ = 589.6)을 제조하였다.In a nitrogen atmosphere, A1-2 (30 g, 66.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (17.7 g, 66.2 mmol) were added to 600 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (27.4 g, 198.5 mmol) was dissolved in 27 ml of water, stirred thoroughly, and then tetrakistriphenyl-phosphino palladium (2.3 g, 2 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in 779 mL of 20 times chloroform, washed twice with water, and the organic layer was separated, and anhydrous magnesium sulfate was added, stirred, and filtered to distill the filtrate under reduced pressure. The concentrated compound is yellow solid compound 2-(4-chloro-2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine(20.3g, 52%, MS: through recrystallization of chloroform and ethyl acetate): [ M+H]+ = 589.6).
제조예 2: 화합물 B1의 제조Preparation Example 2: Preparation of compound B1
Figure PCTKR2019015362-appb-I000042
Figure PCTKR2019015362-appb-I000042
1) 화합물 B1-1의 제조1) Preparation of compound B1-1
질소 분위기에서 (4-chloro-2-fluorophenyl)boronic acid(40 g, 229.4 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(61.4 g, 229.4mmol)를 테트라하이드로 퓨란 800ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(95.1 g, 688.2mmol)를 물95 ml에 녹여 투입하고 충분히 교반한 후 테트라키스트리페닐-포스피노팔라듐(7.9 g, 6.9mmol)을 투입하였다. 1시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 1660 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 흰색의 고체 화합물 B1-1(53.1g, 64%, MS: [M+H]+ = 362.8)을 제조하였다.(4-chloro-2-fluorophenyl)boronic acid (40 g, 229.4 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (61.4 g, 229.4 mmol) tetrahydrofuran in a nitrogen atmosphere It was put into 800 ml, stirred and refluxed. Thereafter, potassium carbonate (95.1 g, 688.2 mmol) was dissolved in 95 ml of water, stirred thoroughly, and then tetrakistriphenyl-phosphino palladium (7.9 g, 6.9 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer and water layer were separated, and then the organic layer was distilled. This was again dissolved in 1660 mL of chloroform 20 times, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added and stirred, and the filtrate was distilled under reduced pressure. The concentrated compound was white solid compound B1-1 (53.1 g, 64%, MS: [M+H] + =362.8) through chloroform and ethyl acetate recrystallization.
2) 화합물 B1-2의 제조2) Preparation of compound B1-2
질소 분위기에서 B1-1(20 g, 55.3 mmol)와 9H-carbazole(9.2 g, 55.3mmol)를 다이메틸포름아마이드 400ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(15.9 g, 165.8mmol)를 투입하고 가온 및 교반하였다. 3시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 844 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 흰색의 고체 화합물 B1-2(17.2g, 61%, MS: [M+H]+ = 510)을 제조하였다.In a nitrogen atmosphere, B1-1 (20 g, 55.3 mmol) and 9H-carbazole (9.2 g, 55.3 mmol) were added to 400 ml of dimethylformamide, stirred and refluxed. After this, sodium tibutoxide (15.9 g, 165.8 mmol) was added and heated and stirred. After the reaction for 3 hours, the resulting solid was filtered after being cooled to room temperature. The solid was dissolved in 844 mL of chloroform 30 times, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a white solid compound B1-2 (17.2g, 61%, MS: [M+H]+ = 510).
3) 화합물 B1의 제조3) Preparation of compound B1
질소 분위기에서 B1-2(30 g, 58.9 mmol)와 비스(피나콜라토)디보론(23.3 g, 58.9mmol)를 Diox 600ml에 넣고 교반 및 환류하였다. 이 후 제3인산칼륨(37.5 g, 176.8mmol)를투입하고 충분히 교반한 후 팔라듐디벤질리덴아세톤팔라듐(1 g, 1.8mmol) 및 트리시클로헥실포스핀 (1 g, 3.5mmol) 을 투입하였다. 3시간 반응 후 상온으로 식인 후 유기층을 필터처리하여 염을 제거 한 후 걸러진 유기층을 증류하였다. 이를 다시 클로로포름 10 배 354 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에탄올재결정을 통해 흰색의 고체 화합물 B1(27.3g, 77%, MS: [M+H]+ = 601.5)을 제조하였다.In a nitrogen atmosphere, B1-2 (30 g, 58.9 mmol) and bis(pinacolato)diboron (23.3 g, 58.9mmol) were added to Diox 600ml, stirred and refluxed. After this, potassium triphosphate (37.5 g, 176.8 mmol) was introduced and sufficiently stirred, and then palladium dibenzylidene acetone palladium (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and then the filtered organic layer was distilled. This was again dissolved in 354 mL of chloroform 10 times, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound B1 (27.3 g, 77%, MS: [M+H] + = 601.5) through chloroform and ethanol recrystallization.
