WO2019078461A1 - Novel heterocyclic compound and organic light-emitting device using same - Google Patents

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

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Publication number
WO2019078461A1
WO2019078461A1 PCT/KR2018/008980 KR2018008980W WO2019078461A1 WO 2019078461 A1 WO2019078461 A1 WO 2019078461A1 KR 2018008980 W KR2018008980 W KR 2018008980W WO 2019078461 A1 WO2019078461 A1 WO 2019078461A1
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group
substituted
unsubstituted
layer
compound
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PCT/KR2018/008980
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French (fr)
Korean (ko)
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하재승
김형석
황성석
이상우
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주식회사 엘지화학
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Priority claimed from KR1020180088200A external-priority patent/KR102103505B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880039540.7A priority Critical patent/CN110741001B/en
Publication of WO2019078461A1 publication Critical patent/WO2019078461A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

Definitions

  • the present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.
  • organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.
  • the organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research is proceeding.
  • the organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode.
  • the organic material layer may have a multilayer structure composed of different materials.
  • the organic material layer may include a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826 DISCLOSURE OF THE INVENTION
  • the present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.
  • the present invention provides a compound represented by the following formula (1).
  • Yi and Y 2 are each independently hydrogen, Substituted or unsubstituted alkyl; Substituted or unsubstituted C 6 -C 60 aryl; Or C 2 - 60 hetaroaryl containing one or more of substituted or unsubstituted 0, N, Si and S,
  • An and Ar 2 are each C independently represents a substituted or unsubstituted 6-60 aryl; Or C 2 - 60 heteroaryl containing at least one of substituted or unsubstituted O, N, Si and S, or A or Ar 2 is bonded to adjacent groups to form a condensed ring,
  • Each of Xi to ⁇ is independently N or CR 'with the proviso that at least one of them is N,
  • R ' is hydrogen; Or a substituted or unsubstituted d-60 alkyl,
  • L are each independently a direct bond; Substituted or unsubstituted C 6 - 60 arylene; Or C 2 - 60 heteroarylene containing any one of the hetero atoms selected from the group consisting of N, O, S and Si,
  • Ri to R 3 are each independently halogen; Time to come; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted d- 60 alkyl; Substituted or unsubstituted d-60 haloalkyl; Substituted or unsubstituted 60 thioalkyl; Substituted or unsubstituted d-60 alkoxy; Substituted or unsubstituted d-60 haloalkoxy; Substituted or unsubstituted C 3 - 60 cycloalkyl; Substituted or unsubstituted d-60 alkenyl; Substituted or unsubstituted C 6 -C 60 aryl; Substituted or unsubstituted C 6 -C 60 aryloxy; Or a substituted or unsubstituted C 2 - 60 heteroaryl containing at least one of O, N, Si and S
  • n is from 0 to 4
  • n is from 0 to 2
  • 0 0 to 3
  • the present invention also provides a plasma display panel comprising: a first electrode; A second electrode opposing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 do.
  • the compound represented by the general formula (1) can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting device.
  • the compound represented by Formula 1 can be used as a hole injecting, hole transporting, hole injecting and transporting, and light emitting material.
  • Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4.
  • FIG. 2 is a plan view of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a hole control layer 7, a light emitting layer 8, an electron control layer 9, And a cathode (4).
  • the present invention provides a compound represented by the above formula (1).
  • I and I mean a bond connected to another substituent.
  • the "substituent group to which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
  • the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • 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 in the ester group. 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,
  • the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.
  • the urea group specifically includes, but not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. Another According to the embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a n-propyl group, an isopropyl group, a butyl group, a n-butyl group, an isobutyl group, Pentyl, neopentyl, tert-pentyl, n-butyl, 1-methylpentyl, 2-methylpentyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylnucyl, 5-methylnucyl and the like.
  • the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms.
  • the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a phenyl group, a biphenyltriphenyl group or the like as the monocyclic aryl group, but is not limited thereto.
  • polycyclic aryl group examples include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.
  • a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. Wherein the fluorenyl group is substituted
  • the heterocyclic group is a heterocyclic group containing at least one of 0, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • heterocyclic group examples include a thiophene group, a furan group, a pyridine group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, an isoquinoline group, an indole group, an isoquinoline group, an isoquinoline group, an isoquinoline group, an isoquinoline group, an isoquinoline group, an isoquinoline group, A benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a phenanthroline group, an isooxazolyl group, a benzooxazolyl group, , A thiadiazolyl group, a
  • the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the exemplified aryl group.
  • the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above.
  • the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group.
  • the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group.
  • the description of the aryl group described above can be applied except that arylene is a divalent group.
  • the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group.
  • the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other.
  • the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other.
  • Y 1 and Y 2 may each independently be methyl or phenyl.
  • m, eta and 0 may be 0.
  • the formula (1) may be any one selected from compounds represented by the following formulas (1-1) to (1-10).
  • L are each independently a direct bond; Substituted or unsubstituted C 6 - 60 arylene; Or C 2 - 60 heteroarylene containing at least one heteroatom selected from the group consisting of N, O, S and Si,
  • An and Ar 2 are each C independently represents a substituted or unsubstituted 6-60 aryl; Or C 2 - 60 heteroaryl containing at least one of substituted or unsubstituted O, N, Si and S, or An or Ar 2 may be bonded to adjacent groups to form a condensed ring.
  • a and Ar 2 are each independently selected from the group consisting of
  • L may be independently selected from the group consisting of
  • the compound represented by the formula (1) may be any one selected from the group consisting of
  • the present invention relates to an organic A light emitting device.
  • the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 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 multilayer 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 hole control layer, a light emitting layer, an electron control layer, an electron transport layer, and 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 an electron transporting layer; An electron control layer; An electron injection layer; A hole blocking layer or a light emitting bulb, and the electron transporting layer; An electron control layer; An electron injection layer; The hole blocking layer or the light emitting layer includes the compound represented by the above formula (1).
  • the organic layer may include a light emitting layer, and the light emitting layer includes a compound represented by the general formula (1).
  • the organic material layer may include an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound represented by the above formula (1).
  • the electron transporting layer, the electron injecting layer, or the layer which simultaneously transports electrons and injects electrons includes the compound represented by the above formula (1).
  • the organic material layer is the electron transport layer, and including a light emitting layer and an electron transport layer may comprise a compound of the formula (1):
  • the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate.
  • the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate.
  • FIG. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4.
  • the compound represented by Formula 1 may be included in the light emitting layer.
  • . 2 is a plan view of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a hole control layer 7, a light emitting layer 8, an electron control layer 9, And a cathode (4).
  • the compound represented by Formula 1 may be contained in at least one of the hole injection layer, the hole transport layer, the hole control layer, the light emitting layer, the electron control layer, and the electron transport layer.
  • the organic light emitting device may further include a hole blocking layer or an electron injection layer. And the compound represented by Formula 1 may be included in the hole blocking layer or the electron injection layer.
  • the organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic layers includes a compound represented by the above formula (1).
  • the organic layers may be formed of the same material or different materials.
  • the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, a sputtering method or an e-beam evaporation method
  • a physical vapor deposition (PVD) method may be used to deposit a metal or A metal oxide having conductivity or an alloy thereof is deposited to form an anode, an organic material layer including a hole injecting charge, a hole transporting layer, a luminescent dopant and an electron transporting layer is formed on the anode, a material usable as a cathode is deposited thereon .
  • PVD physical vapor deposition
  • an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device.
  • the three-solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
  • an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material.
  • 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 and the second electrode is a cathode.
  • the anode material a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer.
  • the positive electrode material include metals such as vanadium chloride, copper, zinc and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (II), indium zinc oxide (IZO); ⁇ 0: ⁇ 1 SN0 or 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, no.
  • the negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include magnes, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, Metals such as aluminum, silver, tin and lead, or alloys thereof; Layer structure materials such as LiF / Al or LiO 2 / Al, but the present invention is not limited thereto.
  • the hole injecting material is a layer for injecting holes from the electrode.
  • the hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material.
  • a compound which prevents migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the ability to form a thin film is preferable.
  • the HOMOChighest occupied molecular orbital of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic layer.
  • the hole injecting material include a metal porphyrin, a thiophene, an organic material of an arylamine series, an organic material of a quinacridone series, a quinacridone series organic material, a perylene perylene based organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material.
  • a hole transport material Is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • the light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence.
  • the light emitting layer may include a host material and a dopant material.
  • the host material is a condensed aromatic ring derivative or a heterocyclic compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds.
  • heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group.
  • styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected 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.
  • the electron transporting material is a layer which transports electrons from the electron injecting layer to the light emitting layer.
  • the electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting dopant, Is suitable.
  • Specific examples include the A1 complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.
  • the electron transporting layer can be used with any desired cathode material as used according to the prior art.
  • a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, fox, ytterbium and samarium, in each case followed by an aluminum or silver layer.
  • the electron injection layer is a layer for injecting electrons from the electrode, And has an electron injecting effect from the cathode, an excellent electron injecting effect on the light emitting layer or the light emitting material, preventing migration of the excitons generated in the light emitting layer to the hole injecting layer, .
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, 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, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphthalato) gallium, and the like But is not limited thereto.
  • the organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.
  • B2-1 was synthesized in the same manner as in the synthesis of A2-1 except that 3-chlorobenzene-1,2-diol was used instead of 4-chlorobenzene-1,2-diol
  • A2-1 (25 g, 70.86 mmol) was dissolved in tetrahydrofuran (325 mL) under nitrogen atmosphere, and the temperature was stabilized and stirred at -10 ° C.
  • the solution is stirred at 0 ° C and then an aqueous solution of ammonium chloride (10.4 g, 194.85 ⁇ ol) dissolved in 100 ml of distilled water is slowly added thereto.
  • the NaOH solution was extracted with distilled water and diethyl ether, and the organic layer solution was dried with magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to prepare A3-1.
  • A3-2 was prepared by the same method except that phenylmagnesium bromide was used instead of methylmagnesium bromide in the synthesis of A3-1. Further, A4-2 was synthesized by the same method except that A3-2 was used instead of A3-1 in the synthesis of A4-1
  • A3-3 A4-3 A3-3 was prepared in the same manner except that A2-2 was used instead of A2-1 in the synthesis of the above A3-1. Further, A4-2 was synthesized by the same method except that A3-3 was used instead of A3-1 in the synthesis of A4-1
  • A3-4 was prepared in the same manner except that phenylmagnesium bromide was used instead of methylmagnesium bromide in the synthesis of A3-3. Further, A4-4 was prepared by synthesizing the same method except that A3-4 was used instead of A3-3 in the synthesis of A4-3
  • A4-2 A5-2 was synthesized by the same method except that A4-2 was used instead of A4-1 in the synthesis of the above A5-1
  • A5-3 was prepared by synthesizing the same method except that A4-3 was used instead of A4-1 in the synthesis of the above A5-1
  • A4-4 A5-4 was synthesized by the same method except that A4-4 was used instead of A4-1 in the synthesis of the above A5-1
  • B4-1 B5-1 B5-1 was synthesized by the same method except that B4-1 was used instead of A4-1 in the synthesis of the above A5-1
  • B4-2 B5-2 B5-2 was synthesized by the same method except that B4-2 was used instead of B4-1 in the synthesis of B5-1 above
  • B5-3 was prepared by the same method except for using B4-3 instead of B4-1 in the synthesis of B5-1
  • B4-4 B5-4 B5-4 was synthesized by the same method except that B4-4 was used instead of B4-1 in the synthesis of B5-1 above
  • A5-3 was used instead of A5-1 in the synthesis of the compound 1 and 2-chloro-4- (4-chlorophenyl) -6-phenyl-pyridine was used instead of 2- (3- 1,3,5-triazine was used to synthesize A6-1.
  • A5-3 was used instead of A5-1 in the synthesis of the compound 1 and 2-chloro-4- (9,9-dimethyl-9H-2- (3-chlorophenyl) Yl) -6-phenyl-1,3,5-triazine was used to prepare compound 5
  • B6-1 was synthesized by the same method except for using 2-chloro-4- (3-chlorophenyl) -6-phenyl-1,3,5-triazine instead of diphenyl pyrimidine.
  • a glass substrate (corning 7059 glass) coated with a thin film of 1,000 A thick indium tin oxide was placed in distilled water containing a dispersant and washed with ultrasonic waves.
  • the detergent was a product of Fischer Co.
  • the distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing with distilled water, isopropyl alcohol, acetone, and methane were ultrasonically washed and dried in the solvent order.
  • HAT hexanitrile hexaazatr iphenylene
  • an ETM1 compound (50A) is deposited on the light emitting layer as an electron control layer
  • Compound 1 synthesized in Production Example 4-1 and LiQ (1: 1) were co-deposited on the electron control layer to form an electron transporting layer having a thickness of 310A.
  • Lithium fluoride (LiF) having a thickness of 10 A and Mg and Ag (10: 1) having a thickness of 150 A were sequentially deposited on the electron transporting layer, and aluminum having a thickness of 1,000 A was deposited thereon to form a cathode.
  • the deposition rate of the organic material was maintained at 1 A / sec
  • the lithium fluoride was 0.2 A / sec
  • the aluminum was deposited at a deposition rate of 3 to 7 A / sec
  • An organic luminescent device was prepared in the same manner as in Example 1, except that the compound shown in the following Table 1 and LIQ were used in a specific ratio instead of Compound 1 and LIQ (1: 1) as the electron transport layer.
  • Example 17 An organic light emitting device was prepared in the same manner as in Example 1 except that Compound 1 was used instead of ETM1 as the electron control layer and ETM2 was used in place of Compound 1 in the electron donor.
  • hole injection layer 6 hole transport layer 7: hole control layer 8: light emission

