WO2017160068A1 - Heterocyclic compound and organic light emitting diode comprising same - Google Patents

Heterocyclic compound and organic light emitting diode comprising same Download PDF

Info

Publication number
WO2017160068A1
WO2017160068A1 PCT/KR2017/002763 KR2017002763W WO2017160068A1 WO 2017160068 A1 WO2017160068 A1 WO 2017160068A1 KR 2017002763 W KR2017002763 W KR 2017002763W WO 2017160068 A1 WO2017160068 A1 WO 2017160068A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
unsubstituted
compound
groups
Prior art date
Application number
PCT/KR2017/002763
Other languages
French (fr)
Korean (ko)
Inventor
차용범
조성미
김정범
홍성길
곽지원
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2018544457A priority Critical patent/JP6628066B2/en
Priority to CN201780017673.XA priority patent/CN108779072B/en
Publication of WO2017160068A1 publication Critical patent/WO2017160068A1/en

Links

Images

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56Ring systems containing three or more rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D403/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D403/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1003Carbocyclic compounds
    • C09K2211/1011Condensed systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1029Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/15Hole transporting layers

Definitions

  • the present specification relates to a heterocyclic compound and an organic light emitting device including the same.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • Described herein is a heterocyclic compound and an organic light emitting device comprising the same.
  • R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R 1 and R 2 combine with each other to form a substituted or unsubstituted ring,
  • L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
  • n and n are the same as or different from each other, and each independently an integer of 0 to 5,
  • L 1 is the same as or different from each other
  • L 2 is the same as or different from each other
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group,
  • R, R 'and R are the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, nitro, hydroxy, carbonyl, ester, imide, amino, substituted or unsubstituted silyl Substituted or unsubstituted boron group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryloxy group; substituted or unsubstituted alkoxy group; substituted or unsubstituted aryloxy group Substituted or unsubstituted alkenyl group; substituted or unsubstituted aralkyl group; substituted or unsubstituted alkylaryl group; substituted or unsubstituted alkylamine group; substituted or unsubstituted aralkylamine group; substituted or unsubstituted Heteroarylamine groups;
  • a and b are the same as or different from each other, and each independently an integer of 0 to 4,
  • R ' is the same as or different from each other
  • R is the same as or different from each other when b is two or more.
  • an exemplary embodiment of the present specification is an organic light emitting device including a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is It provides an organic light emitting device comprising the compound of formula (1).
  • the compound described herein can be used as the material of the organic material layer of the organic light emitting device.
  • the compound according to at least one exemplary embodiment may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode.
  • the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, electron suppression, luminescence, hole suppression, electron transport, or electron injection materials.
  • FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 It is.
  • An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1.
  • the term "substituted or unsubstituted” is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; And it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group, or substituted or unsubstituted two or more substituents of the substituents exe
  • a substituent to which two or more substituents are linked may be interpreted as an aryl group substituted with a heterocyclic group.
  • the "biphenyl group” may be one aryl group or may be interpreted as a phenyl group substituted with a phenyl group.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the silyl group may be represented by the formula of -SiR a R b R c , wherein R a , R b and R c are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.
  • Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. Do not.
  • the boron group may be represented by the formula of -BR a R b , wherein R a and R b are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.
  • the boron group may include, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, and phenylboron group.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C40. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.
  • Substituents comprising alkyl groups, alkoxy groups and other alkyl group moieties described herein include both straight and pulverized forms.
  • the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the alkylamine group is not particularly limited in carbon number, but is preferably 1 to 40.
  • Specific examples of the alkylamine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine Groups, diphenylamine groups, phenylnaphthylamine groups, ditolylamine groups, phenyltolylamine groups, triphenylamine groups and the like, but are not limited thereto.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group.
  • the arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
  • aryl amine group examples include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthra Cenylamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group and the like, but are not limited thereto.
  • examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group.
  • the heteroaryl group in the heteroarylamine group may be a monocyclic hetero ring group or may be a polycyclic hetero ring group.
  • the heteroarylamine group including two or more heterocyclic groups may simultaneously include a monocyclic hetero ring group, a polycyclic hetero ring group, or a monocyclic hetero ring group and a polycyclic hetero ring group.
  • the arylheteroarylamine group means an amine group substituted with an aryl group and a heterocyclic group.
  • examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group.
  • the aryl group in the arylphosphine group may be a monocyclic aryl group, may be a polycyclic aryl group.
  • the arylphosphine group containing two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
  • 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
  • the polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • Spirofluorenyl groups such as (9,9-dimethylfluorenyl group), and It may be a substituted fluorenyl group such as (9,9-diphenyl fluorenyl group).
  • the present invention is not limited thereto.
  • the heterocyclic group is a heterocyclic group including one or more of N, O, P, S, Si, and Se as hetero atoms, and carbon number is not particularly limited, but is preferably 1 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 1 to 30 carbon atoms.
  • heterocyclic group examples include, for example, pyridyl group, pyrrole group, pyrimidyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazole group, pyrazole group, oxazole group, isoxazole group, thiazole group, isothiazole group, Triazole group, oxadiazole group, thiadiazole group, dithiazole group, tetrazole group, pyranyl group, thiopyranyl group, pyrazinyl group, oxazinyl group, thiazinyl group, deoxyyl group, triazinyl group, tetrazinyl group, qui Nolinyl group, isoquinolinyl group, quinolyl group, quinazolinyl group, quinoxalinyl group, naphthyridinyl group, acriridyl group, xanthenyl group
  • the heterocyclic group has a number of 3 to 60 constituting a ring. In another exemplary embodiment, the heterocyclic group has 3 to 40 ring atoms. In one embodiment, the heterocyclic group has 3 to 20 ring atoms.
  • heteroaryl group is aromatic
  • the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, aryl phosphine group, aralkyl group, aralkylamine group, aralkenyl group, alkylaryl group, arylamine group, arylheteroarylamine group is described above.
  • the description of one aryl group may apply.
  • the alkyl group among the alkyl thioxy group, the alkyl sulfoxy group, the aralkyl group, the aralkyl amine group, the alkyl aryl group, and the alkyl amine group may be described with respect to the alkyl group described above.
  • heteroaryl group a heteroarylamine group, and an arylheteroarylamine group among the heteroaryl groups may be applied to the description of the aforementioned heterocyclic group.
  • alkenyl group of the alkenyl group may be applied to the description of the alkenyl group described above.
  • the description of the aryl group described above may be applied except that the arylene group is a divalent group.
  • heteroarylene group is an aromatic divalent group.
  • the aliphatic hydrocarbon ring means a ring composed only of carbon and hydrogen atoms as a ring which is not aromatic.
  • examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, and the like. There is, but is not limited to these.
  • the aromatic hydrocarbon ring means an aromatic ring composed only of carbon and hydrogen atoms.
  • examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, triphenylene, penalene, pyrene, tetracene, chrysene, pentacene, fluorene, indene, acenaph Butylene, benzofluorene, spirofluorene and the like, but is not limited thereto.
  • the aliphatic hetero ring means an aliphatic ring including at least one of heteroatoms.
  • examples of aliphatic hetero rings include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepan, Azocaine, thiocaine and the like, but are not limited to these.
  • the aromatic hetero ring means an aromatic ring including at least one of heteroatoms.
  • aromatic hetero rings include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole , Thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, tetrazine, isoquinoline, quinoline, quinol, quinazoline, quinoxaline, naphthyridine, azine Cridine, phenanthridine, diazanaphthalene, triazaindene, indole, indolizine, benzothiazole, benzoxazole, benzoimid
  • the aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic hetero ring and aromatic hetero ring may be monocyclic or polycyclic.
  • the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula A or Chemical Formula B.
  • R 1 , R 2 , L 1 , L 2 , m, n, Ar 1 , Ar 2 , R, R ′, and R ′′ are the same as in Formula 1 and Formula 2.
  • L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.
  • L 1 and L 2 are the same as or different from each other, and each independently preferably one of any one of the linking groups selected from the group below, but is not limited thereto, the structures below may be further substituted. .
  • the structures are deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amine group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl heteroaryl amine group; Aryl phosphine group; And it may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group.
  • L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group; Substituted or unsubstituted pyridylene group; Substituted or unsubstituted pyrimidinylene group; Substituted or unsubstituted triazinylene group; Substituted or unsubstituted carbazolene group; Substituted or unsubstituted dibenzofuranylene group; Or a substituted or unsubstituted dibenzothiophenylene group.
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group.
  • Ar 1 and Ar 2 may be the same as or different from each other, and each independently may be any one selected from the following structures, and the following structures may be further substituted.
  • the structures are deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amine group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl heteroaryl amine group; Aryl phosphine group; And it may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group.
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Phenyl group; A phenyl group substituted with at least one substituent selected from the group consisting of a phenyl group, a pyridine group, a quinoline group and a quinazoline group; Biphenyl group; Naphthyl group; Anthracenyl group; Anthracenyl group substituted with a phenyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group;
  • Ar 1 is a phenyl group; Naphthyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Carbazole groups; Or a carbazole group substituted with at least one selected from the group consisting of a phenyl group, a biphenyl group and a naphthyl group.
  • Ar 2 is hydrogen; Phenyl group; A phenyl group substituted with at least one substituent selected from the group consisting of a phenyl group, a pyridine group, a quinoline group and a quinazoline group; Biphenyl group; Anthracenyl group; Anthracenyl group substituted with a phenyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Benzimidazole groups; Benzimidazole groups substituted with phenyl groups; Quinoline groups
  • the R One And R 2 are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R 1 and R 2 may combine with each other to form a substituted or unsubstituted ring.