합성예 1: 화합물 1의 제조Synthesis Example 1: Preparation of compound 1
Figure PCTKR2019015362-appb-I000043
Figure PCTKR2019015362-appb-I000043
질소 분위기에서 A1(20 g, 35.8 mmol)와 7H-benzofuro[2,3-b]carbazole(9.2 g, 35.8mmol)를 다이메틸포름아마이드 400ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(10.3 g, 107.4mmol)를 투입하고 가온 및 교반하였다. 2시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 855 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 노랑의 고체 화합물1(16.8g, 59%, MS: [M+H]+ = 796.9)을 제조하였다.In a nitrogen atmosphere, A1 (20 g, 35.8 mmol) and 7H-benzofuro[2,3-b]carbazole (9.2 g, 35.8 mmol) were added to 400 ml of dimethylformamide, stirred and refluxed. After that, sodium tibutoxide (10.3 g, 107.4 mmol) was added and heated and stirred. After the reaction for 2 hours, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 855 mL of chloroform 30 times, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 1 (16.8g, 59%, MS: [M+H]+ = 796.9).
합성예 2: 화합물 2의 제조Synthesis Example 2: Preparation of compound 2
Figure PCTKR2019015362-appb-I000044
Figure PCTKR2019015362-appb-I000044
질소 분위기에서 A1(20 g, 35.8 mmol)와 9H-carbazole(6 g, 35.8mmol)를 다이메틸포름아마이드 400ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(10.3 g, 107.4mmol)를 투입하고 가온 및 교반하였다. 4시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 758 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물2(19g, 75%, MS: [M+H]+ = 706.8)을 제조하였다.In a nitrogen atmosphere, A1 (20 g, 35.8 mmol) and 9H-carbazole (6 g, 35.8 mmol) were added to 400 ml of dimethylformamide, stirred and refluxed. After that, sodium tibutoxide (10.3 g, 107.4 mmol) was added and heated and stirred. After the reaction for 4 hours, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 758 mL 30 times chloroform, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent compound 2 (19 g, 75%, MS: [M+H] + =706.8).
합성예 3: 화합물 3의 제조Synthesis Example 3: Preparation of compound 3
Figure PCTKR2019015362-appb-I000045
Figure PCTKR2019015362-appb-I000045
질소 분위기에서 A1(10 g, 17.9 mmol)와 1-phenyl-9H-carbazole(4.4 g, 17.9mmol)를 다이메틸포름아마이드 200ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(5.2 g, 53.7mmol)를 투입하고 가온 및 교반하였다. 3시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 420 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물3(9g, 64%, MS: [M+H]+ = 782.9)을 제조하였다.In a nitrogen atmosphere, A1 (10 g, 17.9 mmol) and 1-phenyl-9H-carbazole (4.4 g, 17.9 mmol) were added to 200 ml of dimethylformamide, stirred and refluxed. After this, sodium tibutoxide (5.2 g, 53.7 mmol) was added and heated and stirred. After the reaction for 3 hours, the resulting solid was filtered after being cooled to room temperature. The solid was dissolved in 30 times 420 mL of chloroform, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 3 (9 g, 64%, MS: [M+H] + =782.9).
합성예 4: 화합물 4의 제조Synthesis Example 4: Preparation of compound 4
Figure PCTKR2019015362-appb-I000046
Figure PCTKR2019015362-appb-I000046
질소 분위기에서 A1(10 g, 17.9 mmol)와 2-phenyl-9H-carbazole(4.4 g, 17.9mmol)를 다이메틸포름아마이드 200ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(5.2 g, 53.7mmol)를 투입하고 가온 및 교반하였다. 4시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 420 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물4(7g, 50%, MS: [M+H]+ = 782.9)을 제조하였다.In a nitrogen atmosphere, A1 (10 g, 17.9 mmol) and 2-phenyl-9H-carbazole (4.4 g, 17.9 mmol) were added to 200 ml of dimethylformamide, stirred and refluxed. After this, sodium tibutoxide (5.2 g, 53.7 mmol) was added and heated and stirred. After the reaction for 4 hours, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 30 times 420 mL of chloroform, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 4 (7 g, 50%, MS: [M+H] + =782.9).
합성예 5: 화합물 5의 제조Synthesis Example 5: Preparation of compound 5
Figure PCTKR2019015362-appb-I000047
Figure PCTKR2019015362-appb-I000047
질소 분위기에서 A1(10 g, 17.9 mmol)와 3-phenyl-9H-carbazole(4.4 g, 17.9mmol)를 다이메틸포름아마이드 200ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(5.2 g, 53.7mmol)를 투입하고 가온 및 교반하였다. 3시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 420 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물5(8.7g, 62%, MS: [M+H]+ = 782.9)을 제조하였다.In a nitrogen atmosphere, A1 (10 g, 17.9 mmol) and 3-phenyl-9H-carbazole (4.4 g, 17.9 mmol) were added to 200 ml of dimethylformamide, stirred and refluxed. After this, sodium tibutoxide (5.2 g, 53.7 mmol) was added and heated and stirred. After the reaction for 3 hours, the resulting solid was filtered after being cooled to room temperature. The solid was dissolved in 30 times 420 mL of chloroform, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 5 (8.7 g, 62%, MS: [M+H] + =782.9).