Abstract

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

Description

【발명의 명칭】  Title of the Invention
신규한 헤테로 고리 화합물 및 이를 이용한 유기발광 소자  Novel heterocyclic compounds and organic light emitting devices using the same
【기술분야] [Technical Field]
관련 출원 (들)과의 상호 인용 Cross-reference with related application (s)
본 출원은 2017년 10월 18일자 한국 특허 출원 게 10-2017-0135361호 및2018년 7월 27일자 한국 특허 출원 제 10-2018-0088200호에 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. 10-2017-0135361, October 18, 2017, and Korean Patent Application No. 10-2018-0088200, July 27, 2018, The entire contents of which are incorporated herein by reference.
본 발명은 신규한 헤테로 고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.  The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.
【발명의 배경이 되는 기술】 TECHNICAL BACKGROUND OF THE INVENTION
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각， 우수한 콘트라스트， 빠른 웅답 시간을 가지며， 휘도， 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. 유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며， 예컨대 정공추입층， 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 액시톤 (exc on)이 형성되며， 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. 상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다. 【선행기술문헌】 In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research is proceeding. The organic light emitting device generally has a structure including an anode and a cathode, and an organic 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 may have a multilayer structure composed of different materials. For example, the organic material layer may include a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, and an exciton is formed when the injected holes and electrons meet each other. When the exciton falls back to the ground state, it will emit light. There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices. [Prior Art Document]
【특허문헌】  [Patent Literature]
(특허문헌 0001) 한국특허 공개번호 게 10-2000-0051826호 【발명의 내용】  (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 DISCLOSURE OF THE INVENTION
【해결하고자 하는 과제】  [Problem to be solved]
본 발명은 신규한 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다. 【과제의 해결 수단】  The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same. MEANS FOR SOLVING THE PROBLEMS
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.  The present invention provides a compound represented by the following formula (1).
Figure imgf000003_0001
Figure imgf000003_0001
상기 화학식 1에서，  In Formula 1,
Yi 및 Y2는 각각 독립적으로 수소; 치환 또는 비치환된 알킬; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 0， N, Si 및 S 중 1개 이상을 포함하는 C2-60 혜테로아릴이고， Yi and Y 2 are each independently hydrogen, Substituted or unsubstituted alkyl; Substituted or unsubstituted C 6 -C 60 aryl; Or C 2 - 60 hetaroaryl containing one or more of substituted or unsubstituted 0, N, Si and S,
An 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 치환 또는 비치환된 0， N, Si 및 S 중 1개 이상을 포함하는 C2-60 헤테로아릴이거나， 또는 A 또는 Ar2는 서로 인접하는 기와 결합하여 축합 고리를 형성하고， An and Ar 2 are each C independently represents a substituted or unsubstituted 6-60 aryl; Or C 2 - 60 heteroaryl containing at least one of substituted or unsubstituted O, N, Si and S, or A or Ar 2 is bonded to adjacent groups to form a condensed ring,
Xi 내지 ¾은 각각 독립적으로 N 또는 CR' 이고， 단， 이들 중 하나 이상이 N이고，  Each of Xi to 은 is independently N or CR 'with the proviso that at least one of them is N,
R' 은 수소; 또는 치환또는 비치환된 d-60의 알킬이고，  R 'is hydrogen; Or a substituted or unsubstituted d-60 alkyl,
L은 각각 독립적으로 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 N, 0， S 및 Si로 구성되는 군으로부터 선택되는 어느 하나미상의 헤테로 원자를 포함하는 C2-60 헤테로아릴렌이고， L are each independently a direct bond; Substituted or unsubstituted C 6 - 60 arylene; Or C 2 - 60 heteroarylene containing any one of the hetero atoms selected from the group consisting of N, O, S and Si,
Ri 내지 R3은 각각 독립적으로 할로겐; 히도록시기; 시아노; 니트릴; 니트로 ; 아미노; 치환 또는 비치환된 d-60 알킬 ; 치환 또는 비치환된 d-60 할로알킬 ; 치환 또는 비치환된 60 티오알킬 ; 치환 또는 비치환된 d-60 알콕시 ; 치환 또는 비치환된 d-60 할로알콕시 ; 치환 또는 비치환된 C3-60 사이클로알킬 ; 치환 또는 비치환된 d-60 알케닐; 치환 또는 비치환된 C6-60 아릴; 치환 또는 비치환된 C6-60 아릴옥시; 또는 치환 또는 비치환된 0， N , Si 및 S 중 1개 이상을 포함하는 C2-60 헤테로아릴이고， Ri to R 3 are each independently halogen; Time to come; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted d- 60 alkyl; Substituted or unsubstituted d-60 haloalkyl; Substituted or unsubstituted 60 thioalkyl; Substituted or unsubstituted d-60 alkoxy; Substituted or unsubstituted d-60 haloalkoxy; Substituted or unsubstituted C 3 - 60 cycloalkyl; Substituted or unsubstituted d-60 alkenyl; Substituted or unsubstituted C 6 -C 60 aryl; Substituted or unsubstituted C 6 -C 60 aryloxy; Or a substituted or unsubstituted C 2 - 60 heteroaryl containing at least one of O, N, Si and S,
m은 0 내지 4이고，  m is from 0 to 4,
n은 0 내지 2이고，  n is from 0 to 2,
0는 0 내지 3이고，  0 is 0 to 3,
z는 1 내지 4이고， 단 o+z는 4 이하이다. . 또한， 본 발명은 제 1 전극; 상기 제 1 전극과 대향하여 구비된 게 2 전극; 및 상기 제 1 전극과 상기 제 2 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.  z is 1 to 4, provided that o + z is 4 or less. . The present invention also provides a plasma display panel comprising: a first electrode; A second electrode opposing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 do.
【발명의 효과】 【Effects of the Invention】
상술한 화학식 1로 표시되는 화합물은 유기 발광 소자의 유기물 층의 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 재료로 사용될 수 있다.  The compound represented by the general formula (1) can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting device. In particular, the compound represented by Formula 1 can be used as a hole injecting, hole transporting, hole injecting and transporting, and light emitting material.
【도면의 간단한 설명】 BRIEF DESCRIPTION OF THE DRAWINGS
도 1은 기판 ( 1)， 양극 (2)， 발광층 (3) , 음극 (4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.  Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
도 2는 기판 ( 1 ) , 양극 (2)， 정공주입층 (5)， 정공수송층 (6)， 정공조절층 (7)， 발광층 (8)， 전자조절층 (9)， 전자수송층 ( 10 ) 및 음극 (4)로 이루어진 유기 발광 소자의 예를 도시한 것이다. 【발명을 실시하기 위한 구체적인 내용】  2 is a plan view of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a hole control layer 7, a light emitting layer 8, an electron control layer 9, And a cathode (4). DETAILED DESCRIPTION OF THE INVENTION
이하， 본 발명의 이해를 돕기 위하여 보다상세히 설명한다. 본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다. Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention. The present invention provides a compound represented by the above formula (1).
본 명세서에서， I 및 는 다른 치환기에 연결되는 결합을 의미한다. 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 , 0 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. 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 the present specification, I and I mean a bond connected to another substituent. As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected. In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure imgf000005_0001
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.
Figure imgf000006_0001
본 명세서에 있어서， 이미드기의 탄소수는 특별히 한정되지 않으나， 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의
Figure imgf000005_0001
In the present specification, 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 in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure imgf000006_0001
In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically,
.화합물이 될 수 있으나, 이에 한정되는 것은 아니다. But are not limited to, compounds.
Figure imgf000006_0002
본 명세서에 있어서， 실릴기는 구체적으로 트리메틸실릴기， 트리에틸실릴기， t-부틸디메틸실릴기， 비닐디메틸실릴기， 프로필디메틸실릴기， 트리페닐실릴기， 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. 본 명세서에 있어서， ^소기는 구체적으로 트리메틸붕소기， 트리에틸붕소기， t-부틸디메틸붕소기， 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다. 본 명세서에 있어서, 할로겐기의 예로는 불소， 염소， 브름 또는 요오드가 있다. 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， 핵실， n-핵실, 1-메틸펜틸， 2-메틸펜틸， 4-메틸 -2-펜틸， 3 , 3-디메틸부틸， 2-에틸부틸， 헵틸， n-헵틸， 1-메틸핵실， 사이클로펜틸메틸，사이클로핵틸메틸, 옥틸， n-옥틸， tert-옥틸， 1-메틸헵틸， 2-에틸핵실， 2-프로필펜틸, n-노닐， 2 , 2-디메틸헵틸， 1-에틸-프로필， 1，1- 디메틸-프로필， 이소핵실， 2-메틸펜틸， 4-메틸핵실， 5-메틸핵실 등이 있으나， 이들에 한정되지 않는다. 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. 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， 사이클로핵실， 3-메틸사이클로핵실， 4-메틸사이클로핵실， 2 , 3- 디메틸사이클로핵실， 3 , 4, 5-트리메틸사이클로핵실， 4-tert-부틸사이클로핵실, 사이클로헵틸， 사이클로옥틸 등이 있으나， 이에 한정되지 않는다. 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 있으나ᅳ 이에 한정되는 것은 아니다. 본 명세서에 있어서， 플루오레닐기는 치환될 수 있고， 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는
Figure imgf000006_0002
In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto. In the present specification, the urea group specifically includes, but not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group. In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine. In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. Another According to the embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a n-propyl group, an isopropyl group, a butyl group, a n-butyl group, an isobutyl group, Pentyl, neopentyl, tert-pentyl, n-butyl, 1-methylpentyl, 2-methylpentyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylnucyl, 5-methylnucyl and the like. In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another 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, Butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl and styrenyl groups. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyltriphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group. In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. Wherein the fluorenyl group is substituted
Figure imgf000008_0001
Figure imgf000008_0001
등이 될 수 있다. 다만, 이에 한정되는 것ᅳ은 아니다. 본 명세서에 있어서， 헤테로고리기는 이종 원소로 0， N , Si 및 S 중 1개 이상을 포함하는 헤테로고리기로서， 탄소수는 특별히 한정되지 않으나， 탄소수 2 내지 60인 것이 바람직하다. 헤테로고리기의 예로는 티오펜기， 퓨란기， 피를기， 이미다졸기， 티아졸기， 옥사졸기， 옥사디아졸기， 트리아졸기， 피리딜기, 비피리딜기， 피리미딜기， 트리아진기， 아크리딜기, 피리다진기， 피라지닐기， 퀴놀리닐기， 퀴나졸린기， 퀴녹살리닐기， 프탈라지닐기， 피리도 피리미디닐기， 피리도 피라지닐기， 피라지노 피라지닐기， 이소퀴놀린기， 인돌기, 카바졸기， 벤조옥사졸기， 벤조이미다졸기， 벤조티아졸기， 벤조카바졸기， 벤조티오펜기, 디벤조티오펜기， 벤조퓨라닐기， 페난쓰를린기 (phenanthrol ine) , 이소옥사졸릴기， 티아디아졸릴기 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나， 이들에만 한정되는 것은 아니다. 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. 한편， 상기 화학식 1에서， Yi 및 Y2는 각각 독립적으로 메틸 또는 페닐일 수 있다. ' 상기 화학식 1에서， m, η 및 0는 0일 수 있다. 상기 화학식 1에서, ζ는 1일 수 있다. 상기 화학식 1은 하기 화학식 1-1 내지 1-10으로 표시되는 화합물 중에서 선택되는 어느 하나일 수 있다. And the like. However, it is not limited to this. In the present specification, the heterocyclic group is a heterocyclic group containing at least one of 0, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyridine group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, an isoquinoline group, an indole group, an isoquinoline group, an isoquinoline group, an isoquinoline group, an isoquinoline group, an isoquinoline group, A benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a phenanthroline group, an isooxazolyl group, a benzooxazolyl group, , A thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto no. In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the exemplified aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other. In Formula 1, Y 1 and Y 2 may each independently be methyl or phenyl. In the above formula (1), m, eta and 0 may be 0. In the above formula (1),? May be 1. The formula (1) may be any one selected from compounds represented by the following formulas (1-1) to (1-10).
[화학식 1—1] [Formula 1-1]
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0004
Figure imgf000011_0001
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0004
Figure imgf000011_0001
[화학식 1-9] [Chemical Formula 1-9]
Figure imgf000012_0001
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0002
상기 화학식 1ᅳ 1 내지 1-10에서，  In the above Chemical Formulas 1 to 1-10,
L은 각각 독립적으로 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 N, 0， S 및 Si로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로 원자를 포함하는 C2-60 헤테로아릴렌이고， L are each independently a direct bond; Substituted or unsubstituted C 6 - 60 arylene; Or C 2 - 60 heteroarylene containing at least one heteroatom selected from the group consisting of N, O, S and Si,
An 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 치환 또는 비치환된 0， N , Si 및 S 중 1개 이상을 포함하는 C2-60 헤테로아릴이거나， 또는 An 또는 Ar2는 서로 인접하는 기와 결합하여 축합 고리를 형성할 수 있다. 바람직하게는, A 및 Ar2는 각각 독립적으로 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다. An and Ar 2 are each C independently represents a substituted or unsubstituted 6-60 aryl; Or C 2 - 60 heteroaryl containing at least one of substituted or unsubstituted O, N, Si and S, or An or Ar 2 may be bonded to adjacent groups to form a condensed ring. Preferably, A and Ar 2 are each independently selected from the group consisting of
Figure imgf000013_0001
Figure imgf000013_0001
 