  • the R One And R 2 are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.
  • R 1 and R 2 are the same as or different from each other, and each independently an alkyl group or an aryl group.
  • the R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; Or a substituted or unsubstituted phenyl group.
  • R 1 and R 2 are the same as or different from each other, and each independently a methyl group; Or a phenyl group.
  • R, R 'and R are the same as or different from each other, and each independently hydrogen, an alkyl group, an aryl group, or a heterocyclic group.
  • R, R 'and R are all hydrogen.
  • the compound of Formula 1 may be any one selected from the following compounds.
  • the conjugation length of the compound and the energy bandgap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap.
  • compounds having various energy bandgaps can be synthesized by introducing various substituents into the core structure.
  • the HOMO and LUMO energy levels of the compound may be controlled by introducing various substituents into the core structure.
  • the compound represented by Formula A or Formula B may be synthesized using a reaction of the following general formula, but is not limited thereto.
  • Ar 3 to Ar 6 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group, the description of the Ar 1 and Ar 2 can be applied.
  • the compound which has the intrinsic property of the introduced substituent can be synthesize
  • a substituent mainly used in the hole injection layer material, the hole transport material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic light emitting device into the core structure, it is possible to synthesize a material satisfying the requirements of each organic material layer. Can be.
  • the organic light emitting device is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer It is characterized by including the compound.
  • the organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.
  • the compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device.
  • the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.
  • 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 light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.
  • the organic material layer may include at least one layer of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is represented by Formula 1 It may include a compound represented by.
  • the organic material layer may include at least one layer of a hole injection layer, an electron suppression layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is represented by Chemical Formula 1 It may include a compound represented by.
  • the organic material layer may include an electron suppression layer, and the electron suppression layer may include a compound represented by Chemical Formula 1.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.
  • the compound represented by Formula 1 may be included as a host of the light emitting layer.
  • the compound represented by Chemical Formula 1 may be included as a phosphorescent host of the emission layer.
  • the organic material layer including the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1 as a host, and may include another organic compound, a metal, or a metal compound as a dopant.
  • the organic material layer including the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1 as a host, and may be used together with an iridium-based (Ir) dopant.
  • the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include the compound.
  • the organic material layer of the organic electronic device includes a hole transport layer, and the hole transport layer includes a compound represented by Chemical Formula 1.
  • the compound may be included in a light emitting layer, a layer for simultaneously injecting / holes transporting and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting light.
  • the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
  • FIG. 1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1.
  • the compound may be included in the light emitting layer (3).
  • FIG. 2 illustrates an organic light emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, and a cathode 4 are sequentially stacked on a substrate 1.
  • the structure is illustrated.
  • the compound may be included in the hole injection layer 5, the hole transport layer 6, the light emitting layer 3, or the electron transport layer 7.
  • the organic light emitting device uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.
  • PVD metal vapor deposition
  • an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure.
  • the organic material layer may be formed by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method, rather than a deposition method. It can be prepared in layers.
  • the anode material a material having a large work function is usually preferred to facilitate hole injection into the organic material layer.
  • the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
  • the hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.
  • the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.
  • the hole transporting material a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable.
  • a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable.
  • Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • the light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.
  • Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
  • Iridium complex used as a dopant of a light emitting layer is as follows.
  • the electron transporting material is a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer.
  • a material having high mobility to electrons is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
  • the compound according to the present invention may also operate on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.
  • a glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 ⁇ was placed in distilled water in which detergent was dissolved and ultrasonically cleaned.
  • ITO indium tin oxide
  • Fischer Co. product was used as a detergent
  • distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water.
  • ultrasonic washing was performed twice with distilled water for 10 minutes.
  • ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol dried and transported to a plasma cleaner.
  • the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
  • HAT-CN hexaazatriphenylene hexanitrile
  • the following compound 3 was vacuum-deposited to a film thickness of 100 kPa on the said hole transport layer, and the electron suppression layer was formed.
  • the following BH and BD were vacuum-deposited at a weight ratio of 25: 1 on the electron suppression layer with a film thickness of 300 Pa to form a light emitting layer.
  • the compound ET1 and the compound LiQ were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 kPa.
  • lithium fluoride (LiF) and aluminum were deposited to a thickness of 12 kPa in order to form a cathode.
  • the organic light emitting device was manufactured by the same method as Experimental Example 1, except that compound 5 was used instead of compound 3 in Experimental Example 1.
  • the organic light emitting device was manufactured by the same method as Experimental Example 1, except that compound 6 was used instead of compound 3 in Experimental Example 1.
  • An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following EB1 compound instead of compound 1 in Experimental Example 1.
  • An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following EB2 compound instead of compound 1 in Experimental Example 1.
  • An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following EB3 compound instead of compound 3 in Experimental Example 1.
  • the organic light emitting device manufactured by using the compound of the present invention as an electron suppressing layer is a case of using the material of Comparative Example 1 and Comparative Example 2 in which the amine group is connected to another position of the core of the present invention and aryl Compared with the case of using the substance of Comparative Example 3, which is substituted with only a group, the compound of the present invention plays an electron suppressing role and thus exhibits excellent characteristics in terms of efficiency, driving voltage, and / or stability of the organic light emitting device.
  • Experimental Examples 1-1 to 1-3 have a driving voltage of 10% to 12% less than Comparative Examples 1 to 3, and show efficiency of 10% or more.
  • the compound according to the present invention was confirmed that the excellent electron suppression ability can be applied to the organic light emitting device.
  • An organic light emitting diode was manufactured according to the same method as Experimental Example 2 except for using the compound of EB1 instead of compound 3 in Experimental Example 2-1.
  • An organic light emitting diode was manufactured according to the same method as Experimental Example 2 except for using the compound of EB2 instead of compound 3 in Experimental Example 2-1.
  • the organic light emitting device manufactured by using the compound of the present invention as a hole transport layer compared with the case of using the material of Comparative Example 3 and Comparative Example 4 in which the amine group is connected to another position of the core of the present invention
  • the compound of the present invention plays a role of hole transport, it shows excellent properties in terms of efficiency, driving voltage and / or stability of the organic light emitting device.
  • Experimental Examples 2-1 to 2-3 show a driving voltage of 5% to 8% or more, and an efficiency of 7 to 10% or more than the comparative example.
  • the compound according to the present invention is not only excellent in electron suppression ability but also in hole transport ability, and thus can be applied to an organic light emitting device.
  • a green organic light emitting device was manufactured by the following method.
  • a glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 ⁇ was placed in distilled water in which detergent was dissolved and ultrasonically cleaned.
  • ITO indium tin oxide
  • Fischer Co. product was used as a detergent
  • distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water.
  • ultrasonic washing was performed twice with distilled water for 10 minutes.
  • ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol dried and transported to a plasma cleaner.
  • the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
  • the organic light emitting device was manufactured by the same method as Experimental Example 2, except that compound 8 was used instead of CBP in Comparative Example 5.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 9 was used instead of Compound CBP in Comparative Example 5.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 10 was used instead of Compound CBP in Comparative Example 5.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 11 was used instead of Compound CBP in Comparative Example 5.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 12 was used instead of Compound CBP in Comparative Example 5.
  • An organic light emitting device was manufactured in the same manner as in Comparative Example 5, except that the following compound of GH1 was used instead of the compound CBP in Comparative Example 5.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the following compound of GH2 was used instead of the compound CBP in Comparative Example 5.
  • the green organic light emitting device of Experimental Examples 3-1 to 3-5 using the compound of the present invention as a host material of the green light emitting layer is Comparative Example 5 using the conventional CBP and Comparative Example having a structure similar to the core of the present invention. It was confirmed that the organic light emitting device manufactured by using the compounds of 6 and 7 as the green host material showed superior performance in terms of current efficiency and driving voltage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

The present specification provides a heterocyclic compound and an organic light emitting diode comprising the same.

Description

헤테로고리 화합물 및 이를 포함하는 유기 발광 소자Heterocyclic compound and organic light emitting device comprising the same
본 명세서는 2016년 3월 14일에 한국 특허청에 제출된 한국 특허 출원 제10-2016-0030406호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This specification claims the benefit of priority based on Korean Patent Application No. 10-2016-0030406 filed with the Korean Intellectual Property Office on March 14, 2016, and all contents disclosed in the literature of the Korean patent application are part of this specification. Included.
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present specification relates to a heterocyclic compound and an organic light emitting device including the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등으로 이루어 질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.
상기와 같은 유기 발광 소자를 위한 새로운 재료의 개발이 계속 요구되고 있다.There is a continuing need for the development of new materials for such organic light emitting devices.
본 명세서에는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자가 기재된다.Described herein is a heterocyclic compound and an organic light emitting device comprising the same.