합성예 6: 화합물 6의 제조Synthesis Example 6: Preparation of compound 6
Figure PCTKR2019015362-appb-I000048
Figure PCTKR2019015362-appb-I000048
질소 분위기에서 A1(10 g, 17.9 mmol)와 4-phenyl-9H-carbazole(4.4 g, 17.9mmol)를 다이메틸포름아마이드 200ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(5.2 g, 53.7mmol)를 투입하고 가온 및 교반하였다. 4시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 420 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물6(7g, 50%, MS: [M+H]+ = 782.9)을 제조하였다.In a nitrogen atmosphere, A1 (10 g, 17.9 mmol) and 4-phenyl-9H-carbazole (4.4 g, 17.9 mmol) were added to 200 ml of dimethylformamide, stirred and refluxed. After this, sodium tibutoxide (5.2 g, 53.7 mmol) was added and heated and stirred. After the reaction for 4 hours, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 30 times 420 mL of chloroform, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 6 (7 g, 50%, MS: [M+H] + =782.9).
합성예 7: 화합물 7의 제조Synthesis Example 7: Preparation of compound 7
Figure PCTKR2019015362-appb-I000049
Figure PCTKR2019015362-appb-I000049
질소 분위기에서 A1(15 g, 26.9 mmol)와 7H-benzo[4,5]thieno[2,3-b]carbazole(7.3 g, 26.9mmol)를 다이메틸포름아마이드 300ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(7.7 g, 80.6mmol)를 투입하고 가온 및 교반하였다. 2시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 654 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물7(12g, 55%, MS: [M+H]+ = 813)을 제조하였다.In a nitrogen atmosphere, A1 (15 g, 26.9 mmol) and 7H-benzo[4,5]thieno[2,3-b]carbazole (7.3 g, 26.9 mmol) were placed in 300 ml of dimethylformamide, stirred and refluxed. After that, sodium tibutoxide (7.7 g, 80.6 mmol) was added and heated and stirred. After the reaction for 2 hours, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 654 mL of chloroform 30 times, washed twice with water, and the organic layer was separated, and anhydrous magnesium sulfate was added, stirred, and filtered to distill the filtrate under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 7 (12 g, 55%, MS: [M+H] + = 813).
합성예 8: 화합물 8의 제조Synthesis Example 8: Preparation of compound 8
Figure PCTKR2019015362-appb-I000050
Figure PCTKR2019015362-appb-I000050
질소 분위기에서 A1(15 g, 26.9 mmol)와 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole(7.6 g, 26.9mmol)를 다이메틸포름아마이드 300ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(7.7 g, 80.6mmol)를 투입하고 가온 및 교반하였다. 3시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 662 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물8(11.3g, 51%, MS: [M+H]+ = 822)을 제조하였다.In a nitrogen atmosphere, A1 (15 g, 26.9 mmol) and 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (7.6 g, 26.9 mmol) were placed in 300 ml of dimethylformamide, stirred and refluxed. . After that, sodium tibutoxide (7.7 g, 80.6 mmol) was added and heated and stirred. After the reaction for 3 hours, the resulting solid was filtered after being cooled to room temperature. The solid was dissolved in 662 mL of chloroform 30 times, washed twice with water, and the organic layer was separated, and anhydrous magnesium sulfate was added and stirred, followed by filtration to distill the filtrate under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent compound 8 (11.3 g, 51%, MS: [M+H] + =822).
합성예 9: 화합물 9의 제조Synthesis Example 9: Preparation of compound 9
Figure PCTKR2019015362-appb-I000051
Figure PCTKR2019015362-appb-I000051
질소 분위기에서 A1(15 g, 26.9 mmol)와 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole(8.9 g, 26.9mmol)를 다이메틸포름아마이드 300ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(7.7 g, 80.6mmol)를 투입하고 가온 및 교반하였다. 4시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 702 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물9(14.3g, 61%, MS: [M+H]+ = 872)을 제조하였다.In a nitrogen atmosphere, A1 (15 g, 26.9 mmol) and 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole (8.9 g, 26.9 mmol) were placed in 300 ml of dimethylformamide, stirred and refluxed. After that, sodium tibutoxide (7.7 g, 80.6 mmol) was added and heated and stirred. After the reaction for 4 hours, after cooling to room temperature, the resulting solid was filtered. The solid was added to 702 mL of chloroform 30 times to dissolve, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 9 (14.3 g, 61%, MS: [M+H] + = 872).