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000015_0002
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000017_0001
바람직하게는， L은 각각 독립적으로 하기로 구성되는 군으로부터 선택 하나일 수 있다. Preferably, L may be independently selected from the group consisting of
Figure imgf000018_0001
Figure imgf000018_0001
바람직하게는, 상기 화학식 1로 표시되는 화합물은， 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다. Preferably, the compound represented by the formula (1) may be any one selected from the group consisting of
Figure imgf000019_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0001
W0 2019/078461 W0 2019/078461
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000032_0001
//: O8ϊ02Μ12AV //: O 8 ϊ0 2 M12AV
Figure imgf000034_0001
Figure imgf000034_0001
PC^KR2018/008980 PC ^ KR2018 / 008980
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000037_0001
Li Li
Figure imgf000038_0001
86800/8l0iH¾/XJd
Figure imgf000038_0001
86800 / 8l0iH¾ / XJd
I9f8. /6I0∑; I9f8. / 6I0Σ;
Figure imgf000039_0001
Figure imgf000039_0001

Figure imgf000040_0001

Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000042_0001
41 41
Figure imgf000043_0001
Figure imgf000043_0001
42 42
Figure imgf000044_0001
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000044_0002
43
Figure imgf000045_0001
43
Figure imgf000045_0001
// O8ϊ02Μ12A // O 8ϊ0 2M12A
Figure imgf000046_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
6P
Figure imgf000048_0001
Figure imgf000049_0001
6P
Figure imgf000050_0001
Figure imgf000050_0001
T9 8Z,0/6T0∑: OAV
Figure imgf000051_0001
T9 8Z, 0 / 6T0Σ: OAV
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000052_0001
51 P51 P
WO 2019/078461WO 2019/078461
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000056_0001
55 55
Figure imgf000057_0001
Figure imgf000057_0001
 
Figure imgf000058_0001
Figure imgf000058_0001
086800/8r0i¾¾/XJd 2S 086800 / 8r0i¾¾ / XJ d 2S
Figure imgf000059_0001
Figure imgf000059_0001
86800/8I0^DI/ljd 86800 / 810D / DI / dj d
t9f8LO/6roz: O
Figure imgf000060_0001
t9F8LO / 6roz: O
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
0868
Figure imgf000061_0001
Figure imgf000062_0001
0868
Figure imgf000063_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000065_0001
64 64
Figure imgf000066_0001
Figure imgf000066_0001
65
Figure imgf000067_0001
65
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000069_0001
086800/8lo¾/al:><l 086800 / 8lo¾ / al:>< l
Figure imgf000070_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000072_0001
71 71
Figure imgf000073_0001
Figure imgf000073_0001
72
Figure imgf000074_0001
72
Figure imgf000074_0001
//: O8ϊ02Μ12AV //: O 8 ϊ0 2 M12AV
Figure imgf000075_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000076_0001
086800/8ΐΟΖΗΜ/Χ3<Ι Ϊ9178Ζ.0/6Ϊ0Ζ OAV 086800 / 8ΐΟΖΗΜ / Χ3 <Ι Ϊ9178ZZ.0 / 6Ϊ0Ζ OAV
Figure imgf000077_0001
Figure imgf000077_0001
76
Figure imgf000078_0001
76
Figure imgf000078_0001
8/. 8/.
Figure imgf000079_0001
Figure imgf000079_0001
086800/810^3¾/13<1 Ϊ9^8Ζ.0/6Ϊ0Ζ OAV 086800/810 ^ 3¾ / 13 <1 Ϊ9 ^ 8 Ζ.0 / 6Ϊ0Ζ OAV
Figure imgf000080_0001
Figure imgf000080_0001