본 명세서의 일 실시상태는 하기 화학식 1로 표시되는 화합물을 제공한다: An exemplary embodiment of the present specification provides a compound represented by Formula 1:
[화학식 1][Formula 1]
Figure PCTKR2017002763-appb-I000001
Figure PCTKR2017002763-appb-I000001
상기 화학식 1에 있어서,In Chemical Formula 1,
R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이거나, R1 및 R2가 서로 결합하여 치환 또는 비치환된 고리를 형성하며,R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R 1 and R 2 combine with each other to form a substituted or unsubstituted ring,
L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이며,L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
m 및 n은 서로 같거나 상이하고, 각각 독립적으로 0 내지 5의 정수이며,m and n are the same as or different from each other, and each independently an integer of 0 to 5,
m이 2 이상인 경우에 L1은 서로 같거나 상이하고,when m is 2 or more, L 1 is the same as or different from each other,
n이 2 이상인 경우에 L2는 서로 같거나 상이하며,when n is 2 or more, L 2 is the same as or different from each other,
Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 아릴아민기; 치환 또는 비치환된 헤테로고리기; 또는 치환 또는 비치환된 포스핀옥사이드기이며,Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group,
R, R' 및 R"는 서로 같거나 상이하고, 각각 독립적으로 수수소; 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 아르알킬기; 치환 또는 비치환된 알킬아릴기; 치환 또는 비치환된 알킬아민기; 치환 또는 비치환된 아랄킬아민기; 치환 또는 비치환된 헤테로아릴아민기; 치환 또는 비치환된 아릴아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기이며,R, R 'and R "are the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, nitro, hydroxy, carbonyl, ester, imide, amino, substituted or unsubstituted silyl Substituted or unsubstituted boron group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryloxy group; substituted or unsubstituted alkoxy group; substituted or unsubstituted aryloxy group Substituted or unsubstituted alkenyl group; substituted or unsubstituted aralkyl group; substituted or unsubstituted alkylaryl group; substituted or unsubstituted alkylamine group; substituted or unsubstituted aralkylamine group; substituted or unsubstituted Heteroarylamine groups; substituted or unsubstituted arylamine groups; substituted or unsubstituted arylphosphine groups; substituted or unsubstituted phosphine oxide groups; substituted or unsubstituted aryl groups; substituted or unsubstituted heterocyclic groups Is,
a 및 b는 서로 같거나 상이하고, 각각 독립적으로 0 내지 4의 정수이며,a and b are the same as or different from each other, and each independently an integer of 0 to 4,
a가 2 이상인 경우에 R'은 서로 같거나 상이하고,when a is 2 or more, R 'is the same as or different from each other,
b가 2 이상인 경우에 R"는 서로 같거나 상이하다.R "is the same as or different from each other when b is two or more.
또한, 본 명세서의 일 실시상태는 제1 전극, 제2 전극, 및 상기 제1 전극과 제2 전극 사이에 배치된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1의 화합물을 포함하는 것인 유기 발광 소자를 제공한다.In addition, an exemplary embodiment of the present specification is an organic light emitting device including a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is It provides an organic light emitting device comprising the compound of formula (1).
본 명세서에 기재된 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있다. 적어도 하나의 실시상태에 따른 화합물은 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 본 명세서에 기재된 화합물은 정공 주입, 정공 수송, 정공 주입과 정공 수송, 전자억제, 발광, 정공억제, 전자 수송, 또는 전자 주입 재료로 사용될 수 있다.The compound described herein can be used as the material of the organic material layer of the organic light emitting device. The compound according to at least one exemplary embodiment may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, electron suppression, luminescence, hole suppression, electron transport, or electron injection materials.
도 1은 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
도 2는 기판(1), 양극(2), 정공 주입층(5), 정공 수송층(6), 발광층(3), 전자 수송층(7) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 It is.
이하 본 명세서에 대하여 더욱 상세히 설명한다. Hereinafter, the present specification will be described in more detail.
본 명세서의 일 실시상태는 상기 화학식 1로 표시되는 화합물을 제공한다. An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1.
상기 치환기들의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다. Examples of the substituents are described below, but are not limited thereto.
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; 시클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴포스핀기; 및 헤테로 고리기로 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 헤테로고리기로 치환된 아릴기로 해석될 수 있다. 또한, 보다 구체적인 예로서, "바이페닐기"는 1개의 아릴기일 수도 있고, 페닐기가 치환된 페닐기로 해석될 수도 있다.As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; And it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group, or substituted or unsubstituted two or more substituents of the substituents exemplified above. For example, "a substituent to which two or more substituents are linked" may be interpreted as an aryl group substituted with a heterocyclic group. As a more specific example, the "biphenyl group" may be one aryl group or may be interpreted as a phenyl group substituted with a phenyl group.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
Figure PCTKR2017002763-appb-I000002
Figure PCTKR2017002763-appb-I000002
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 40의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 30의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2017002763-appb-I000003
Figure PCTKR2017002763-appb-I000003
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
Figure PCTKR2017002763-appb-I000004
Figure PCTKR2017002763-appb-I000004
본 명세서에 있어서, 실릴기는 -SiRaRbRc의 화학식으로 표시될 수 있고, 상기 Ra, Rb 및 Rc는 각각 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기일 수 있다. 상기 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. In the present specification, the silyl group may be represented by the formula of -SiR a R b R c , wherein R a , R b and R c are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. Do not.
본 명세서에 있어서, 붕소기는 -BRaRb의 화학식으로 표시될 수 있고, 상기 Ra 및 Rb는 각각 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기일 수 있다. 상기 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group may be represented by the formula of -BR a R b , wherein R a and R b are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group may include, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, and phenylboron group.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 시클로펜틸메틸, 시클로헥실메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, i-프로필옥시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시, 벤질옥시, p-메틸벤질옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C40. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.
본 명세서에 기재된 알킬기, 알콕시기 및 그 외 알킬기 부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함한다.Substituents comprising alkyl groups, alkoxy groups and other alkyl group moieties described herein include both straight and pulverized forms.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 시클로알킬기의 탄소수는 3 내지 40이다. 또 하나의 실시상태에 따르면, 상기 시클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 시클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 시클로프로필, 시클로부틸, 시클로펜틸, 3-메틸시클로펜틸, 2,3-디메틸시클로펜틸, 시클로헥실, 3-메틸시클로헥실, 4-메틸시클로헥실, 2,3-디메틸시클로헥실, 3,4,5-트리메틸시클로헥실, 4-tert-부틸시클로헥실, 시클로헵틸, 시클로옥틸 등이 있으나, 이에 한정되지 않는다. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.
본 명세서에 있어서, 알킬아민기는 탄소수는 특별히 한정되지 않으나, 1 내지 40인 것이 바람직하다. 알킬아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 비페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, 페닐나프틸아민기, 디톨릴아민기, 페닐톨릴아민기, 트리페닐아민기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the alkylamine group is not particularly limited in carbon number, but is preferably 1 to 40. Specific examples of the alkylamine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine Groups, diphenylamine groups, phenylnaphthylamine groups, ditolylamine groups, phenyltolylamine groups, triphenylamine groups and the like, but are not limited thereto.
본 명세서에 있어서, 아릴아민기의 예로는 치환 또는 비치환된 모노아릴아민기, 치환 또는 비치환된 디아릴아민기, 또는 치환 또는 비치환된 트리아릴아민기가 있다. 상기 아릴아민기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기일 수 있다. 상기 2 이상의 아릴기를 포함하는 아릴아민기는 단환식 아릴기, 다환식 아릴기, 또는 단환식아릴기와 다환식 아릴기를 동시에 포함할 수 있다. In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
아릴 아민기의 구체적인 예로는 페닐아민, 나프틸아민, 비페닐아민, 안트라세닐아민, 3-메틸-페닐아민, 4-메틸-나프틸아민, 2-메틸-비페닐아민, 9-메틸-안트라세닐아민, 디페닐 아민기, 페닐 나프틸 아민기, 디톨릴 아민기, 페닐 톨릴 아민기, 카바졸 및 트리페닐 아민기 등이 있으나, 이에 한정되는 것은 아니다.Specific examples of the aryl amine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthra Cenylamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group and the like, but are not limited thereto.
본 명세서에 있어서, 헤테로아릴아민기의 예로는 치환 또는 비치환된 모노헤테로아릴아민기, 치환 또는 비치환된 디헤테로아릴아민기, 또는 치환 또는 비치환된 트리헤테로아릴아민기가 있다. 상기 헤테로아릴아민기 중의 헤테로아릴기는 단환식 헤테로 고리기일 수 있고, 다환식 헤테로 고리기일 수 있다. 상기 2 이상의 헤테로 고리기를 포함하는 헤테로아릴아민기는 단환식 헤테로 고리기, 다환식 헤테로 고리기, 또는 단환식 헤테로 고리기와 다환식 헤테로 고리기를 동시에 포함할 수 있다. In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic hetero ring group or may be a polycyclic hetero ring group. The heteroarylamine group including two or more heterocyclic groups may simultaneously include a monocyclic hetero ring group, a polycyclic hetero ring group, or a monocyclic hetero ring group and a polycyclic hetero ring group.
본 명세서에 있어서, 아릴헤테로아릴아민기는 아릴기 및 헤테로 고리기로 치환된 아민기를 의미한다.In the present specification, the arylheteroarylamine group means an amine group substituted with an aryl group and a heterocyclic group.
본 명세서에 있어서, 아릴포스핀기의 예로는 치환 또는 비치환된 모노아릴포스핀기, 치환 또는 비치환된 디아릴포스핀기, 또는 치환 또는 비치환된 트리아릴포스핀기가 있다. 상기 아릴포스핀기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기일 수 있다. 상기 아릴기가 2 이상을 포함하는 아릴포스핀기는 단환식 아릴기, 다환식 아릴기, 또는 단환식 아릴기와 다환식 아릴기를 동시에 포함할 수 있다.In the present specification, examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group. The aryl group in the arylphosphine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylphosphine group containing two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2017002763-appb-I000005
,
Figure PCTKR2017002763-appb-I000006
등의 스피로플루오레닐기,
Figure PCTKR2017002763-appb-I000007
(9,9-디메틸플루오레닐기), 및
Figure PCTKR2017002763-appb-I000008
(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.