합성예 10: 화합물 10의 제조Synthesis Example 10: Preparation of compound 10
Figure PCTKR2019015362-appb-I000052
Figure PCTKR2019015362-appb-I000052
질소 분위기에서 A1(10 g, 17.9 mmol)와 2,7-diphenyl-9H-carbazole(5.7 g, 17.9mmol)를 다이메틸포름아마이드 200ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(5.2 g, 53.7mmol)를 투입하고 가온 및 교반하였다. 1시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 461 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물10(10g, 65%, MS: [M+H]+ = 858)을 제조하였다.In a nitrogen atmosphere, A1 (10 g, 17.9 mmol) and 2,7-diphenyl-9H-carbazole (5.7 g, 17.9 mmol) were added to 200 ml of dimethylformamide, stirred and refluxed. After this, sodium tibutoxide (5.2 g, 53.7 mmol) was added and heated and stirred. After the reaction for 1 hour, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 461 mL of chloroform 30 times, washed twice with water, and the organic layer was separated. After adding anhydrous magnesium sulfate and stirring, the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent colored solid compound 10 (10 g, 65%, MS: [M+H] + =858).
합성예 11: 화합물 11의 제조Synthesis Example 11: Preparation of compound 11
Figure PCTKR2019015362-appb-I000053
Figure PCTKR2019015362-appb-I000053
질소 분위기에서 A1(20 g, 35.8 mmol)와 3,6-diphenyl-9H-carbazole(11.4 g, 35.8mmol)를 다이메틸포름아마이드 400ml에 넣고 교반 및 환류하였다. 이 후 소듐티부톡사이드(10.3 g, 107.4mmol)를 투입하고 가온 및 교반하였다. 1시간 반응 후 상온으로 식인 후 생성된 고체를 여과하였다. 고체를 클로로포름 30 배 922 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 형광색의 고체 화합물11(15.7g, 51%, MS: [M+H]+ = 859)을 제조하였다.In a nitrogen atmosphere, A1 (20 g, 35.8 mmol) and 3,6-diphenyl-9H-carbazole (11.4 g, 35.8 mmol) were added to 400 ml of dimethylformamide, stirred and refluxed. After that, sodium tibutoxide (10.3 g, 107.4 mmol) was added and heated and stirred. After the reaction for 1 hour, after cooling to room temperature, the resulting solid was filtered. The solid was dissolved in 922 mL of chloroform 30 times, washed twice with water, and the organic layer was separated, and anhydrous magnesium sulfate was added and stirred, followed by filtration to distill the filtrate under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a fluorescent compound 11 (15.7 g, 51%, MS: [M+H] + = 859).
합성예 12: 화합물 12의 제조Synthesis Example 12: Preparation of compound 12
Figure PCTKR2019015362-appb-I000054
Figure PCTKR2019015362-appb-I000054
질소 분위기에서 B1(20 g, 33.3 mmol)와 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine(12.9 g, 33.3mmol)를 테트라하이드로 퓨란 400ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(13.8 g, 99.9mmol)를 물14 ml에 녹여 투입하고 충분히 교반한 후 비스(트리 터셔리-부틸포스핀)팔라듐(0.5 g, 1mmol)을 투입하였다. 1시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 521 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 형광색의 고체 화합물 12(13.5g, 52%, MS: [M+H]+ = 782.9)을 제조하였다.In a nitrogen atmosphere, B1 (20 g, 33.3 mmol) and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (12.9 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran and stirred and refluxed. Did. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer and water layer were separated, and then the organic layer was distilled. This was again dissolved in 521 mL of 20 times chloroform, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered to distill the filtrate under reduced pressure. A concentrated compound 12 (13.5 g, 52%, MS: [M+H] + =782.9) of fluorescent color was prepared by recrystallization of the concentrated compound using chloroform and ethyl acetate.
합성예 13: 화합물 13의 제조Synthesis Example 13: Preparation of compound 13
Figure PCTKR2019015362-appb-I000055
Figure PCTKR2019015362-appb-I000055
질소 분위기에서 B1(20 g, 33.3 mmol)와 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine(12.9 g, 33.3mmol)를 테트라하이드로 퓨란 400ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(13.8 g, 99.9mmol)를 물14 ml에 녹여 투입하고 충분히 교반한 후 비스(트리 터셔리-부틸포스핀)팔라듐(0.5 g, 1mmol)을 투입하였다. 2시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 521 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 형광색의 고체 화합물 13(14.6g, 56%, MS: [M+H]+ = 782.9)을 제조하였다.In a nitrogen atmosphere, B1 (20 g, 33.3 mmol) and 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (12.9 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran and stirred and refluxed. Did. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in 521 mL of 20 times chloroform, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered to distill the filtrate under reduced pressure. A concentrated compound 13 (14.6 g, 56%, MS: [M+H] + =782.9) of a fluorescent color was prepared by recrystallizing the concentrated compound from chloroform and ethyl acetate.