Figure imgf000081_0001

Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000083_0001
086800/8lOZMM/X3d Ϊ9^8Ζ.0/6Ϊ0Ζ OAV
Figure imgf000084_0001
Figure imgf000085_0001
086800 / 8lOZMM / X3d Ϊ9 ^ 8 Ζ.0 / 6Ϊ0Ζ OAV
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000086_0001
85 85
Figure imgf000087_0001
Figure imgf000087_0001
86
Figure imgf000088_0001
86
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000089_0001
88 //: O8ϊ02Μ12AV 88 //: O 8 ϊ0 2 M12AV
Figure imgf000090_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000091_0001
90 90
Figure imgf000092_0001
Figure imgf000092_0001
상기 화학식 1로 표시되는 화합물은 일례로 각각 하기 반응식 1 및 2와 같은 제조 방법으로 제조할 수 있다. 상기 제조 방법은 후술할 제조예에서 보다구체화될 수 있다.
Figure imgf000093_0001
상기 반웅식 1 및 2에서， L, Xi, ¾， ， An, 및 Ar2에 대한 설명은 한 바와 같다. 또한， 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다. 일례로， 본 발명은 제 1 전극; 상기 제 1 전극과 대향하여 구비된 제 2 전극; 및 상기 제 1 전극과 상기 게 2 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. 본 발명의 유기 발광 소자의 유기물 층은 단충 구조로 이루어질 수도 있으나， 2충 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대， 본 발명의 유기 발광 소자는 유기물 층으로서 정공주입층， 정공수송층， 정공조절층， 발광층， 전자조절층， 전자수송층， 전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기층을 포함할수 있다. 또한， 상기 유기물 층은 전자수송층; 전자조절층; 전자주입층; 정공차단층 또는 발광충을 포함할 수 있고, 상기 전자수송층; 전자조절층; 전자주입층; 정공차단층 또는 발광층은 상기 화학식 1로 표시되는 화합물을 포함한다. 또한， 상기 유기물 층은 발광층을 포함할 수 있고， 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함한다. 또한， 상기 유기물 층은 전자수송층， 또는 전자주입층을 포함할 수 있고， 상기 전자수송층， 또는 전자주입층은 상기 화학식 1로 표시되는 화합물을 포함한다. 또한, 상기 전자수송층, 전자주입층， 또는 전자수송 및 전자주입을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함한다. 또한， 상기 유기물 층은 발광층 및 전자수송층을 포함하고， 상기 전자수송층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다 : 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 및 2에 예시되어 있다. 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. The compounds represented by the above formula (1) can be prepared, for example, according to the following reaction schemes 1 and 2, respectively. The above production method can be more specific in the production example to be described later.
Figure imgf000093_0001
In the above Equations 1 and 2, L, Xi, ¾, An, and Ar 2 are as described. In addition, the present invention relates to an organic A light emitting device is provided. In one embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 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 multilayer 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 hole control layer, a light emitting layer, an electron control layer, an electron transport layer, and 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. The organic material layer may include an electron transporting layer; An electron control layer; An electron injection layer; A hole blocking layer or a light emitting bulb, and the electron transporting layer; An electron control layer; An electron injection layer; The hole blocking layer or the light emitting layer includes the compound represented by the above formula (1). In addition, the organic layer may include a light emitting layer, and the light emitting layer includes a compound represented by the general formula (1). The organic material layer may include an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound represented by the above formula (1). Further, the electron transporting layer, the electron injecting layer, or the layer which simultaneously transports electrons and injects electrons includes the compound represented by the above formula (1). In addition, the organic material layer is the electron transport layer, and including a light emitting layer and an electron transport layer may comprise a compound of the formula (1): In addition, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.
. 도 2는 기판 (1)， 양극 (2)， 정공주입층 (5), 정공수송층 (6)， 정공조절층 (7)， 발광층 (8)， 전자조절층 (9)， 전자수송층 (10) 및 음극 (4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공주입층， 정공수송층， 정공조절층， 발광층， 전자조절층 및 전자수송층 중 1층 이상에 포함될 수 있다. 또한， 상기 유기 발광 소자는 정공차단층 또는 전자주입층 등을 더 -. 포함할 수 있으며， 상기 화학식 1로 표시되는 화합물은 상기 정공차단층 또는 전자주입층에 포함될 수 있다. 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. 예컨대， 본 발명에 따른 유기 발광 소자는 기판 상에 제 1 전극， 유기물층 및 게 2 전극을 순차적으로 적층시켜 제조할 수 있다. 이때， 스퍼터링법 (sputtering)이나 전자빔 증발법 (e_beam evaporation)과 같은 . 2 is a plan view of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a hole control layer 7, a light emitting layer 8, an electron control layer 9, And a cathode (4). In such a structure, the compound represented by Formula 1 may be contained in at least one of the hole injection layer, the hole transport layer, the hole control layer, the light emitting layer, the electron control layer, and the electron transport layer. The organic light emitting device may further include a hole blocking layer or an electron injection layer. And the compound represented by Formula 1 may be included in the hole blocking layer or the electron injection layer. The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic layers includes a compound represented by the above formula (1). In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials. For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, a sputtering method or an e-beam evaporation method
PVD(physical Vapor Deposit ion)방법을 이용하여， 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고， 그 위에 정공주입충， 정공수송층， 발광충 및 전자수송층을 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. 또한， 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 와하여 유기물 층으로 형성될 수 있다. 여기세 용액 도포법이라 함은 스핀 코팅， 딥코팅， 닥터 블레이딩， 잉크젯 프린팅， 스크린 프린팅, 스프레이법， 롤 코팅 등을 의미하지만， 이들만으로 한정되는 것은 아니다. 이와 같은 방법 외에도， 기판 상에 음극 물질로부터 유기물층， 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다 0TO 2003/012890) . 다만, 제조 방법이 이에 한정되는 것은 아니다. 일례로, 상기 제 1 전극은 양극이고， 상기 제 2 전극은 음극이거나， 또는 상기 게 1 전극은 음극이고， 상기 제 2 전극은 양극이다. 상기 양극 물질로는 통상 유기물 층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐 크름, 구리 , 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물， 인듐 산화물, 인듐주석 산화물 ( ΠΌ) , 인듐아연 산화물 ( IZ0)과 같은 금속 산화물; Ζη0:Α1 또는 SN02 : Sb와 같은 금속과 산화물의 조합; 폴리 (3- 메틸티오펜)， 폴리 [3 , 4- (에틸렌 -1 , 2-디옥시 )티오펜] (PED0T) , 폴리피를 및 폴리아닐린과 같은 전도성 고분자 등이 있으나， 이들에만 한정되는 것은 아니다. 상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 음극 물질의 구체적인 예로는 마그네슴， 칼슘， 나트륨， 칼륨， 티타늄， 인듐, 이트륨， 리튬， 가돌리늄， 알루미늄， 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 Li02/Al과 같은 다층 구조 물질 등이 있으나， 이들에만 한정되는 것은 아니다. 상기 정공 주입 물질로는 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 이동^ 방지하며， 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMOChighest occupied molecular orbi tal )가 양극 물질의 일함수와 주변 유기물 층의 HOMO사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린 (porphyr in) , 을리고티오펜， 아릴아민 계열의 유기물， 핵사니트릴핵사아자트리페닐렌 계열의 유기물， 퀴나크리돈 (quinacr idone)계열의 유기물, 페릴렌 (perylene) 계열의 유기물， 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나， 이들에만 한정 되는 것은 아니다. 상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로， 정공 수송 물질로 양극이나 정공주입층으로부터 정공을 수송 받아 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. 상기 발광 물질로는 정공수송층과 전자 송층으로부터 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 (dimer i zed styryl ) 화합물; BAlq; 10-히드록시벤조 퀴놀린 -금속 화합물; 벤족사졸， 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리 (P- 페닐렌비닐렌) (PPV) 계열의 고분자; 스피로 (spi ro) 화합물; 폴리플루오렌， 루브렌 등이 있으나， 이들에만 한정되는 것은 아니다. 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. 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. 상기 전자 수송 물질로는 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광충으로 옮겨줄 수 있는 물질로서， 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 A1 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본 -금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자수송층은 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， 칼슴， 이테르븀 및 사마륨이고， 각 경우 알루미늄 층 또는 실버층이 뒤따른다. 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. 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) (0-크레졸라토)갈륨， 비스 (2—메틸 -8-퀴놀리나토) (1-나프를라토)알루미늄， 비스 (2—메틸 -8- 퀴놀리나토) (2-나프를라토)갈륨 등이 있으나， 이에 한정되지 않는다. 본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형， 후면 발광형 또는 양면 발광형일 수 있다. 또한， 상기 화학식 1로 표시되는 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는ᅳ유기 트랜지스터에 포함될 수 있다. 이하， 발명의 이해를 돕기 위하여 바람직한 실시예들이 제시된다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐， 본 발명을 이들만으로 한정하는 것은 아니다. 제조예 1-1 A physical vapor deposition (PVD) method may be used to deposit a metal or A metal oxide having conductivity or an alloy thereof is deposited to form an anode, an organic material layer including a hole injecting charge, a hole transporting layer, a luminescent dopant and an electron transporting layer is formed on the anode, a material usable as a cathode is deposited thereon . In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device. Here, the three-solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto. In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material. However, the manufacturing method is not limited thereto. 