When the fluorenyl group is substituted,
Figure PCTKR2017002763-appb-I000005
,
Figure PCTKR2017002763-appb-I000006
Spirofluorenyl groups, such as
Figure PCTKR2017002763-appb-I000007
(9,9-dimethylfluorenyl group), and
Figure PCTKR2017002763-appb-I000008
It may be a substituted fluorenyl group such as (9,9-diphenyl fluorenyl group). However, the present invention is not limited thereto.
본 명세서에 있어서, 헤테로 고리기는 이종원자로 N, O, P, S, Si 및 Se 중 1개 이상을 포함하는 헤테로 고리기로서, 탄소수는 특별히 한정되지 않으나 탄소수 1 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 헤테로 고리기의 탄소수는 1 내지 30이다. 헤테로 고리기의 예로는 예로는 피리딜기, 피롤기, 피리미딜기, 피리다지닐기, 퓨라닐기, 티오페닐기, 이미다졸기, 피라졸기, 옥사졸기, 이소옥사졸기, 티아졸기, 이소티아졸기, 트리아졸기, 옥사디아졸기, 티아디아졸기, 디티아졸기, 테트라졸기, 피라닐기, 티오피라닐기, 피라지닐기, 옥사지닐기, 티아지닐기, 디옥시닐기, 트리아지닐기, 테트라지닐기, 퀴놀리닐기, 이소퀴놀리닐기, 퀴놀릴기, 퀴나졸리닐기, 퀴녹살리닐기, 나프티리디닐기, 아크리딜기, 크산테닐기, 페난트리디닐기, 디아자나프탈레닐기, 트리아자인데닐기, 인돌기, 인돌리닐기, 인돌리지닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 벤조티아졸기, 벤즈옥사졸기, 벤즈이미다졸기, 벤조티오펜기, 벤조퓨라닐기, 디벤조티오페닐기, 디벤조퓨라닐기, 카바졸기, 벤조카바졸기, 디벤조카바졸기, 인돌로카바졸기, 인데노카바졸기, 페나지닐기, 이미다조피리딘기, 페녹사지닐기, 페난트리딘기, 페난트롤린(phenanthroline)기, 페노티아진(phenothiazine)기, 이미다조피리딘기, 이미다조페난트리딘기. 벤조이미다조퀴나졸린기, 또는 벤조이미다조페난트리딘기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heterocyclic group including one or more of N, O, P, S, Si, and Se as hetero atoms, and carbon number is not particularly limited, but is preferably 1 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 1 to 30 carbon atoms. Examples of the heterocyclic group include, for example, pyridyl group, pyrrole group, pyrimidyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazole group, pyrazole group, oxazole group, isoxazole group, thiazole group, isothiazole group, Triazole group, oxadiazole group, thiadiazole group, dithiazole group, tetrazole group, pyranyl group, thiopyranyl group, pyrazinyl group, oxazinyl group, thiazinyl group, deoxyyl group, triazinyl group, tetrazinyl group, qui Nolinyl group, isoquinolinyl group, quinolyl group, quinazolinyl group, quinoxalinyl group, naphthyridinyl group, acriridyl group, xanthenyl group, phenanthridinyl group, diazanaphthalenyl group, triazaininyl group, indole group , Indolinyl group, indolinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, benzothiazole group, benzoxazole group, benzimidazole group, benzothiophene group , Benzofuranyl group, dibenzothiophenyl group, dibenzofuranyl , Carbazole group, benzocarbazole group, dibenzocarbazole group, indolocarbazole group, indenocarbazole group, phenazinyl group, imidazopyridine group, phenoxazinyl group, phenanthridine group, phenanthroline group, phenanthroline group, phenanthroline group Phenothiazine, imidazopyridine and imidazophenanthridine groups. Although there exists a benzoimidazoquinazoline group or a benzoimidazophenanthridine group, it is not limited only to these.
본 명세서의 일 실시상태에 있어서, 상기 헤테로 고리기는 고리를 이루는 원소의 수가 3 내지 60이다. 또 하나의 실시상태에 있어서, 상기 헤테로 고리기는 고리를 이루는 원소의 수가 3 내지 40이다. 일 실시상태에 있어서, 상기 헤테로 고리기는 고리를 이루는 원소의 수가 3 내지 20이다.In one embodiment of the present specification, the heterocyclic group has a number of 3 to 60 constituting a ring. In another exemplary embodiment, the heterocyclic group has 3 to 40 ring atoms. In one embodiment, the heterocyclic group has 3 to 20 ring atoms.
본 명세서에 있어서, 헤테로아릴기는 방향족인 것을 제외하고는 전술한 헤테로 고리기에 관한 설명이 적용될 수 있다.In the present specification, the description of the aforementioned hetero ring group may be applied except that the heteroaryl group is aromatic.
본 명세서에 있어서, 아릴옥시기, 아릴티옥시기, 아릴술폭시기, 아릴포스핀기, 아르알킬기, 아랄킬아민기, 아르알케닐기, 알킬아릴기, 아릴아민기, 아릴헤테로아릴아민기 중의 아릴기는 전술한 아릴기에 관한 설명이 적용될 수 있다.In the present specification, the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, aryl phosphine group, aralkyl group, aralkylamine group, aralkenyl group, alkylaryl group, arylamine group, arylheteroarylamine group is described above. The description of one aryl group may apply.
본 명세서에 있어서, 알킬티옥시기, 알킬술폭시기, 아르알킬기, 아랄킬아민기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기에 관한 설명이 적용될 수 있다. In the present specification, the alkyl group among the alkyl thioxy group, the alkyl sulfoxy group, the aralkyl group, the aralkyl amine group, the alkyl aryl group, and the alkyl amine group may be described with respect to the alkyl group described above.
본 명세서에 있어서, 헤테로아릴기, 헤테로아릴아민기, 아릴헤테로아릴아민기 중 헤테로아릴기는 전술한 헤테로 고리기에 관한 설명이 적용될 수 있다. In the present specification, a heteroaryl group, a heteroarylamine group, and an arylheteroarylamine group among the heteroaryl groups may be applied to the description of the aforementioned heterocyclic group.
본 명세서에 있어서, 아르알케닐기 중 알케닐기는 전술한 알케닐기에 관한 설명이 적용될 수 있다. In the present specification, the alkenyl group of the alkenyl group may be applied to the description of the alkenyl group described above.
본 명세서에 있어서, 아릴렌기는 2가기인 것을 제외하고는 전술한 아릴기에 관한 설명이 적용될 수 있다. In the present specification, the description of the aryl group described above may be applied except that the arylene group is a divalent group.
본 명세서에 있어서, 헤테로아릴렌기는 방향족의 2가기인 것을 제외하고는 전술한 헤테로 고리기에 관한 설명이 적용될 수 있다.In the present specification, the description of the aforementioned hetero ring group may be applied except that the heteroarylene group is an aromatic divalent group.
본 명세서에 있어서, 지방족 탄화수소 고리란 방향족이 아닌 고리로서 탄소와 수소 원자로만 이루어진 고리를 의미한다. 구체적으로, 지방족 탄화수소 고리의 예로는 시클로프로판, 시클로부탄, 시클로부텐, 시클로펜탄, 시클로펜텐, 시클로헥산, 시클로헥센, 1,4-시클로헥사디엔, 시클로헵탄, 시클로헵텐, 시클로옥탄, 시클로옥텐 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the aliphatic hydrocarbon ring means a ring composed only of carbon and hydrogen atoms as a ring which is not aromatic. Specifically, examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, and the like. There is, but is not limited to these.
본 명세서에 있어서, 방향족 탄화수소 고리란 탄소와 수소 원자로만 이루어진 방향족의 고리를 의미한다. 구체적으로, 방향족 탄화수소 고리의 예로는 벤젠, 나프탈렌, 안트라센, 페난트렌, 페릴렌, 플루오란텐, 트리페닐렌, 페날렌, 피렌, 테트라센, 크라이센, 펜타센, 플루오렌, 인덴, 아세나프틸렌, 벤조플루오렌, 스피로플루오렌 등이 있으나 이들에만 한정되는 것은 아니다.In the present specification, the aromatic hydrocarbon ring means an aromatic ring composed only of carbon and hydrogen atoms. Specifically, examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, triphenylene, penalene, pyrene, tetracene, chrysene, pentacene, fluorene, indene, acenaph Butylene, benzofluorene, spirofluorene and the like, but is not limited thereto.
본 명세서에 있어서, 지방족 헤테로 고리란 헤테로원자 중 1개 이상을 포함하는 지방족 고리를 의미한다. 구체적으로, 지방족 헤테로 고리의 예로는 옥시레인(oxirane), 테트라하이드로퓨란, 1,4-디옥세인(1,4-dioxane), 피롤리딘, 피페리딘, 모르폴린(morpholine), 옥세판, 아조케인, 티오케인 등이 있으나 이들에만 한정되는 것은 아니다.In the present specification, the aliphatic hetero ring means an aliphatic ring including at least one of heteroatoms. Specifically, examples of aliphatic hetero rings include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepan, Azocaine, thiocaine and the like, but are not limited to these.