합성예 14: 화합물 14의 제조Synthesis Example 14: Preparation of compound 14
Figure PCTKR2019015362-appb-I000056
Figure PCTKR2019015362-appb-I000056
질소 분위기에서 B1(20 g, 33.3 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine(9.3 g, 33.3mmol)를 테트라하이드로 퓨란 400ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(13.8 g, 99.9mmol)를 물14 ml에 녹여 투입하고 충분히 교반한 후 비스(트리 터셔리-부틸포스핀)팔라듐(0.5 g, 1mmol)을 투입하였다. 1시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 479 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 형광색의 고체 화합물 14(17.7g, 74%, MS: [M+H]+ = 719.8)을 제조하였다.In a nitrogen atmosphere, B1 (20 g, 33.3 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (9.3 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, and the organic layer and water layer were separated, and then the organic layer was distilled. This was again dissolved in 479 mL of chloroform 20 times, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered to distill the filtrate under reduced pressure. A concentrated compound 14 (17.7 g, 74%, MS: [M+H] + =719.8) of fluorescent color was prepared by recrystallization of the concentrated compound using chloroform and ethyl acetate.
합성예 15: 화합물 15의 제조Synthesis Example 15: Preparation of compound 15
Figure PCTKR2019015362-appb-I000057
Figure PCTKR2019015362-appb-I000057
질소 분위기에서 B1(20 g, 33.3 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine(9.9 g, 33.3mmol)를 테트라하이드로 퓨란 400ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(13.8 g, 99.9mmol)를 물14 ml에 녹여 투입하고 충분히 교반한 후 비스(트리 터셔리-부틸포스핀)팔라듐(0.5 g, 1mmol)을 투입하였다. 3시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 489 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 형광색의 고체 화합물 15(15.7g, 64%, MS: [M+H]+ = 735.9)을 제조하였다.In a nitrogen atmosphere, B1 (20 g, 33.3 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (9.9 g, 33.3mmol) were added to 400 ml of tetrahydrofuran and stirred and refluxed. Did. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and then the organic layer was distilled. This was again dissolved in 489 mL of chloroform 20 times, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and filtered to distill the filtrate under reduced pressure. A concentrated compound 15 (15.7 g, 64%, MS: [M+H] + = 735.9) of a fluorescent color was prepared by recrystallizing the concentrated compound from chloroform and ethyl acetate.
합성예 16: 화합물 16의 제조Synthesis Example 16: Preparation of compound 16
Figure PCTKR2019015362-appb-I000058
Figure PCTKR2019015362-appb-I000058
질소 분위기에서 B1(20 g, 33.3 mmol)와 2-chlorobenzo[d]thiazole(5.6 g, 33.3mmol)를 테트라하이드로 퓨란 400ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(13.8 g, 99.9mmol)를 물14 ml에 녹여 투입하고 충분히 교반한 후 비스(트리 터셔리-부틸포스핀)팔라듐(0.5 g, 1mmol)을 투입하였다. 3시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 405 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 형광색의 고체 화합물 16(10.3g, 51%, MS: [M+H]+ = 608.7)을 제조하였다.In a nitrogen atmosphere, B1 (20 g, 33.3 mmol) and 2-chlorobenzo[d]thiazole (5.6 g, 33.3 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in 14 ml of water, stirred sufficiently, and bis(tri tertiary-butylphosphine)palladium (0.5 g, 1 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and then the organic layer was distilled. This was again dissolved in 405 mL of 20 times chloroform, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was prepared by chloroform and ethyl acetate recrystallization to prepare a solid compound 16 of fluorescent color (10.3 g, 51%, MS: [M+H] + =608.7).