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 a cathode. As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer. Specific examples of the positive electrode material include metals such as vanadium chloride, copper, zinc and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (II), indium zinc oxide (IZO); Ζη0: Α1 SN0 or 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, no. The negative electrode 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 magnes, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, Metals such as aluminum, silver, tin and lead, or alloys thereof; Layer structure materials such as LiF / Al or LiO 2 / Al, but the present invention is not limited thereto. The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the ability to form a thin film is preferable. The HOMOChighest occupied molecular orbital of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include a metal porphyrin, a thiophene, an organic material of an arylamine series, an organic material of a quinacridone series, a quinacridone series organic material, a perylene perylene based organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto. The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto. The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Poly (P-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto. The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected 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. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto. The electron transporting material is a layer which transports electrons from the electron injecting layer to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting dopant, Is suitable. Specific examples include the A1 complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, fox, ytterbium and samarium, in each case followed by an aluminum or silver layer. The electron injection layer is a layer for injecting electrons from the electrode, And has an electron injecting effect from the cathode, an excellent electron injecting effect on the light emitting layer or the light emitting material, preventing migration of the excitons generated in the light emitting layer to the hole injecting layer, . Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, 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, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphthalato) gallium, and the like But is not limited thereto. The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used. In addition, the compound represented by Formula 1 may be included in an organic solar cell or organic transistor in addition to an organic light emitting device. Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto. Production Example 1-1
Figure imgf000100_0001
Figure imgf000100_0001
A1-1 A1-1
1) Al-1의 합성  1) Synthesis of Al-1
(2，3-디플루오로페닐)보로닉산 (50. Og, 316.6隱 ol)과 메틸 -2- 브로모벤조에이트 (71.49g, 332.4醒 ol)을 디옥산 (300ml)에 완전히 녹인 후 2M 포타슘카보네이트 수용액 (150ml)을 첨가하고， 테트라키스트리페닐- 포스피노팔라듐 (7.31g, 2niol%)를 넣은 후， 10시간 동안 가열교반하였다. 상온으로 온도를 낮추고 반웅을 종결한 후 포타슘카보네이트 수용액을 제거하여 층분리하였다. 용매 제거 후 흰색의 고체를 핵산으로 재결정하여 A1- 1(62.87g, 수율 80%)을 제조하였다.  (71.49 g, 332.4 mg ol) was completely dissolved in dioxane (300 ml), and 2M potassium (3-fluorophenyl) boronic acid (50.Og, 316.6 ol ol) and methyl-2-bromobenzoate Carbonate solution (150 ml) was added, and tetraquistriphenylphosphinopalladium (7.31 g, 2niol%) was added thereto, followed by heating and stirring for 10 hours. After lowering the temperature to room temperature and terminating the reaction, the aqueous potassium carbonate solution was removed to separate the layers. After removal of the solvent, the white solid was recrystallized from the nucleic acid to give A1- 1 (62.87 g, yield 80%).
MS[M+H]+= 249.23 MS [M + H] &lt; + &gt; = 249.23
Figure imgf000100_0002
Figure imgf000100_0002
2) A2-1의 합성 2) Synthesis of A2-1
A1-K30 g, 120.8隱01), 4-클로로벤젠 -1,2-디올 (17.91 g, 124.8mmol) 포타슘카보네이트 (50.08g, 362.4隱 ol)를 디메틸포름아마이드 (300ml)에 첨가한후 3시간 동안 가열교반하였다. 상온으로 온도를 낮추고 반응을 종결한 후 물을 첨가한 후 필터하고 클로로포름에 용해하여 추출한 뒤， 에틸아세테이트와 핵산으로 컬럼하여 상기 A2-1 (12.7 g, 수율 30%)를 제조하였다.  After adding potassium carbonate (50.08 g, 362.4 ol ol) to dimethylformamide (300 ml), 3-chlorobenzene-1,2-diol (17.91 g, 124.8 mmol) Lt; / RTI &gt; After the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was filtered, dissolved in chloroform, and extracted with ethyl acetate and nucleic acid to obtain A2-1 (12.7 g, yield 30%).
MS[M+H]+= 353.77 MS [M + H] &lt; + &gt; = 353.77
Figure imgf000101_0001
Figure imgf000101_0001
3) A2-2의 합성 3) Synthesis of A2-2
상기 A2-1의 합성에서와동일한 방법으로 합성하여 A2-2를 제조하였다 MS[M+H]+= 353.77  Was synthesized in the same manner as in the synthesis of A2-1 above to give A2-2. MS [M + H] &lt; + &gt; = 353.77
Figure imgf000101_0002
Figure imgf000101_0002
1) B2-1의 합성  1) Synthesis of B2-1
상기 A2-1의 합성에서 4-클로로벤젠— 1， 2-디올 대신 3-클로로벤젠 -1， 2- 디올을 사용한 것을 제외하고는 동일한 방법으로 합성하여 B2-1을 제조하였다  B2-1 was synthesized in the same manner as in the synthesis of A2-1 except that 3-chlorobenzene-1,2-diol was used instead of 4-chlorobenzene-1,2-diol
MS[M+H]+= 353.77 MS [M + H] &lt; + &gt; = 353.77
Figure imgf000101_0003
Figure imgf000101_0003
2) B2-2의 합성  2) Synthesis of B2-2
상기 B2-1의 합성에서와 동일한 방법으로 합성하여 B2-2를 제조하였다 MS[M+H]+= 353.77
Figure imgf000102_0001
The synthesis was carried out in the same manner as in the synthesis of B2-1 above to give B2-2. MS [M + H] &lt; + &gt; = 353.77
Figure imgf000102_0001
A2-1 A3-1 A2-1 A3-1
1) A3-1의 합성  1) Synthesis of A3-1
질소 분위기 하에서 A2-1 (25g, 70.86mmol )을 테트라하이드로퓨란 (325mL) 에 투입하여 용해시킨 후 -10°C로 온도안정화 및 교반 하였다. 3.0M 메틸마그네슘브로마이드 54mL (디에틸에테르 내， 162.4mmol )을 30분간 천천히 적가하고 반웅액을 상온으로 승온하고 질소 분위기 하에 10시간 교반 하였다. 반웅액을 0°C로 넁각한 후 여기에 암모늄클로라이드 ( 10.4g, 194.85隱 ol )을 증류수 lOOmL 에 녹인 수용액을 천천히 가한다. 반웅액을 증류수와 디에틸 에테르로 추출하고 유기층 용액을 마그네슘설페이트로 건조， 여과하고 여과액을 감압농축하여 A3-1을 제조하였다. A2-1 (25 g, 70.86 mmol) was dissolved in tetrahydrofuran (325 mL) under nitrogen atmosphere, and the temperature was stabilized and stirred at -10 ° C. 54 mL of 3.0 M methylmagnesium bromide (162.4 mmol in diethyl ether) was slowly added dropwise over 30 minutes, the reaction mixture was warmed to room temperature, and stirred for 10 hours under a nitrogen atmosphere. The solution is stirred at 0 ° C and then an aqueous solution of ammonium chloride (10.4 g, 194.85  ol) dissolved in 100 ml of distilled water is slowly added thereto. The NaOH solution was extracted with distilled water and diethyl ether, and the organic layer solution was dried with magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to prepare A3-1.
Figure imgf000102_0002
Figure imgf000102_0002
A3-1 A4-1 A3-1 A4-1
2) A4— 1의 합성 , 2) Synthesis of A4-1 ,
제조된 A3-1을 디클로로메탄 325mL에 투입하고 용해시킨 후 0°C로 넁각 및 교반 하였다. 여기에 보론트리플루오라이드 디에틸 이써레이트 (4mL , 32.5mmol )을 10분간 천천히 가하고 실온으로 승온한후 12시간 동안 교반한다. 반응이 종료되면 중탄산나트륨 수용액을 0°C에서 천천히 가한후 30분간 교반한다. 반웅액을 디클로로메탄으로 추출하고 생성물을 디클로로메탄과 핵산으로 실리카 컬럼으로 정제하여 A4-l(23.72 g, 수율 70%)을 제조하였다. MS[M+H] += 335.80 The prepared A3-1 was added to 325 mL of dichloromethane and dissolved, followed by stirring at 0 ° C and stirring. Boron trifluoride diethylsulfate (4 mL, 32.5 mmol) was slowly added thereto for 10 minutes, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. When the reaction is complete, slowly add aqueous sodium bicarbonate solution at 0 ° C and stir for 30 minutes. The crude product was extracted with dichloromethane and the product was purified by silica column with dichloromethane and a nucleic acid to give A4-1 (23.72 g, yield 70%). MS [M + H] &lt; + &gt; = 335.80
Figure imgf000103_0001
상기 A3-1의 합성에서 메틸마그네슘브로마이드 대신 페닐마그네슘브로마이드를 사용한 것을 제외하고는 동일한 방법으로 A3-2를 제조하였다. 또한, A4-1의 합성에서 A3-1 대신 A3-2를 사용한 것을 제외하고는 동일한 방법으로 합성하여 A4-2를 제조하였다
Figure imgf000103_0001
A3-2 was prepared by the same method except that phenylmagnesium bromide was used instead of methylmagnesium bromide in the synthesis of A3-1. Further, A4-2 was synthesized by the same method except that A3-2 was used instead of A3-1 in the synthesis of A4-1
MS[M+H]+= 459.94 MS [M + H] &lt; + &gt; = 459.94
Figure imgf000103_0002
Figure imgf000103_0002
A2-2  A2-2
A3-3 A4-3 상기 A3-1의 합성에서 A2-1 대신 A2-2를 사용한 것을 제외하고는 동일한 방법으로 A3-3을 제조하였다. 또한， A4-1의 합성에서 A3-1 대신 A3-3을 사용한 것을 제외하고는 동일한 방법으로 합성하여 A4-2를 제조하였다  A3-3 A4-3 A3-3 was prepared in the same manner except that A2-2 was used instead of A2-1 in the synthesis of the above A3-1. Further, A4-2 was synthesized by the same method except that A3-3 was used instead of A3-1 in the synthesis of A4-1