본 명세서에 있어서, 방향족 헤테로 고리란 헤테로원자 중 1개 이상을 포함하는 방향족 고리를 의미한다. 구체적으로, 방향족 헤테로 고리의 예로는 피리딘, 피롤, 피리미딘, 피리다진, 퓨란, 티오펜, 이미다졸, 피라졸, 옥사졸, 이소옥사졸, 티아졸, 이소티아졸, 트리아졸, 옥사디아졸, 티아디아졸, 디티아졸, 테트라졸, 피란, 티오피란, 디아진, 옥사진, 티아진, 다이옥신, 트리아진, 테트라진, 이소퀴놀린, 퀴놀린, 퀴놀, 퀴나졸린, 퀴녹살린, 나프티리딘, 아크리딘, 페난트리딘, 디아자나프탈렌, 트리아자인덴, 인돌, 인돌리진, 벤조티아졸, 벤조옥사졸, 벤조이미다졸, 벤조티오펜, 벤조퓨란, 디벤조티오펜, 디벤조퓨란, 카바졸, 벤조카바졸, 디벤조카바졸, 페나진, 이미다조피리딘, 페녹사진, 페난트리딘, 인돌로카바졸, 인데노카바졸 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the aromatic hetero ring means an aromatic ring including at least one of heteroatoms. Specifically, examples of aromatic hetero rings include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole , Thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, tetrazine, isoquinoline, quinoline, quinol, quinazoline, quinoxaline, naphthyridine, azine Cridine, phenanthridine, diazanaphthalene, triazaindene, indole, indolizine, benzothiazole, benzoxazole, benzoimidazole, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, carbazole , Benzocarbazole, dibenzocarbazole, phenazine, imidazopyridine, phenoxazine, phenanthridine, indolocarbazole, indenocarbazole, and the like, but are not limited thereto.
본 명세서에 있어서, 상기 지방족 탄화수소 고리, 방향족 탄화수소 고리, 지방족 헤테로 고리 및 방향족 헤테로 고리는 단환 또는 다환일 수 있다. In the present specification, the aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic hetero ring and aromatic hetero ring may be monocyclic or polycyclic.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 A 또는 화학식 B로 표시될 수 있다.In one embodiment of the present specification, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula A or Chemical Formula B.
[화학식 A][Formula A]
Figure PCTKR2017002763-appb-I000009
Figure PCTKR2017002763-appb-I000009
[화학식 B][Formula B]
Figure PCTKR2017002763-appb-I000010
Figure PCTKR2017002763-appb-I000010
상기 화학식 A 및 화학식 B에 있어서, In Chemical Formula A and Chemical Formula B,
R1, R2, L1, L2, m, n, Ar1, Ar2, R, R' 및 R"의 정의는 화학식 1 및 화학식 2에서와 같다.The definitions of R 1 , R 2 , L 1 , L 2 , m, n, Ar 1 , Ar 2 , R, R ′, and R ″ are the same as in Formula 1 and Formula 2.
본 명세서의 일 실시상태에 있어서, L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이다. In one embodiment of the present specification, L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.
또한, 본 명세서에서 L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 아래의 군으로부터 선택되는 어느 하나의 연결기인 것이 바람직하나, 이에 한정되지 않으며, 아래의 구조들은 추가로 치환될 수 있다.Also, in the present specification, L 1 and L 2 are the same as or different from each other, and each independently preferably one of any one of the linking groups selected from the group below, but is not limited thereto, the structures below may be further substituted. .
Figure PCTKR2017002763-appb-I000011
Figure PCTKR2017002763-appb-I000011
상기 구조들은 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아민기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 시클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴헤테로아릴아민기; 아릴포스핀기; 및 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환될 수 있다.The structures are deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amine group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl heteroaryl amine group; Aryl phosphine group; And it may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group.
본 명세서의 일 실시상태에 있어서, L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 피리딜렌기; 치환 또는 비치환된 피리미디닐렌기; 치환 또는 비치환된 트리아지닐렌기; 치환 또는 비치환된 카바졸렌기; 치환 또는 비치환된 디벤조퓨라닐렌기; 또는 치환 또는 비치환된 디벤조티오페닐렌기이다.In one embodiment of the present specification, L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted phenylene group; Substituted or unsubstituted pyridylene group; Substituted or unsubstituted pyrimidinylene group; Substituted or unsubstituted triazinylene group; Substituted or unsubstituted carbazolene group; Substituted or unsubstituted dibenzofuranylene group; Or a substituted or unsubstituted dibenzothiophenylene group.
본 명세서의 일 실시상태에 따르면, 상기 Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 아릴아민기; 치환 또는 비치환된 헤테로고리기; 또는 치환 또는 비치환된 포스핀옥사이드기이다.According to an exemplary embodiment of the present specification, Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group.
또한, 본 명세서의 일 실시상태에 따르면, 상기 Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 하기 구조들에서 선택된 어느 하나일 수 있고, 하기 구조들은 추가로 치환될 수 있다.In addition, according to an exemplary embodiment of the present specification, Ar 1 and Ar 2 may be the same as or different from each other, and each independently may be any one selected from the following structures, and the following structures may be further substituted.
Figure PCTKR2017002763-appb-I000012
Figure PCTKR2017002763-appb-I000012
Figure PCTKR2017002763-appb-I000013
Figure PCTKR2017002763-appb-I000013
Figure PCTKR2017002763-appb-I000014
Figure PCTKR2017002763-appb-I000014
Figure PCTKR2017002763-appb-I000015
Figure PCTKR2017002763-appb-I000015
Figure PCTKR2017002763-appb-I000016
Figure PCTKR2017002763-appb-I000016
Figure PCTKR2017002763-appb-I000017
Figure PCTKR2017002763-appb-I000017
Figure PCTKR2017002763-appb-I000018
Figure PCTKR2017002763-appb-I000018
Figure PCTKR2017002763-appb-I000019
Figure PCTKR2017002763-appb-I000019
Figure PCTKR2017002763-appb-I000020
Figure PCTKR2017002763-appb-I000020
Figure PCTKR2017002763-appb-I000021
Figure PCTKR2017002763-appb-I000021
Figure PCTKR2017002763-appb-I000022
Figure PCTKR2017002763-appb-I000022
Figure PCTKR2017002763-appb-I000023
Figure PCTKR2017002763-appb-I000023
Figure PCTKR2017002763-appb-I000024
Figure PCTKR2017002763-appb-I000024
구체적으로, 상기 구조들은 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아민기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 시클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴헤테로아릴아민기; 아릴포스핀기; 및 헤테로 고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환될 수 있다.Specifically, the structures are deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amine group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl heteroaryl amine group; Aryl phosphine group; And it may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group.
본 명세서의 일 실시상태에 따르면, 상기 Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 수소; 페닐기; 페닐기, 피리딘기, 퀴놀린기 및 퀴나졸린기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 페닐기; 바이페닐기; 나프틸기; 안트라세닐기; 페닐기로 치환된 안트라세닐기; 피리딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리딘기; 피리미딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리미딘기; 트리아진기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 트리아진기; 벤즈이미다졸기; 페닐기로 치환된 벤즈이미다졸기; 퀴놀린기; 페닐기로 치환된 퀴놀린기; 퀴나졸린기; 페닐기로 치환된 퀴나졸린기; 카바졸기; 페닐기, 바이페닐기 및 나프틸기로 이루어진 군에서 선택된 1 이상으로 치환된 카바졸기; 디벤조퓨란기; 디벤조티오펜기; 페닐기, 바이페닐기 및 플루오렌기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 아민기; 또는 페닐기로 치환된 포스핀옥사이드기이다.According to an exemplary embodiment of the present specification, Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Phenyl group; A phenyl group substituted with at least one substituent selected from the group consisting of a phenyl group, a pyridine group, a quinoline group and a quinazoline group; Biphenyl group; Naphthyl group; Anthracenyl group; Anthracenyl group substituted with a phenyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Benzimidazole groups; Benzimidazole groups substituted with phenyl groups; Quinoline groups; Quinoline groups substituted with phenyl groups; Quinazoline group; A quinazoline group substituted with a phenyl group; Carbazole groups; A carbazole group substituted with at least one selected from the group consisting of a phenyl group, a biphenyl group and a naphthyl group; Dibenzofuran group; Dibenzothiophene group; An amine group substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group and a fluorene group; Or a phosphine oxide group substituted with a phenyl group.
일 실시상태에 따르면, 상기 Ar1은 페닐기; 나프틸기; 피리딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리딘기; 피리미딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리미딘기; 트리아진기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 트리아진기; 카바졸기; 또는 페닐기, 바이페닐기 및 나프틸기로 이루어진 군에서 선택된 1 이상으로 치환된 카바졸기이다.According to an exemplary embodiment, Ar 1 is a phenyl group; Naphthyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Carbazole groups; Or a carbazole group substituted with at least one selected from the group consisting of a phenyl group, a biphenyl group and a naphthyl group.