[실험예][Experimental Example]
실험예 1Experimental Example 1
ITO(Indium Tin Oxide)가 1,400 Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.ITO (Indium Tin Oxide) was coated with a thin film coated with a thickness of 1,400 Å in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer Co. was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에, 하기 HT-A 화합물과 하기 PD 화합물을 95:5의 중량비로 100 Å의 두께로 열 진공 증착하고, 이어서 하기 HT-A 화합물만 1150 Å의 두께로 증착하여 정공수송층을 형성하였다. 상기 정공수송층 위에, 하기 HT-B 화합물을 450 Å의 두께로 열 진공 증착하여 전자차단층을 형성하였다. 상기 전자차단층 위에, 앞서 제조한 화합물 1과 하기 GD 화합물을 85:15의 중량비로 400 Å의 두께로 진공 증착하여 발광층을 형성하였다. 상기 발광층 위에, 하기 ET-A 화합물을 50 Å의 두께로 진공 증착하여 정공차단층을 형성하였다. 상기 정공차단층 위에, 하기 ET-B 화합물과 하기 Liq 화합물을 2:1의 중량비로 250 Å의 두께로 열 진공 증착하고, 이어서 LiF와 마그네슘을 1:1의 중량비로 30 Å의 두께로 진공 증착하여 전자 수송 및 주입층을 형성하였다. 상기 전자주입층 위에, 마그네슘과 은을 1:4의 중량비로 160 Å의 두께로 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.On the prepared ITO transparent electrode, the following HT-A compound and the following PD compound were thermally vacuum-deposited to a thickness of 100 로 at a weight ratio of 95:5, and then the following HT-A compound was deposited to a thickness of 1150 Å to form a hole transport layer. Formed. On the hole transport layer, the following HT-B compound was thermally vacuum-deposited to a thickness of 450 MPa to form an electron blocking layer. On the electron blocking layer, Compound 1 and the following GD compound prepared above were vacuum-deposited at a weight ratio of 85:15 to a thickness of 400 Pa to form a light emitting layer. On the light emitting layer, a hole blocking layer was formed by vacuum-depositing the following ET-A compound to a thickness of 50 MPa. On the hole blocking layer, the following ET-B compound and the following Liq compound were thermally vacuum-deposited to a thickness of 250 로 at a weight ratio of 2:1, and then vacuum-deposited LiF and magnesium at a thickness of 30 로 at a weight ratio of 1:1. To form an electron transport and injection layer. On the electron injection layer, magnesium and silver were deposited to a thickness of 160 4 in a weight ratio of 1:4 to form a cathode, thereby manufacturing an organic light emitting device.
Figure PCTKR2019015362-appb-I000059
Figure PCTKR2019015362-appb-I000059
상기의 과정에서 유기물의 증착속도는 0.4~0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3 Å/sec, 은과 마그네슘은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2×10-7 ~ 5×10-6 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 Å/sec for silver and magnesium, and 2 Å/sec for silver and magnesium. An organic light emitting device was manufactured by maintaining 10× 7 −5×10 −6 torr.
실험예 2 내지 16Experimental Examples 2 to 16
화합물 1 대신 하기 표 1에 기재된 화합물을 사용한 것을 제외하고는, 상기 실험예 1과 동일한 방법으로 유기 발광 소자를 제조하였다.An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 below was used instead of Compound 1.
비교실험예 1 내지 2Comparative Experimental Examples 1 to 2
화합물 1 대신 하기 표 1에 기재된 화합물을 사용한 것을 제외하고는, 상기 실험예 1과 동일한 방법으로 유기 발광 소자를 제조하였다. 하기 표 1에서, 화합물 GH-A 및 GH-B는 각각 하기와 같다.An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 below was used instead of Compound 1. In Table 1 below, the compounds GH-A and GH-B are as follows.
Figure PCTKR2019015362-appb-I000060
Figure PCTKR2019015362-appb-I000060
상기 실험예 및 비교실험예에서 제조한 유기 발광 에 전류를 인가하여 전압, 효율, 수명(T95)을 측정하고 그 결과를 하기 표 1에 나타내었다. 이때, 전압 및 효율은 10 mA/cm2의 전류 밀도를 인가하여 측정하였다. 또한, 하기 표 1의 T95은 전류 밀도 20 mA/cm2에서 초기 휘도가 95%로 저하할 때까지 측정한 시간을 의미한다.Voltage, efficiency, and lifetime (T95) were measured by applying a current to the organic luminescence prepared in the Experimental Examples and Comparative Experimental Examples, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm 2 . In addition, T95 in Table 1 below means the time measured until the initial luminance decreases to 95% at a current density of 20 mA/cm 2 .
Figure PCTKR2019015362-appb-T000001
Figure PCTKR2019015362-appb-T000001
화학식 1의 화합물은 분자 내에 전자 주개 역할을 하는 화학식 2-1 내지 화학식 2-4으로 표시되는 치환기와 전자 받개 역할을 하는 단환의 함질소헤테로고리가 서로 오쏘 위치에 결합되어 있어 intra charge transfer가 쉽게 이루어질 수 있다.In the compound of Formula 1, intra charge transfer is easy because the substituents represented by Formulas 2-1 to 2-4 that serve as electron donors and the monocyclic nitrogen-containing heterocycle that serves as the electron acceptor are bonded to each other at the ortho positions. It can be done.