MS[M+H] += 335.80 MS [M + H] &lt; + &gt; = 335.80
Figure imgf000103_0003
상기 A3-3의 합성에서 메틸마그네슘브로마이드 대신 페닐마그네슘브로마이드를 사용한 것을 제외하고는 동일한 방법으로 A3-4를 제조하였다. 또한， A4-3 의 합성에서 A3-3 대신 A3-4를 사용한 것을 제외하고는 동일한 방법으로 합성하여 A4-4를 제조하였다
Figure imgf000103_0003
A3-4 was prepared in the same manner except that phenylmagnesium bromide was used instead of methylmagnesium bromide in the synthesis of A3-3. Further, A4-4 was prepared by synthesizing the same method except that A3-4 was used instead of A3-3 in the synthesis of A4-3
MS[M+H]+= 459.94 MS [M + H] &lt; + &gt; = 459.94
Figure imgf000104_0001
Figure imgf000104_0001
화합물 A4-1 (20 g , 59.73 mmol ) , 비스 (피나콜라토)디보론 (Bi s(pinacolato)diborone) ( 15.92g, 62.72mmo 1 ) , 포타슘아세테이트 (potassium acetate) ( 11.4 g, 119.4 睡 ol )를 1 , 4-다이옥산 (300mL)에 투입하고， 환류 교반 상태에서 디벤질리덴아세톤팔라듐 (686mg, 0.02mol%)과 트리시클로핵실포스핀 (645mg, 0.04mol%)을 첨가하고 12시간 환류 교반시켰다. 반웅이 종결되면 흔합물을 실온으로 넁각하고， 샐라이트를 통해 여과한다. 여액을 감압 하에 농축한 후 잔류물에 클로로포름을 넣고 녹인 후 물로 세척하여 유기층을 분리한 후 무수황산 마그네슴 (Magnesium sul fate)으로 건조하였다. 이를 감압 증류하고， 에틸아세테이트로 재결정하여 A5-1 (21.38g, 수율 84 %)을 제조하였다. The compound A4-1 (20 g, 59.73 mmol), bis (pinacolato) diborone (15.92 g, 62.72 mmol), potassium acetate (11.4 g, ) Was added to 1,4-dioxane (300 mL), and dibenzylidene acetone palladium (686 mg, 0.02 mol%) and tricyclohexylphosphine (645 mg, 0.04 mol%) were added under reflux and stirring. . When the reaction is complete, the mixture is stirred at room temperature and filtered through a salite. The filtrate was concentrated under reduced pressure, and the residue was dissolved in chloroform. The separated organic layer was washed with water and dried over anhydrous magnesium sulfate (Magnesium sul fate). This was distilled under reduced pressure, and recrystallized from ethyl acetate to obtain A5-1 (21.38 g, yield 84%).
MS[M+H]+= 427.32 제조예 3-2: A5-2의 합성
Figure imgf000105_0001
MS [M + H] &lt; + &gt; = 427.32 Preparation Example 3-2: Synthesis of A5-2
Figure imgf000105_0001
A5-2 A5-2
A4-2 상기 A5-1 의 합성에서 A4-1 대신 A4-2를 사용한 것을 제외하고는 동일한 방법으로 합성하여 A5-2를 제조하였다  A4-2 A5-2 was synthesized by the same method except that A4-2 was used instead of A4-1 in the synthesis of the above A5-1
MS[M+H]+= 551.46 제조예 3-3 : A5-3의 합성 MS [M + H] &lt; + &gt; = 551.46 Preparation Example 3-3: Synthesis of A5-3
Figure imgf000105_0002
Figure imgf000105_0002
A4-3  A4-3
A5-3  A5-3
상기 A5-1의 합성에서 A4-1 대신 A4-3을 사용한 것을 제외하고는 동일한 방법으로 합성하여 A5-3을 제조하였다  A5-3 was prepared by synthesizing the same method except that A4-3 was used instead of A4-1 in the synthesis of the above A5-1
MS[M+H]+= 427.32 제조예 3-4： A5-4의 합성 MS [M + H] &lt; + &gt; = 427.32 Preparation Example 3-4: Synthesis of A5-4
Figure imgf000105_0003
Figure imgf000105_0003
A5-4 A5-4
A4-4 상기 A5-1의 합성에서 A4-1 대신 A4-4를 사용한 것을 제외하고는 동일한 방법으로 합성하여 A5-4를 제조하였다 A4-4 A5-4 was synthesized by the same method except that A4-4 was used instead of A4-1 in the synthesis of the above A5-1
MS[M+H]+= 551.46 、 제조예 3-5： B5-1의 합성 MS [M + H] &lt; + &gt; = 551.46, PREPARATION 3-5: Synthesis of B5-1
Figure imgf000106_0001
Figure imgf000106_0001
B4-1 B5-1 상기 A5-1의 합성에서 A4-1 대신 B4-1을 사용한 것을 제외하고는 동일한 방법으로 합성하여 B5-1을 제조하였다 B4-1 B5-1 B5-1 was synthesized by the same method except that B4-1 was used instead of A4-1 in the synthesis of the above A5-1
MS[M+H]+= 427.32 제조예 3-6： B5-2의 합성 MS [M + H] &lt; + &gt; = 427.32 Preparation Example 3-6: Synthesis of B5-2
Figure imgf000106_0002
Figure imgf000106_0002
B4-2 B5-2 상기 B5-1의 합성에서 B4-1 대신 B4-2를 사용한 것을 제외하고 동일한 방법으로 합성하여 B5-2를 제조하였다  B4-2 B5-2 B5-2 was synthesized by the same method except that B4-2 was used instead of B4-1 in the synthesis of B5-1 above
MS[M+H]+= 551.46 제조예 3-7： B5-3의 합성
Figure imgf000107_0001
MS [M + H] &lt; + &gt; = 551.46 Preparation Example 3-7: Synthesis of B5-3
Figure imgf000107_0001
B4-3 B5-3  B4-3 B5-3
상기 B5-1의 합성에서 B4-1 대신 B4-3을 사용한 것을 제외하고는 동일한 방법으로 합성하여 B5-3을 제조하였다  B5-3 was prepared by the same method except for using B4-3 instead of B4-1 in the synthesis of B5-1
MS[M+H]+= 427.32 제조예 3-8： B5-4의 합성 MS [M + H] &lt; + &gt; = 427.32 Preparation Example 3-8: Synthesis of B5-4
Figure imgf000107_0002
Figure imgf000107_0002
B4-4 B5-4 상기 B5-1의 합성에서 B4-1 대신 Β4-4Ϊ 사용한 것을 제외하고는 동일한 방법으로 합성하여 B5-4를 제조하였다 B4-4 B5-4 B5-4 was synthesized by the same method except that B4-4 was used instead of B4-1 in the synthesis of B5-1 above
MS[M+H]+= 551.46 제조예 4-1: 화합물 1의 합성 MS [M + H] &lt; + &gt; = 551.46 Preparation Example 4-1: Synthesis of Compound 1
Figure imgf000108_0001
상기 화합물 A5-1 ( 10.0g, 23.45mmol )과 2-(3-클로로페닐) -4，6_ 디페닐피리미딘 (8.2g, 23.92隱 ol )을 테트라하이드로퓨란 (300ml )에 완전히 녹인 후 2M 포타슘카보네이트 수용액 ( 150ml )을 첨가하고， 테트라키스트리페닐- 포스피노팔라듐 (542mg, 2mol%)를 넣은 후, 10시간 동안 가열교반하였다. 상온으로 은도를 낮추고 반응을 종결한 후 포타슴카보네이트 수용액을 제거하여 층분리하였다. 용매 제거 후 흰색의 고체를 테트라하이드로푸란과 에틸아세테이트로 재결정하여 상기 화합물 1( 11.09 g, 수율 78%)을 제조하였다.
Figure imgf000108_0001
The compound A5-1 (10.0 g, 23.45 mmol) and 2- (3-chlorophenyl) -4,6-diphenylpyrimidine (8.2 g, 23.92 ol ol) were completely dissolved in 300 ml of tetrahydrofuran, Carbonate aqueous solution (150 ml) was added, tetrakistriphenylphosphinopalladium (542 mg, 2 mol%) was added, and the mixture was heated with stirring for 10 hours. After lowering the silver concentration to room temperature and terminating the reaction, the layer was separated by removing the aqueous solution of the potassium carbonate. After removing the solvent, the white solid was recrystallized from tetrahydrofuran and ethyl acetate to give Compound 1 (11.09 g, yield 78%).
MS[M+H]+= 607.73 MS [M + H] &lt; + &gt; = 607.73
Figure imgf000108_0002
상기 화합물 1의 합성에서 A5-1 대신 A5-2 를， 2-(3-클로로페닐) -4 , 6- 디페닐피리미딘 대신 2-(4-클로로페닐) -4 , 6-디페닐 -1，3，5-트리아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 2를 제조하였다
Figure imgf000108_0002
A5-2 was used instead of A5-1 in the synthesis of Compound 1, and 2- (4-chlorophenyl) -4,6-diphenyl-1, , 3,5-triazine was used to prepare Compound 2
MS[M+H]+= 732.86 제조예 4-3: 화합물 3의 합성 MS [M + H] &lt; + &gt; = 732.86 Preparation Example 4-3: Synthesis of Compound 3
Figure imgf000109_0001
상기 화합물 1의 합성에서 A5-1 대신 A5-2를， 2-(3-클로로페닐) -4，6- 디페닐피리미딘 대신 2-클로로 -4 , 6-디페닐피리미딘을 사용한 것을 계외하고는 동일한 방법으로 합성하여 화합물 3을 제조하였다
Figure imgf000109_0001
A5-2 was used instead of A5-1 in the synthesis of the compound 1, and 2-chloro-4,6-diphenylpyrimidine was used instead of 2- (3-chlorophenyl) -4,6-diphenylpyrimidine Were synthesized in the same manner to give Compound 3
MS[M+H]+= 654.78 제조예 4-4: 화합물 4의 합성 MS [M + H] &lt; + &gt; = 654.78 Preparation Example 4-4: Synthesis of Compound 4
1) A6-1의 합성 1) Synthesis of A6-1
Figure imgf000110_0001
Figure imgf000110_0001
상기 화합물 1의 합성에서 A5-1 대신 A5-3를， 2-(3-클로로페닐) -4，6- 디페닐피리미딘 대신 2-클로로 -4-(4-클로로페닐) -6-페닐 -1,3， 5—트리아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 A6-1을 합성하였다. A5-3 was used instead of A5-1 in the synthesis of the compound 1 and 2-chloro-4- (4-chlorophenyl) -6-phenyl-pyridine was used instead of 2- (3- 1,3,5-triazine was used to synthesize A6-1.
MS[M+H]+= 567.06 MS [M + H] &lt; + &gt; = 567.06
2) 화합물 4의 합성 2) Synthesis of Compound 4
Figure imgf000110_0002
Figure imgf000110_0002
A6-1  A6-1
A6-1 (15g, 26.4 mmol)과， 9H-카바졸 (15g, 27.3 隱 ol), 소듐 -t_ 부특사이드 (4.56g, 59.2mol)을 자일렌에 넣고 가열 교반한 뒤 환류시키고 [비스 (트라이 -t-부틸포스핀)]팔라듐 (269mg. 2瞧 olW을 넣는다. 상온으로 온도를 낮추고 반웅을 종결한 후， 테트라하이드로퓨란과 에틸아세테이트를 이용해 재결정하여 화합물 4 (15.08g, 82%)을 제조하였다. MS[M+H] = 697.81 제조예 4-5: 화합물 5의 합성 (15 g, 26.3 mmol), 9H-carbazole (15 g, 27.3  ol) and sodium-t_specificide (4.56 g, 59.2 mol) were added to xylene and the mixture was heated under reflux, butylphosphine)] palladium (269 mg, 2 瞧 ol W) was added to the reaction mixture, the temperature was lowered to room temperature, and the reaction mixture was terminated and then recrystallized from tetrahydrofuran and ethyl acetate to prepare Compound 4 (15.08 g, 82% Respectively. MS [M + H] = 697.81 Preparation Example 4-5: Synthesis of Compound 5
Figure imgf000111_0001
상기 화합물 1의 합성에서 A5-1 대신 A5-3을， 2-(3-클로로페닐) -4,6- 디페닐피리미딘 대신 2-클로로 -4-(9，9ᅳ디메틸 -9H-2-일) -6-페닐— 1,3,5- 트라아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 5를 제조하였다
Figure imgf000111_0001
A5-3 was used instead of A5-1 in the synthesis of the compound 1 and 2-chloro-4- (9,9-dimethyl-9H-2- (3-chlorophenyl) Yl) -6-phenyl-1,3,5-triazine was used to prepare compound 5
MS[M+H]+= 724.88 제조예 4-6: 화합물 6의 합성 MS [M + H] &lt; + &gt; = 724.88 Preparation Example 4-6: Synthesis of Compound 6
Figure imgf000112_0001
Figure imgf000112_0001