일 실시상태에 따르면, 상기 Ar2는 수소; 페닐기; 페닐기, 피리딘기, 퀴놀린기 및 퀴나졸린기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 페닐기; 바이페닐기; 안트라세닐기; 페닐기로 치환된 안트라세닐기; 피리딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리딘기; 피리미딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리미딘기; 트리아진기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 트리아진기; 벤즈이미다졸기; 페닐기로 치환된 벤즈이미다졸기; 퀴놀린기; 페닐기로 치환된 퀴놀린기; 퀴나졸린기; 페닐기로 치환된 퀴나졸린기; 카바졸기; 페닐기, 바이페닐기 및 플루오렌기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 아민기; 페닐기로 치환된 카바졸기; 디벤조퓨란기; 디벤조티오펜기; 또는 페닐기로 치환된 포스핀옥사이드기이다.According to an exemplary embodiment, Ar 2 is hydrogen; Phenyl group; A phenyl group substituted with at least one substituent selected from the group consisting of a phenyl group, a pyridine group, a quinoline group and a quinazoline group; Biphenyl group; Anthracenyl group; Anthracenyl group substituted with a phenyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Benzimidazole groups; Benzimidazole groups substituted with phenyl groups; Quinoline groups; Quinoline groups substituted with phenyl groups; Quinazoline group; A quinazoline group substituted with a phenyl group; Carbazole groups; An amine group substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group and a fluorene group; Carbazole groups substituted with phenyl groups; Dibenzofuran group; Dibenzothiophene group; Or a phosphine oxide group substituted with a phenyl group.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이거나, R1 및 R2가 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, the R One And R 2 Are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R 1 and R 2 may combine with each other to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, the R One And R 2 Are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.
일 실시상태에 따르면, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 알킬기 또는 아릴기이다.According to an exemplary embodiment, R 1 and R 2 are the same as or different from each other, and each independently an alkyl group or an aryl group.
또 하나의 실시상태에 따르면, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 메틸기; 또는 치환 또는 비치환된 페닐기이다.According to another exemplary embodiment, the R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; Or a substituted or unsubstituted phenyl group.
일 실시상태에 따르면, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 메틸기; 또는 페닐기이다.According to an exemplary embodiment, R 1 and R 2 are the same as or different from each other, and each independently a methyl group; Or a phenyl group.
본 명세서의 일 실시상태에 있어서, R, R' 및 R"는 서로 같거나 상이하고, 각각 독립적으로 수소; 알킬기; 아릴기; 또는 헤테로고리기이다.In one embodiment of the present specification, R, R 'and R "are the same as or different from each other, and each independently hydrogen, an alkyl group, an aryl group, or a heterocyclic group.
일 실시상태에 있어서, R, R' 및 R"는 모두 수소이다.In one embodiment, R, R 'and R "are all hydrogen.
본 발명의 일 실시상태에 있어서, 상기 화학식 1의 화합물은 하기 화합물들 중에서 선택된 어느 하나일 수 있다.In one embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.
Figure PCTKR2017002763-appb-I000025
Figure PCTKR2017002763-appb-I000025
Figure PCTKR2017002763-appb-I000026
Figure PCTKR2017002763-appb-I000026
Figure PCTKR2017002763-appb-I000027
Figure PCTKR2017002763-appb-I000027
Figure PCTKR2017002763-appb-I000028
Figure PCTKR2017002763-appb-I000028
Figure PCTKR2017002763-appb-I000029
Figure PCTKR2017002763-appb-I000029
Figure PCTKR2017002763-appb-I000030
Figure PCTKR2017002763-appb-I000030
Figure PCTKR2017002763-appb-I000031
Figure PCTKR2017002763-appb-I000031
Figure PCTKR2017002763-appb-I000032
Figure PCTKR2017002763-appb-I000032
Figure PCTKR2017002763-appb-I000033
Figure PCTKR2017002763-appb-I000033
Figure PCTKR2017002763-appb-I000034
Figure PCTKR2017002763-appb-I000034
Figure PCTKR2017002763-appb-I000035
Figure PCTKR2017002763-appb-I000035
Figure PCTKR2017002763-appb-I000036
Figure PCTKR2017002763-appb-I000036
Figure PCTKR2017002763-appb-I000037
Figure PCTKR2017002763-appb-I000037
Figure PCTKR2017002763-appb-I000038
Figure PCTKR2017002763-appb-I000038
화합물의 컨쥬게이션 길이와 에너지 밴드갭은 밀접한 관계가 있다. 구체적으로, 화합물의 컨쥬게이션 길이가 길수록 에너지 밴드갭이 작아진다. The conjugation length of the compound and the energy bandgap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap.
본 발명에서는 상기 코어 구조에 다양한 치환기를 도입함으로써 다양한 에너지 밴드갭을 갖는 화합물을 합성할 수 있다. 또한, 본 발명에서는 상기 코어 구조에 다양한 치환기를 도입함으로써 화합물의 HOMO 및 LUMO 에너지 준위도 조절할 수 있다.In the present invention, compounds having various energy bandgaps can be synthesized by introducing various substituents into the core structure. In addition, in the present invention, the HOMO and LUMO energy levels of the compound may be controlled by introducing various substituents into the core structure.
상기 화학식 A 또는 화학식 B로 표시되는 화합물은 하기의 일반식의 반응을 이용하여 합성할 수 있으며, 이에 한정되는 것은 아니다.The compound represented by Formula A or Formula B may be synthesized using a reaction of the following general formula, but is not limited thereto.
(1) 화학식 A로 표시되는 화합물의 일반적인 합성 방법(1) General Synthesis Method of Compound Represented by Formula (A)
Figure PCTKR2017002763-appb-I000039
Figure PCTKR2017002763-appb-I000039
Figure PCTKR2017002763-appb-I000040
Figure PCTKR2017002763-appb-I000040
Figure PCTKR2017002763-appb-I000041
Figure PCTKR2017002763-appb-I000041
④-1④-1
Figure PCTKR2017002763-appb-I000042
Figure PCTKR2017002763-appb-I000042
④-2④-2
Figure PCTKR2017002763-appb-I000043
Figure PCTKR2017002763-appb-I000043
(2) 화학식 B로 표시되는 화합물의 일반적인 합성 방법(2) General Synthesis Method of Compound Represented by Formula B
Figure PCTKR2017002763-appb-I000044
Figure PCTKR2017002763-appb-I000044
Figure PCTKR2017002763-appb-I000045
Figure PCTKR2017002763-appb-I000045
Figure PCTKR2017002763-appb-I000046
Figure PCTKR2017002763-appb-I000046
④-1'④-1 '
Figure PCTKR2017002763-appb-I000047
Figure PCTKR2017002763-appb-I000047
④-2'④-2 '
Figure PCTKR2017002763-appb-I000048
Figure PCTKR2017002763-appb-I000048
상기 Ar3 내지 Ar6은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 아릴아민기; 치환 또는 비치환된 헤테로고리기; 또는 치환 또는 비치환된 포스핀옥사이드기이며, 상기 Ar1 및 Ar2에 대한 설명이 적용될 수 있다.Ar 3 to Ar 6 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group, the description of the Ar 1 and Ar 2 can be applied.
또한, 상기와 같은 구조의 코어 구조에 다양한 치환기를 도입함으로써 도입된 치환기의 고유 특성을 갖는 화합물을 합성할 수 있다. 예컨대, 유기 발광 소자 제조시 사용되는 정공 주입층 물질, 정공 수송용 물질, 발광층 물질 및 전자 수송층 물질에 주로 사용되는 치환기를 상기 코어 구조에 도입함으로써 각 유기물층에서 요구하는 조건들을 충족시키는 물질을 합성할 수 있다.Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. For example, by incorporating a substituent mainly used in the hole injection layer material, the hole transport material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic light emitting device into the core structure, it is possible to synthesize a material satisfying the requirements of each organic material layer. Can be.
또한, 본 발명에 따른 유기 발광 소자는 제1 전극, 제2 전극, 및 상기 제1 전극과 제2 전극 사이에 배치된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화합물을 포함하는 것을 특징으로 한다.In addition, the organic light emitting device according to the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer It is characterized by including the compound.
본 발명의 유기 발광 소자는 전술한 화합물을 이용하여 한 층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기 발광 소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.
상기 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥 코팅, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.The compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.
본 발명의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물층으로서 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등을 포함하는 구조를 가질 수 있다. 그러나, 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기물층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a 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 light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.
따라서, 본 발명의 유기 발광 소자에서, 상기 유기물층은 정공 주입층, 정공 수송층, 및 정공 주입과 정공 수송을 동시에 하는 층 중 1층 이상을 포함할 수 있고, 상기 층들 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.Accordingly, in the organic light emitting device of the present invention, the organic material layer may include at least one layer of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is represented by Formula 1 It may include a compound represented by.
일 실시상태에 있어서, 상기 유기물층은 정공 주입층, 전자 억제층, 정공 수송층, 및 정공 주입과 정공 수송을 동시에 하는 층 중 1층 이상을 포함할 수 있고, 상기 층들 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In an exemplary embodiment, the organic material layer may include at least one layer of a hole injection layer, an electron suppression layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is represented by Chemical Formula 1 It may include a compound represented by.
또 하나의 예로서, 상기 유기물층은 전자 억제층을 포함하고, 상기 전자 억제층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.As another example, the organic material layer may include an electron suppression layer, and the electron suppression layer may include a compound represented by Chemical Formula 1.
또 하나의 실시 상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층이 상기 화학식 1로 표시되는 화합물을 포함한다. 하나의 예로서, 상기 화학식 1로 표시되는 화합물은 발광층의 호스트로서 포함될 수 있다. 또 하나의 예로서, 상기 화학식 1로 표시되는 화합물은 발광층의 인광 호스트로서 포함될 수 있다.In another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1. As one example, the compound represented by Formula 1 may be included as a host of the light emitting layer. As another example, the compound represented by Chemical Formula 1 may be included as a phosphorescent host of the emission layer.