또한 분자 내에 전자 받개 역할을 하는 단환의 함질소헤테로고리가 서로 파라 위치에 결합되어 있어 분자의 안정성이 높고, 정공과 전자 수송에 모두 유리하다.In addition, the monocyclic nitrogen-containing heterocycle that serves as an electron acceptor in the molecule is linked to each other at a para position, so that the stability of the molecule is high, and it is advantageous for both hole and electron transport.
따라서 상기 표 1에 나타난 바와 같이, 화학식 1의 화합물을 유기발광소자의 호스트로서 사용할 경우, 저전압, 고효율, 장수명의 특성이 나타남을 확인할 수 있다.Therefore, as shown in Table 1, when the compound of Formula 1 is used as a host for an organic light emitting device, it can be seen that characteristics of low voltage, high efficiency, and long life appear.
[부호의 설명][Description of codes]
1: 기판 2: 양극1: substrate 2: anode
3: 발광층 4: 음극3: light emitting layer 4: cathode
5: 정공주입층 6: 정공수송층5: hole injection layer 6: hole transport layer
7: 발광층 8: 전자수송층7: light emitting layer 8: electron transport layer
9: 전자차단층 10: 정공차단층9: electron blocking layer 10: hole blocking layer
11: 전자주입층11: Electronic injection layer

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019015362-appb-I000061
    Figure PCTKR2019015362-appb-I000061
    상기 화학식 1에서,In Chemical Formula 1,
    X는 각각 독립적으로 N 또는 CH이고, 단 X 중 2 이상은 N이고,X are each independently N or CH, provided that 2 or more of X are N,
    Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
    L은 단일결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 치환 또는 비치환된 C5-60 헤테로아릴렌이고,L is a single bond; Substituted or unsubstituted C 6-60 arylene; Or a substituted or unsubstituted C 5-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
    E는 N을 1 이상 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,E is a substituted or unsubstituted C 5-60 heteroaryl containing N or more,
    D는 하기 화학식 2-1 내지 2-4 중 어느 하나로 표시되는 치환기이고,D is a substituent represented by any one of the following formulas 2-1 to 2-4,
    [화학식 2-1][Formula 2-1]
    Figure PCTKR2019015362-appb-I000062
    Figure PCTKR2019015362-appb-I000062
    [화학식 2-2][Formula 2-2]
    Figure PCTKR2019015362-appb-I000063
    Figure PCTKR2019015362-appb-I000063
    [화학식 2-3][Formula 2-3]
    Figure PCTKR2019015362-appb-I000064
    Figure PCTKR2019015362-appb-I000064
    [화학식 2-4][Formula 2-4]
    Figure PCTKR2019015362-appb-I000065
    Figure PCTKR2019015362-appb-I000065
    상기 화학식 2-1 내지 2-4에서,In Chemical Formulas 2-1 to 2-4,
    A는 인접한 두 개의 오각 고리와 융합된 벤젠 고리이고,A is a benzene ring fused with two adjacent pentagonal rings,
    Y1은 O 또는 S이고,Y 1 is O or S,
    Y2는 O; S; NR3, 또는 CR4R5이고,Y 2 is O; S; NR 3 , or CR 4 R 5 ,
    n은 각각 독립적으로 0 내지 4의 정수이고,n is each independently an integer from 0 to 4,
    R1은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,R 1 is each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
    R2 내지 R5는 각각 독립적으로 치환 또는 비치환된 C1-60 알킬; 또는 치환 또는 비치환된 C6-60 아릴이다.R 2 to R 5 are each independently substituted or unsubstituted C 1-60 alkyl; Or substituted or unsubstituted C 6-60 aryl.
  2. 제1항에 있어서,According to claim 1,
    E는 하기 화학식 3-1 내지 3-5 중 어느 하나로 표시되는, 화합물:E is a compound represented by any one of the following formulas 3-1 to 3-5:
    [화학식 3-1][Formula 3-1]
    Figure PCTKR2019015362-appb-I000066
    Figure PCTKR2019015362-appb-I000066
    [화학식 3-2][Formula 3-2]
    Figure PCTKR2019015362-appb-I000067
    Figure PCTKR2019015362-appb-I000067
    [화학식 3-3][Formula 3-3]
    Figure PCTKR2019015362-appb-I000068
    Figure PCTKR2019015362-appb-I000068
    [화학식 3-4][Formula 3-4]
    Figure PCTKR2019015362-appb-I000069
    Figure PCTKR2019015362-appb-I000069
    [화학식 3-5][Formula 3-5]
    Figure PCTKR2019015362-appb-I000070
    Figure PCTKR2019015362-appb-I000070
    상기 화학식 3-1 내지 3-5에서,In Chemical Formulas 3-1 to 3-5,
    Z는 각각 독립적으로 N 또는 CH이고, 단 Z 중 1 이상은 N이고,Z is each independently N or CH, provided that at least one of Z is N,
    Ar3 및 Ar4는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이고,Ar 3 and Ar 4 are each independently substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
    Ar5는 치환 또는 비치환된 C6-60 아릴이고,Ar 5 is substituted or unsubstituted C 6-60 aryl,
    Y3은 O 또는 S이고,Y 3 is O or S,
    m은 각각 독립적으로 0 내지 4의 정수이고,m are each independently an integer from 0 to 4,
    R6은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 치환 또는 비치환된 C5-60 헤테로아릴이다.R 6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 5-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.