상기 화합물 1의 합성에서 A5-1 대신 B5-1을, 2-(3-클로로페닐)ᅳ 4,6- 디페닐피리미딘 대신 2-클로로 -4-(4- (디벤조 [b,d]푸란 -4-일)페닐) -6-페닐- 1，3，5-트라아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 6을 제조하였다 B5-1 was used instead of A5-1 in the synthesis of the compound 1 and 2-chloro-4- (4- (dibenzo [b, d] pyridin- Furan-4-yl) phenyl) -6-phenyl-1,3,5-triazine was used to prepare compound 6
MS[M+H]+= 697.81 MS [M + H] &lt; + &gt; = 697.81
Figure imgf000112_0002
디페닐피리미딘 대신 2-클로로 -4-(3-클로로페닐) -6-페닐 -1，3，5-트리아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 B6-1을 합성하였다.
Figure imgf000112_0002
B6-1 was synthesized by the same method except for using 2-chloro-4- (3-chlorophenyl) -6-phenyl-1,3,5-triazine instead of diphenyl pyrimidine.
MS[M+H]+= 690.21 MS [M + H] &lt; + &gt; = 690.21
Figure imgf000113_0001
Figure imgf000113_0001
B6- 상기 화합물 1의 합성에서 A3-1 대신 B6-1을， 2-(3-클로로페닐) -4 , 6- 디페닐피리미딘 대신 (3-시아노페닐)보로닉산을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 7을 합성하였다.  B6-Except that B6-1 was used instead of A3-1 in the synthesis of the compound 1 and (3-cyanophenyl) boronic acid was used instead of 2- (3-chlorophenyl) -4,6-diphenylpyrimidine Compound 7 was synthesized by the same method.
MS[M+H]+= 756.88 MS [M + H] &lt; + &gt; = 756.88
Figure imgf000113_0002
상기 화합물 1의 합성에서 A5-1 대신 B5-3을， 2-(3-클로로페닐) -4，6- 디페닐피리미딘 대신 2-클로로 -4， 6-디페닐 -1,3, 5—트리아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 8을 제조하였다
Figure imgf000113_0002
B5-3 was used instead of A5-1 in the synthesis of the compound 1, and 2-chloro-4,6-diphenyl-1,3,5-trichlorobenzene was used instead of 2- (3-chlorophenyl) Compound 8 was prepared by the same method except that triazine was used
MS[M+H]+= 532.62 제조예 4-9: 화합물 9의 합성 MS [M + H] &lt; + &gt; = 532.62 Preparation Example 4-9: Synthesis of Compound 9
Figure imgf000114_0001
상기 화합물 1의 합성에서 A5-1 대신 B5— 4를， 2-(3-클로로페닐) -4，6- 디페닐피리미딘 대신 2-([1，1' -비페닐] -3-일) -4-클로로 -6-페닐 -1,3,5- 트리아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 9를 제조하였다
Figure imgf000114_0001
B5- 4 was used in place of A5-1 in the synthesis of the compound 1 and 2 - ([l, l ' -biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5-triazine, the compound 9 was prepared
MS[M+H]+= 808.95 제조예 4-10: 화합물 10의 합성 MS [M + H] &lt; + &gt; = 808.95 Preparation Example 4-10: Synthesis of Compound 10
Figure imgf000115_0001
Figure imgf000115_0001
Β5·4 10 Β5 · 4 10
상기 화합물 1의 합성에서 A5-1 대신 Β5-4를， 2-(3-클로로페닐) -4，6- 디페닐피리미딘 대신 2-클로로 -4- (나프탈렌 -2-일) -6-페닐 -1，3， 5-트리아진을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 10을 제조하였다 In the synthesis of the compound 1, Β5-4 was used instead of A5-1, and 2-chloro-4- (naphthalen-2-yl) -6-phenyl -1,3,5-triazine was used to prepare Compound 10
MS[M+H]+= 706.82 실시예 1  MS [M + H] &lt; + &gt; = 706.82 Example 1
ΠΌ (인듐 주석 산화물)가 1,000 A 두께로 박막 코팅된 유리 기판 (corning 7059 glass)을， 분산제를 녹인 증류수에 넣고 초음파로 세척하였다. 세제는 Fischer Co.의 제품을 사용하였으며， 증류수는 Millipore Co. 제품의 필터 (Filter)로 2차 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후， 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후 이소프로필알콜， 아세톤， 메탄을 용제 순서로 초음파 세척을 하고 건조시켰다.  A glass substrate (corning 7059 glass) coated with a thin film of 1,000 A thick indium tin oxide was placed in distilled water containing a dispersant and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing with distilled water, isopropyl alcohol, acetone, and methane were ultrasonically washed and dried in the solvent order.
이렇게 준비된 IT0 투명 전극 위에 HAT (핵사니트릴 핵사아자트리페닐기렌， hexanitrile hexaazatr iphenylene)를 500A의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 그 위에 정공을 수송하는 물질인 HT1 (900A)을 진공증착하여 정공수송층을 형성한 후， 이어서 상기 정공수송층 위에 HT2를 막두께 50A으로 진공증착하여 정공조절층을 형성하였다. 발광층으로 호스트 HI과 도판트 D1 화합물 (25:1)을 300A의 두께로 진공 증착하였다. 이어서 상기 발광층 위에 ETM1 화합물 (50A)을 전자조절층으로 형성시키고， 상기 전자조절층 위에 제조예 4-1에서 합성한 화합물 1과 LiQ (1:1)를 공증착시켜 310A의 두께로 전자수송층을 형성하였다. 상기 전자수송층 위에 10A 두께의 리튬 플루오라이드 (LiF)와 150A 두께의 Mg와 Ag(10:l)를 순차적으로 증착하고 1,000 A 두께의 알루미늄을 증착하여 음극을 형성하여， 유기 발광 소자를 제조하였다. HAT (hexanitrile hexaazatr iphenylene) was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500A to form a hole injection layer. HT1 (900A), which is a material for transporting holes, was vacuum deposited to form a hole transport layer. Subsequently, HT2 was vacuum deposited on the HTL to a thickness of 50 A to form a hole control layer. A host HI and a dopant D1 compound (25: 1) were vacuum deposited as a light emitting layer to a thickness of 300A. Then, an ETM1 compound (50A) is deposited on the light emitting layer as an electron control layer And Compound 1 synthesized in Production Example 4-1 and LiQ (1: 1) were co-deposited on the electron control layer to form an electron transporting layer having a thickness of 310A. Lithium fluoride (LiF) having a thickness of 10 A and Mg and Ag (10: 1) having a thickness of 150 A were sequentially deposited on the electron transporting layer, and aluminum having a thickness of 1,000 A was deposited thereon to form a cathode.
상기의 과정에서 유기물의 증착속도는 1 A/sec를 유지하였고 리튬플루라이드는 0.2 A/sec, 알루미늄은 3 내지 7 A/sec의 증착속도  In the above process, the deposition rate of the organic material was maintained at 1 A / sec, the lithium fluoride was 0.2 A / sec, the aluminum was deposited at a deposition rate of 3 to 7 A / sec
Figure imgf000116_0001
Figure imgf000116_0001
ETM1  ETM1
H1 D1  H1 D1
실시예 2내지 16 Examples 2 to 16
상기 실시예 1에서 전자수송층으로 화합물 1 및 LIQ (1:1) 대신 하기 표 1에 기재된 화합물과 LIQ를 특정 비율로 사용한다는 점을 제외하고는 동일한 방법으로 유기 발광소자를 제조하였다. 실시예 17 상기 실시예 1에서 전자조절층으로 ETM1 대신 화합물 1을 사용하고， 전자수송충에서 화합물 1 대신 하기 ETM2를 사용한 것을 제외하고는 동일한 방법으로 유기 발광소자를 제조하였다. An organic luminescent device was prepared in the same manner as in Example 1, except that the compound shown in the following Table 1 and LIQ were used in a specific ratio instead of Compound 1 and LIQ (1: 1) as the electron transport layer. Example 17 An organic light emitting device was prepared in the same manner as in Example 1 except that Compound 1 was used instead of ETM1 as the electron control layer and ETM2 was used in place of Compound 1 in the electron donor.
Figure imgf000117_0001
Figure imgf000117_0001
ETM2 실시예 18내지 23  ETM2 Examples 18 to 23
상기 실시예 17에서 전자조절층으로 화합물 1 대신 하기 표 2에 기재된 화합물을 사용하고， 전자수송층에서 ETM2와 LIQ를 하기 표 2에 기재된 특정 비율로 사용하는 점을 제외하고는 동일한 방법으로 유기 발광 소자를 제조하였다.  Except that the compounds described in the following Table 2 were used in place of the compound 1 as the electron control layer in Example 17 and ETM2 and LIQ in the electron transporting layer were used in the specific ratios shown in Table 2 below, .
실시예 24내지 32 Examples 24 to 32
상기 실시예 1에서 전자조절층으로 ETM1 대신 하기 표 3에 기재된 화합물을 사용하고， 전자수송층으로 화합물 1 및 LIQ (1 : 1) 대신 하기 표 3에 기재된 화합물을 특정 비율로사용하는 점을 제외하고는 동일하게 실험하였다. 비교예 1 내지 13  Except that the compound described in the following Table 3 was used in place of ETM1 as the electron control layer in Example 1 and the compound shown in the following Table 3 was used in place of Compound 1 and LIQ (1: 1) as the electron transporting layer in the following ratio Were tested in the same manner. Comparative Examples 1 to 13
상기 실시예 1에서 전자조절층으로 ETM1 대신 하기 표 3에 기재된 화합물을 사용하고， 전자수송층으로 화합물 1 및 LIQ (1 : 1) 대신 하기 표 3에 기재된 화합물을 특정 비율로 사용하는 점을 제외하고는 동일하게 실험하였다. 상기 실시예 1 내지 32 및 비교예 1 내지 13에서 제조한 유기 발광 소자에 전류 (20mA/cm2)를 인가하여， 전압， 효율， 색좌표 및 수명을 측정하고 그 결과를 하기 표 1 내지 3에 각각 나타내었다. 【표 1】
Figure imgf000118_0001
Except that the compound described in the following Table 3 was used in place of ETM1 as the electron control layer in Example 1 and the compound shown in the following Table 3 was used in place of Compound 1 and LIQ (1: 1) as the electron transporting layer in the following ratio Were tested in the same manner. The current, (20 mA / cm 2 ) was applied to the organic light-emitting devices prepared in Examples 1 to 32 and Comparative Examples 1 to 13 to measure voltage, efficiency, color coordinates and lifetime. The results are shown in Tables 1 to 3 Respectively. [Table 1]
Figure imgf000118_0001
【표 2]
Figure imgf000118_0002
【표 3] [Table 2]
Figure imgf000118_0002
[Table 3]
Figure imgf000119_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000120_0002
Figure imgf000120_0001
Figure imgf000120_0002
Figure imgf000120_0003
Figure imgf000120_0003
상기 표 1 내지 3에 따르면， 실시예 1 내지 32는， 비교예 1 내지 13에 비하여， 전압이 낮고， 효을 및 수명이 현저히 우수한 특성을 나타냄을 확인했다. According to Tables 1 to 3, it was confirmed that Examples 1 to 32 exhibited lower voltage and significantly superior effect and lifetime compared with Comparative Examples 1 to 13.
【부호의 설명】 DESCRIPTION OF REFERENCE NUMERALS
1 기판 2: 양극 3: 발광층 4: 음극  1 substrate 2: anode 3: light emitting layer 4: cathode
5 정공주입층 6: 정공수송층 7: 정공조절층 8: 발광  5 hole injection layer 6: hole transport layer 7: hole control layer 8: light emission
9 전자조절층 10: 전자수송층  9 electron control layer 10: electron transport layer