또 하나의 예로서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 상기 화학식 1로 표시되는 화합물을 호스트로서 포함하고, 다른 유기화합물, 금속 또는 금속화합물을 도펀트로 포함할 수 있다.As another example, the organic material layer including the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1 as a host, and may include another organic compound, a metal, or a metal compound as a dopant.
또 하나의 예로서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 상기 화학식 1로 표시되는 화합물을 호스트로서 포함하고, 이리듐계(Ir) 도펀트와 함께 사용할 수 있다.As another example, the organic material layer including the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1 as a host, and may be used together with an iridium-based (Ir) dopant.
또한, 상기 유기물층은 전자 수송층, 전자 주입층, 및 전자 수송과 전자 주입을 동시에 하는 층 중 1층 이상을 포함할 수 있고, 상기 층들 중 1층 이상이 상기 화합물을 포함할 수 있다.In addition, the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include the compound.
또 하나의 실시상태에 있어서, 상기 유기 전자 소자의 유기물층은 정공 수송층을 포함하고, 상기 정공 수송층이 상기 화학식 1로 표시되는 화합물을 포함한다.In another exemplary embodiment, the organic material layer of the organic electronic device includes a hole transport layer, and the hole transport layer includes a compound represented by Chemical Formula 1.
이와 같은 다층 구조의 유기물층에서 상기 화합물은 발광층, 정공 주입/정공 수송과 발광을 동시에 하는 층, 정공 수송과 발광을 동시에 하는 층, 또는 전자 수송과 발광을 동시에 하는 층 등에 포함될 수 있다.In the organic layer of the multilayer structure, the compound may be included in a light emitting layer, a layer for simultaneously injecting / holes transporting and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting light.
예컨대, 본 발명의 유기 발광 소자의 구조는 도 1 및 도 2에 나타낸 것과 같은 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
도 1에는 기판(1) 위에 양극(2), 발광층(3) 및 음극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서, 상기 화합물은 상기 발광층(3)에 포함될 수 있다.1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In such a structure, the compound may be included in the light emitting layer (3).
도 2에는 기판(1) 위에 양극(2), 정공 주입층(5), 정공 수송층(6), 발광층(3), 전자 수송층(7) 및 음극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서, 상기 화합물은 상기 정공 주입층(5), 정공 수송층(6), 발광층(3) 또는 전자 수송층(7)에 포함될 수 있다.2 illustrates an organic light emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, and a cathode 4 are sequentially stacked on a substrate 1. The structure is illustrated. In such a structure, the compound may be included in the hole injection layer 5, the hole transport layer 6, the light emitting layer 3, or the electron transport layer 7.
예컨대, 본 발명에 따른 유기 발광 소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수도 있다.For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
상기 유기물층은 정공 주입층, 정공 수송층, 발광층 및 전자 수송층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. 또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용매 공정(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method, rather than a deposition method. It can be prepared in layers.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO : Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸화합물의), 폴리[3,4-(에틸렌-1,2-디옥시)화합물의](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
상기 정공 주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입 받을 수 있는 물질로서, 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리화합물의 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.
상기 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다.As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
상기 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로는 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다.The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
발광층의 도펀트로 사용되는 이리듐계 착물은 하기와 같다.Iridium complex used as a dopant of a light emitting layer is as follows.
[Ir(piq)3]        [Btp2Ir(acac)]Ir (piq) 3 [Btp 2 Ir (acac)]
Figure PCTKR2017002763-appb-I000049
Figure PCTKR2017002763-appb-I000049
[Ir(ppy)3]         [Ir(ppy)2(acac)][Ir (ppy) 3 ] [Ir (ppy) 2 (acac)]
Figure PCTKR2017002763-appb-I000050
Figure PCTKR2017002763-appb-I000050
[Ir(mpyp)3]       [F2Irpic]Ir (mpyp) 3 [F 2 Irpic]
Figure PCTKR2017002763-appb-I000051
Figure PCTKR2017002763-appb-I000051
[(F2ppy)2Ir(tmd)]        [Ir(dfppz)3][(F 2 ppy) 2 Ir (tmd)] [Ir (dfppz) 3 ]
Figure PCTKR2017002763-appb-I000052
Figure PCTKR2017002763-appb-I000052
상기 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다.The electron transporting material is a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer. A material having high mobility to electrons is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
본 발명에 따른 화합물은 유기 태양 전지, 유기 감광체, 유기 트랜지스터 등을 비롯한 유기 전자 소자에서도 유기 발광 소자에 적용되는 것과 유사한 원리로 작용할 수 있다.The compound according to the present invention may also operate on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.
상기 화학식 1의 화합물의 제조방법 및 이들을 이용한 유기 발광 소자의 제조는 이하의 실시예에서 구체적으로 설명한다. 그러나, 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.The preparation method of the compound of Formula 1 and the preparation of the organic light emitting device using the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
<< 합성예Synthesis Example 1> 중간체의 합성 1> Synthesis of Intermediates
하기와 같은 반응에 의하여 중간체를 합성하였다.An intermediate was synthesized by the following reaction.
중간체 A-1 및 A-2의 합성Synthesis of Intermediates A-1 and A-2
Figure PCTKR2017002763-appb-I000053
Figure PCTKR2017002763-appb-I000053
Figure PCTKR2017002763-appb-I000054
Figure PCTKR2017002763-appb-I000054
Figure PCTKR2017002763-appb-I000055
Figure PCTKR2017002763-appb-I000055
중간체 B-1 및 B-2의 합성Synthesis of Intermediates B-1 and B-2
Figure PCTKR2017002763-appb-I000056
Figure PCTKR2017002763-appb-I000056
Figure PCTKR2017002763-appb-I000057
Figure PCTKR2017002763-appb-I000057
Figure PCTKR2017002763-appb-I000058
Figure PCTKR2017002763-appb-I000058
중간체 C-1 및 C-2의 합성Synthesis of Intermediates C-1 and C-2
Figure PCTKR2017002763-appb-I000059
Figure PCTKR2017002763-appb-I000059
Figure PCTKR2017002763-appb-I000060
Figure PCTKR2017002763-appb-I000060
Figure PCTKR2017002763-appb-I000061
Figure PCTKR2017002763-appb-I000061
중간체 D-1 및 D-2의 합성Synthesis of Intermediates D-1 and D-2
Figure PCTKR2017002763-appb-I000062
Figure PCTKR2017002763-appb-I000062
Figure PCTKR2017002763-appb-I000063
Figure PCTKR2017002763-appb-I000063
Figure PCTKR2017002763-appb-I000064
Figure PCTKR2017002763-appb-I000064
중간체 E-1 및 E-2의 합성Synthesis of Intermediates E-1 and E-2
Figure PCTKR2017002763-appb-I000065
Figure PCTKR2017002763-appb-I000065
Figure PCTKR2017002763-appb-I000066
Figure PCTKR2017002763-appb-I000066
Figure PCTKR2017002763-appb-I000067
Figure PCTKR2017002763-appb-I000067
중간체 F-1 및 F-2의 합성Synthesis of Intermediates F-1 and F-2
Figure PCTKR2017002763-appb-I000068
Figure PCTKR2017002763-appb-I000068
Figure PCTKR2017002763-appb-I000069
Figure PCTKR2017002763-appb-I000069
Figure PCTKR2017002763-appb-I000070
Figure PCTKR2017002763-appb-I000070
중간체 G-1 및 G-2의 합성Synthesis of Intermediates G-1 and G-2
Figure PCTKR2017002763-appb-I000071
Figure PCTKR2017002763-appb-I000071
Figure PCTKR2017002763-appb-I000072
Figure PCTKR2017002763-appb-I000072
Figure PCTKR2017002763-appb-I000073
Figure PCTKR2017002763-appb-I000073
중간체 H-1 및 H-2의 합성Synthesis of Intermediates H-1 and H-2
Figure PCTKR2017002763-appb-I000074
Figure PCTKR2017002763-appb-I000074
Figure PCTKR2017002763-appb-I000075
Figure PCTKR2017002763-appb-I000075
Figure PCTKR2017002763-appb-I000076
Figure PCTKR2017002763-appb-I000076
또한, 상기 중간체의 합성 방법에서 반응 물질을 적절하게 변경하여 아래와 같이 다양한 중간체를 합성하였다.In addition, various intermediates were synthesized as follows by appropriately changing the reaction material in the synthesis method of the intermediate.
Figure PCTKR2017002763-appb-I000077
Figure PCTKR2017002763-appb-I000077
Figure PCTKR2017002763-appb-I000078
Figure PCTKR2017002763-appb-I000078
<합성예 1> 화학식 1의 화합물의 합성Synthesis Example 1 Synthesis of Compound of Formula 1
제조예Production Example 1:  One: 하기 화합물 3의 합성Synthesis of the Following Compound 3
[화합물 3][Compound 3]
Figure PCTKR2017002763-appb-I000079
Figure PCTKR2017002763-appb-I000079
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 A-2 (6.00g, 12.63mmol), N-([1,1'-바이페닐]-4-yl)-N-(4-브로모페닐)-[1,1'-바이페닐]-4-아민(N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1'-biphenyl]-4-amine) (6.74g, 13.89mmol)을 테트라하이드로퓨란 320ml에 완전히 녹인 후 2M 탄산칼륨수용액(160ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.44g, 0.38mmol)을 넣은 후 3시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 250ml으로 재결정하여 화합물 3(8.22g, 86%)을 제조하였다.Compound A-2 (6.00 g, 12.63 mmol), N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl)-[1 in a 500 ml round bottom flask under nitrogen atmosphere , 1'-biphenyl] -4-amine (N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl)-[1,1'-biphenyl] -4-amine) (6.74g, 13.89mmol) was dissolved completely in 320ml of tetrahydrofuran, 2M potassium carbonate solution (160ml) was added, and tetrakis- (triphenylphosphine) palladium (0.44g, 0.38mmol) was added for 3 hours. It stirred by heating. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of tetrahydrofuran to prepare compound 3 (8.22 g, 86%).