  3. 제2항에 있어서,According to claim 2,
    Ar3 및 Ar4는 각각 독립적으로 하기로 구성되는 군으로부터 선택되는 어느 하나인, 화합물:Ar 3 and Ar 4 are each independently any one selected from the group consisting of:
    Figure PCTKR2019015362-appb-I000071
    Figure PCTKR2019015362-appb-I000071
  4. 제2항에 있어서,According to claim 2,
    Ar5는 페닐인, 화합물.Ar 5 is phenyl.
  5. 제1항에 있어서,According to claim 1,
    상기 화학식 2-4는 하기 화학식 4-1 내지 4-4 중 어느 하나로 표시되는, 화합물:Formula 2-4 is a compound represented by any one of the following formulas 4-1 to 4-4:
    [화학식 4-1][Formula 4-1]
    Figure PCTKR2019015362-appb-I000072
    Figure PCTKR2019015362-appb-I000072
    [화학식 4-2][Formula 4-2]
    Figure PCTKR2019015362-appb-I000073
    Figure PCTKR2019015362-appb-I000073
    [화학식 4-3][Formula 4-3]
    Figure PCTKR2019015362-appb-I000074
    Figure PCTKR2019015362-appb-I000074
    [화학식 4-4][Formula 4-4]
    Figure PCTKR2019015362-appb-I000075
    Figure PCTKR2019015362-appb-I000075
  6. 제1항에 있어서,According to claim 1,
    X는 모두 N인, 화합물.A compound in which X is all N.
  7. 제1항에 있어서,According to claim 1,
    Ar1 및 Ar2는 각각 독립적으로 하기로 구성되는 군으로부터 선택되는 어느 하나인, 화합물.Ar 1 and Ar 2 are each independently any one selected from the group consisting of:
    Figure PCTKR2019015362-appb-I000076
    Figure PCTKR2019015362-appb-I000076
  8. 제1항에 있어서,According to claim 1,
    L은 단일결합, 페닐렌, 비페닐디일, 나프탈렌디일, 디벤조퓨란디일, 또는 디벤조티오펜디일인, 화합물.L is a single bond, phenylene, biphenyldiyl, naphthalenediyl, dibenzofurandiyl, or dibenzothiophendiyl.
  9. 제1항에 있어서,According to claim 1,
    상기 화학식 1로 표시되는 화합물은, 하기로 구성되는 군으로부터 선택되는 어느 하나인, 화합물:The compound represented by Formula 1 is any one selected from the group consisting of:
    Figure PCTKR2019015362-appb-I000077
    Figure PCTKR2019015362-appb-I000077
    Figure PCTKR2019015362-appb-I000078
    Figure PCTKR2019015362-appb-I000078
    Figure PCTKR2019015362-appb-I000079
    Figure PCTKR2019015362-appb-I000079
    Figure PCTKR2019015362-appb-I000080
    Figure PCTKR2019015362-appb-I000080
    Figure PCTKR2019015362-appb-I000081
    Figure PCTKR2019015362-appb-I000081
    Figure PCTKR2019015362-appb-I000082
    Figure PCTKR2019015362-appb-I000082
    Figure PCTKR2019015362-appb-I000083
    Figure PCTKR2019015362-appb-I000083
    Figure PCTKR2019015362-appb-I000084
    Figure PCTKR2019015362-appb-I000084
    Figure PCTKR2019015362-appb-I000085
    Figure PCTKR2019015362-appb-I000085
    Figure PCTKR2019015362-appb-I000086
    Figure PCTKR2019015362-appb-I000086
    Figure PCTKR2019015362-appb-I000087
    Figure PCTKR2019015362-appb-I000087
    Figure PCTKR2019015362-appb-I000088
    Figure PCTKR2019015362-appb-I000088
    Figure PCTKR2019015362-appb-I000089
    Figure PCTKR2019015362-appb-I000089
    Figure PCTKR2019015362-appb-I000090
    Figure PCTKR2019015362-appb-I000090
    Figure PCTKR2019015362-appb-I000091
    Figure PCTKR2019015362-appb-I000091
  10. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 제1항 내지 제9항 중 어느 하나의 항에 따른 화합물을 포함하는 것인, 유기 발광 소자.A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 9. That is, an organic light emitting device.
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