Claims

【청구범위】 Claims:
【청구항 1】  [Claim 1]
하기 화학식 1로 표시되는 화합물:  A compound represented by the following formula (1):
Figure imgf000121_0001
Figure imgf000121_0001
상기 화학식 1에서， In Formula 1,
l 및 Υ2는 각각 독립적으로 수소; 치환 또는 비치환된 d-40 알킬; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 0， N , Si 및 S 중 1개 이상을 포함하는 C2-60 헤테로아릴이고， 1 and 2 each independently represent hydrogen; Substituted or unsubstituted d-40 alkyl; Substituted or unsubstituted C 6 -C 60 aryl; Or a substituted or unsubstituted C 2 - 60 heteroaryl containing at least one of O, N, Si and S,
An 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6— 60 아릴; 치환 또는 비치환된 0, N , Si 및 S 중 1개 이상을 포함하는 C2-60 헤테로아릴이거나， 또는 A 또는 Ar2는 서로 인접하는 기와 결합하여 축합 고리를 형성하고， An and Ar 2 are each C independently represents a substituted or unsubstituted 6-60 aryl; Or C 2 - 60 heteroaryl containing at least one of substituted or unsubstituted O, N, Si and S, or A or Ar 2 is bonded to adjacent groups to form a condensed ring,
Xi 내지 ¾은 각각 독립적으로 N 또는 CR' 이고， 단， 이들 중 하나 이상이 N이고，  Each of Xi to 은 is independently N or CR 'with the proviso that at least one of them is N,
R' 은 수소 ; 또는 치환 또는 비치환된 d-60의 알킬이고 ,  R 'is hydrogen; Or a substituted or unsubstituted d-60 alkyl,
L은 각각 독립적으로 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 N , 0, S 및 Si로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로 원자를 포함하는 C2-60 헤테로아릴렌이고， L are each independently a direct bond; Substituted or unsubstituted C 6 - 60 arylene; Or C 2 - 60 heteroarylene containing at least one heteroatom selected from the group consisting of N, O, S and Si,
Ri 내지 R3은 각각 독립적으로 할로겐; 히도록시기; 시아노; 니트릴; 니트로; 아미노; 치환 또는 비치환된 d-60 알킬; 치환 또는 비치환된 d-60 할로알킬 ; 치환 또는 비치환된 d-60 티오알킬 ; 치환 또는 비치환된 d-60 알콕시 ; 치환 또는 비치환된 C o 할로알콕시 ; 치환 또는 비치환된 C3-60 사이클로알킬 ; 치환 또는 비치환된 d-60 알케닐; 치환 또는 비치환된 C6-60 아릴; 치환 또는 비치환된 C6-60 아릴옥시; 또는 치환 또는 비치환된 0， N, Si 및 S중 1개 이상을 포함하는 C2-60 헤테로아릴이고， Ri to R 3 are each independently halogen; Time to come; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted d- 60 alkyl; Substituted or unsubstituted d- 60 haloalkyl; Substituted or unsubstituted d-60 thioalkyl; Substituted or unsubstituted d-60 alkoxy; Substituted or unsubstituted C0 haloalkoxy; Substituted or unsubstituted C 3 - 60 cycloalkyl; Substituted or unsubstituted d-60 alkenyl; Substituted or unsubstituted C 6 -C 60 aryl; Substituted or unsubstituted C 6 -C 60 aryloxy; Or a substituted or unsubstituted C 2 - 60 heteroaryl containing at least one of O, N, Si and S,
m은 0 내지 4이고,  m is from 0 to 4,
n은 0 내지 2이고, o는 0 내지 3이고， n is from 0 to 2, o is 0 to 3,
z는 1 내지 4이고， 단 o+z는 4 이하이다.  z is 1 to 4, provided that o + z is 4 or less.
【청구항 2] [Claim 2]
게 1항에 있어서，  In Item 1,
Yi 및 Y2는 각각 독립적으로 메틸 또는 페닐인， 화합물. Yi and Y 2 are each independently methyl or phenyl, the compound.
【청구항 3] [3]
제 1항에 있어서,  The method according to claim 1,
m , η 및 0는 0인， 화합물.  m, eta and 0 are zero.
【청구항 4] [4]
거 U항에 있어서，  In the above,
ζ는 1인， 화합물 .  and zeta is 1.
【청구항 5】  [Claim 5]
제 1항에 있어서，  The method according to claim 1,
상기 화학식 1은 하기 화학식 1-1 내지 1-10으로 표시되는 화합물 중에서 선택되는 어느 하나인, 화합물:  Wherein the formula 1 is any one selected from the compounds represented by the following formulas 1-1 to 1-10:
Figure imgf000122_0001
Figure imgf000122_0002
[화학식 1-3]
Figure imgf000122_0001
Figure imgf000122_0002
[Formula 1-3]
Figure imgf000123_0001
Figure imgf000123_0001
[화학식 1-7] [Chemical Formula 1-7]
Figure imgf000124_0001
Figure imgf000124_0001
Figure imgf000124_0002
Figure imgf000124_0002
Figure imgf000124_0003
Figure imgf000124_0003
Figure imgf000124_0004
Figure imgf000124_0004
상기 화학식 1ᅳ 1 내지 l-io에서 L, A 및 Ar2에 대한설명은 제 1항에서 정의한 바와 같다. In the above formulas (1) to (1-io) L, A and Ar &lt; 2 &gt; are as defined in claim 1.
【청구항 6] [Claim 6]
게 1에 있어서  In Crab 1
An 및 Ar2는 각각 독립적으로 하기로 구성되는 군으로부터 선택되는 An and Ar &lt; 2 &gt; are each independently selected from the group consisting of
Figure imgf000125_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000127_0001
//: O8ϊ02Μ12AV //: O 8 ϊ0 2 M12AV
Figure imgf000128_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000129_0001
Figure imgf000129_0002
Figure imgf000129_0002
Figure imgf000129_0003
Figure imgf000129_0003
【청구항 7】 7.
제 1에 있어서，  In the first aspect,
L은 각각 독립적으로 직접결합 또는 하기로 구성되는 군으로부터 선택 되는 어느 하나인， 화합물. L is each independently a direct bond or any one selected from the group consisting of
Figure imgf000130_0001
Figure imgf000130_0001
【청구항 8】 8.
제 1항에 있어서，  The method according to claim 1,
상기 화학식 1로 표시되는 화합물은 하기 화합물로 구성되는 군으로부 터 선택되는 어느 하나인 것을 특징으로 하는， 화합물: The compound represented by Formula 1 is any one selected from the group consisting of the following compounds:
Figure imgf000131_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000132_0001
Figure imgf000133_0001
//: O8ϊ02Μ12AV
Figure imgf000133_0001
//: O 8 ϊ0 2 M12AV
Figure imgf000135_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000139_0001
6ei 6ei
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000147_0001
I9f8^0/6 //: O8ϊ02Μ12AV I9f8 ^ 0/6 //: O 8 ϊ0 2 M12AV
Figure imgf000148_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000149_0001
PCT/KR2018/008980
Figure imgf000150_0001
PCT / KR2018 / 008980
Figure imgf000150_0001
Figure imgf000150_0002
Figure imgf000150_0002
Figure imgf000151_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000152_0001
I I
Figure imgf000153_0001
Figure imgf000153_0001
ι0ε 0A //: O8ϊ02Μ12AV ι 0ε 0A //: O 8 ϊ0 2 M12AV
Figure imgf000154_0001
Figure imgf000154_0001
Figure imgf000154_0002
Figure imgf000154_0002
Figure imgf000155_0001
Figure imgf000155_0001
154 154
PCT/KR2018/008980
Figure imgf000156_0001
PCT / KR2 018/008980
Figure imgf000156_0001
Figure imgf000156_0002
ĹSI
Figure imgf000156_0002
NSI
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000159_0001
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000160_0001
159
Figure imgf000161_0001
Figure imgf000162_0001
159
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000162_0002
Figure imgf000162_0002
16
Figure imgf000163_0001
16
Figure imgf000163_0001
ί9\ ί9 \
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000165_0002
//: O8ϊ02Μ12AV
Figure imgf000165_0002
//: O 8 ϊ0 2 M12AV
Figure imgf000166_0001
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000167_0001
L91 L91
Figure imgf000168_0001
Figure imgf000168_0001
086800/8ΐΟΖΗΜ/Χ3<Ι Ϊ9^8Ζ.0/6Ϊ0Ζ O 086800 / 8ΐΟΖΗΜ / Χ3 <Ι Ϊ9 ^ 8Ζ.0 / 6Ϊ0Ζ O
Figure imgf000169_0001
Figure imgf000169_0001
Figure imgf000169_0002
Figure imgf000169_0002
168 168
Figure imgf000170_0001
Figure imgf000170_0001
Figure imgf000170_0002
Figure imgf000170_0002
169
Figure imgf000171_0001
169
Figure imgf000171_0001
Figure imgf000172_0001
Figure imgf000172_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000176_0001
Figure imgf000177_0001
Figure imgf000177_0001
176 176
Figure imgf000178_0001
Figure imgf000178_0001
177
Figure imgf000179_0001
177
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000181_0001
Figure imgf000182_0001
Figure imgf000182_0001
Figure imgf000183_0001
Figure imgf000183_0001
Figure imgf000184_0001
Figure imgf000184_0001
183 183
Figure imgf000185_0001
Figure imgf000185_0001
184
Figure imgf000186_0001
184
Figure imgf000186_0001
//: O8ϊ02Μ12AV //: O 8 ϊ0 2 M12AV
Figure imgf000187_0001
Figure imgf000187_0001
Figure imgf000188_0001
Figure imgf000188_0001
Figure imgf000188_0002
Figure imgf000188_0002
Figure imgf000188_0003
Figure imgf000188_0003
187 187
Figure imgf000189_0001
Figure imgf000189_0001
188
Figure imgf000190_0001
188
Figure imgf000190_0001
Figure imgf000191_0001
Figure imgf000191_0001
190
Figure imgf000192_0001
190
Figure imgf000192_0001
Figure imgf000193_0001
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000194_0001
Figure imgf000195_0001
Figure imgf000196_0001
Figure imgf000195_0001
Figure imgf000196_0001
Figure imgf000197_0001
Figure imgf000197_0001
Figure imgf000198_0001
Figure imgf000198_0001
197 197
Figure imgf000199_0001
Figure imgf000199_0001
198
Figure imgf000200_0001
198
Figure imgf000200_0001
ooz ooz
Figure imgf000201_0001
Figure imgf000201_0001
086800/8ΐΟΖΗΜ/Χ3<Ι Ϊ9178Ζ.0/6Ϊ0Ζ OAV //: O8ϊ02Μ12AV 086800 / 8ΐΟΖΗΜ / Χ3 <Ι Ϊ9178ZZ.0 / 6Ϊ0Ζ OAV //: O 8 ϊ0 2 M12AV
Figure imgf000202_0001
Figure imgf000202_0001
Figure imgf000203_0001
Figure imgf000203_0001
Figure imgf000204_0001
Figure imgf000204_0001
【청구항 9】 [Claim 9]
거 U 전극; 상기 제 1 전극과 대향하여 구비된 제 2 전극; 및 상기 제 1 전극과 상가 게 2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서， 상기 유기물층 중 1층 이상은 게 1항 내지 게 8항 중 어느 하나의 항에 따른 화합물을 포함하는 것인, 유기 발광 소자. Gau electrode; A second electrode facing the first electrode; And one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes at least one of the first to eighth And a compound according to one of the claims.
【청구항 10] [Claim 10]
'제 9항에 있어서，  The method of claim 9,
상기 화합물을 포함하는 유기물층은 전자수송층; 전자조절층; 전자주입층; 정공차단층; 또는 발광층인 것을 특징으로 하는， 유기 발광 소자.  The organic material layer containing the compound may include an electron transporting layer; An electron control layer; An electron injection layer; A hole blocking layer; Or a light emitting layer.
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