MS[M+H]+= 755MS [M + H] + = 755
제조예 2: Preparation Example 2: 하기 화합물 5의 합성Synthesis of the Following Compound 5
[화합물 5][Compound 5]
Figure PCTKR2017002763-appb-I000080
Figure PCTKR2017002763-appb-I000080
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 C-2 (11.00g, 18.06mmol), N-(4-브로모페닐)-9,9-디메틸-N-페닐-9H-플루오렌-2-아민(N-(4-bromophenyl)-9,9-dimethyl-N-phenyl-9H-fluoren-2-amine) (7.55g, 17.16mmol)을 테트라하이드로퓨란 220ml에 완전히 녹인 후 2M 탄산칼륨수용액(110ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.21g, 0.18mmol)을 넣은 후 3시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 220ml으로 재결정하여 화합물 5(12.24g, 80%)를 제조하였다.Compound C-2 (11.00 g, 18.06 mmol), N- (4-bromophenyl) -9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (N in a 500 ml round bottom flask in nitrogen atmosphere -(4-bromophenyl) -9,9-dimethyl-N-phenyl-9H-fluoren-2-amine) (7.55g, 17.16mmol) is completely dissolved in 220ml of tetrahydrofuran and 2M potassium carbonate solution (110ml) is added. Then, tetrakis- (triphenylphosphine) palladium (0.21 g, 0.18 mmol) was added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of tetrahydrofuran to prepare compound 5 (12.24 g, 80%).
MS[M+H]+= 843MS [M + H] + = 843
제조예 3:Preparation Example 3: 하기 화합물 6의 합성 Synthesis of the Following Compound 6
[화합물 6][Compound 6]
Figure PCTKR2017002763-appb-I000081
Figure PCTKR2017002763-appb-I000081
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 B-2 (12.00g, 24.74mmol), 4-브로모-N,N-디페닐아닐린(4-bromo-N,N-diphenylaniline) (7.59g, 23.51mmol)을 테트라하이드로퓨란 280ml에 완전히 녹인 후 2M 탄산칼륨수용액(140ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.86g, 0.74 mmol)을 넣은 후 3시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 170ml으로 재결정하여 화합물 6(11.07g, 74%)을 제조하였다.Compound B-2 (12.00 g, 24.74 mmol), 4-bromo-N, N-diphenylaniline (7.59 g, 23.51 mmol) in a 500 ml round bottom flask in nitrogen atmosphere After completely dissolved in 280ml of tetrahydrofuran, 2M aqueous potassium carbonate solution (140ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.86g, 0.74 mmol) was added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 170 ml of tetrahydrofuran to prepare compound 6 (11.07 g, 74%).
MS[M+H]+= 603MS [M + H] + = 603
제조예 4: Preparation Example 4: 하기 화합물 8의 합성Synthesis of the Following Compound 8
[화합물 8][Compound 8]
Figure PCTKR2017002763-appb-I000082
Figure PCTKR2017002763-appb-I000082
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 A-2 (10.00g, 20.62mmol), 2-(3-브로모페닐)-4,6-디페닐-1,3,5-트리아진(2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine) (7.58g, 19.59mmol)을 테트라하이드로퓨란 280ml에 완전히 녹인 후 2M 탄산칼륨수용액(140ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.71g, 0.62mmol)을 넣은 후 5시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 220ml으로 재결정하여 화합물 8(11.17g, 81%)을 제조하였다.Compound A-2 (10.00 g, 20.62 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2- (3) in a 500 ml round bottom flask in a nitrogen atmosphere. -bromophenyl) -4,6-diphenyl-1,3,5-triazine) (7.58 g, 19.59 mmol) was completely dissolved in 280 ml of tetrahydrofuran, and then 2M aqueous potassium carbonate solution (140 ml) was added thereto, followed by tetrakis- (tri Phenylphosphine) palladium (0.71 g, 0.62 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of tetrahydrofuran to prepare compound 8 (11.17 g, 81%).
MS[M+H]+= 667MS [M + H] + = 667
제조예 5: Preparation Example 5: 하기 화합물 9의 합성Synthesis of the Following Compound 9
[화합물 9][Compound 9]
Figure PCTKR2017002763-appb-I000083
Figure PCTKR2017002763-appb-I000083
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 I-2 (9.00g, 13.55mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) (3.39g, 12.69mmol)을 테트라하이드로퓨란 260ml에 완전히 녹인 후 2M 탄산칼륨수용액(130ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.07g, 0.13mmol)을 넣은 후 3시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 210ml으로 재결정하여 화합물 9 (8.17g, 81%)를 제조하였다.Compound I-2 (9.00 g, 13.55 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-) in a 500 ml round bottom flask under nitrogen atmosphere 1,3,5-triazine) (3.39 g, 12.69 mmol) was completely dissolved in 260 ml of tetrahydrofuran, and then 2M aqueous potassium carbonate solution (130 ml) was added, followed by tetrakis- (triphenylphosphine) palladium (0.07 g, 0.13 mmol), and the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of tetrahydrofuran to prepare compound 9 (8.17 g, 81%).
MS[M+H]+= 756MS [M + H] + = 756
제조예 6: Preparation Example 6: 하기 화합물 10의 합성Synthesis of the Following Compound 10
[화합물 10][Compound 10]
Figure PCTKR2017002763-appb-I000084
Figure PCTKR2017002763-appb-I000084
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 I-2 (8.00g, 12.31mmol), 2-(3-브로모페닐)-4,6-디페닐-1,3,5-트리아진(2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine) (4.52g, 11.69mmol)을 테트라하이드로퓨란 220ml에 완전히 녹인 후 2M 탄산칼륨수용액(110ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.43g, 0.37mmol)을 넣은 후 4시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 230ml으로 재결정하여 화합물 10 (7.46g, 73%)를 제조하였다.Compound I-2 (8.00 g, 12.31 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2- (3) in a 500 ml round bottom flask under nitrogen atmosphere -bromophenyl) -4,6-diphenyl-1,3,5-triazine) (4.52 g, 11.69 mmol) was completely dissolved in 220 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (110 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.43 g, 0.37 mmol) was added thereto, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of tetrahydrofuran to prepare compound 10 (7.46 g, 73%).
MS[M+H]+= 832MS [M + H] + = 832
제조예 7: Preparation Example 7: 하기 화합물 11의 합성Synthesis of the Following Compound 11
[화합물 11][Compound 11]
Figure PCTKR2017002763-appb-I000085
Figure PCTKR2017002763-appb-I000085
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 B-2 (9.00g, 18.56mmol), 2-(3-브로모페닐)-4,6-디페닐-1,3,5-트리아진(2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine) (6.82g, 17.63mmol)을 테트라하이드로퓨란 240ml에 완전히 녹인 후 2M 탄산칼륨수용액(120ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.64g, 0.56mmol)을 넣은 후 5시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 170ml으로 재결정하여 화합물 11 (9.72g, 79%)를 제조하였다.Compound B-2 (9.00 g, 18.56 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2- (3) in a 500 ml round bottom flask in a nitrogen atmosphere -bromophenyl) -4,6-diphenyl-1,3,5-triazine) (6.82 g, 17.63 mmol) was completely dissolved in 240 ml of tetrahydrofuran and 2M aqueous potassium carbonate solution (120 ml) was added, followed by tetrakis- (tri Phenylphosphine) palladium (0.64 g, 0.56 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 170 ml of tetrahydrofuran to prepare compound 11 (9.72 g, 79%).
MS[M+H]+= 667MS [M + H] + = 667
제조예 8: Preparation Example 8: 하기 화합물 12의 합성Synthesis of the Following Compound 12
[화합물 12][Compound 12]
Figure PCTKR2017002763-appb-I000086
Figure PCTKR2017002763-appb-I000086
질소 분위기에서 500ml 둥근 바닥 플라스크에 화합물 B-2 (9.00g, 18.56mmol), 2-([1,1'-바이페닐]-4-일)-4-(3-브로모페닐)-6-페닐-1,3,5-트리아진(2-([1,1'-biphenyl]-4-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine) (8.16g, 17.63mmol)을 테트라하이드로퓨란 360ml에 완전히 녹인 후 2M 탄산칼륨수용액(180ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.64g, 0.56mmol)을 넣은 후 5시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 220ml으로 재결정하여 화합물 12 (11.29g, 82%)를 제조하였다.Compound B-2 (9.00 g, 18.56 mmol), 2-([1,1'-biphenyl] -4-yl) -4- (3-bromophenyl) -6- in a 500 ml round bottom flask in a nitrogen atmosphere Phenyl-1,3,5-triazine (2-([1,1'-biphenyl] -4-yl) -4- (3-bromophenyl) -6-phenyl-1,3,5-triazine) (8.16 g, 17.63 mmol) was completely dissolved in 360 ml of tetrahydrofuran, and then 2M aqueous potassium carbonate solution (180 ml) was added thereto, followed by addition of tetrakis- (triphenylphosphine) palladium (0.64 g, 0.56 mmol), followed by heating and stirring for 5 hours. It was. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of tetrahydrofuran to prepare compound 12 (11.29 g, 82%).
MS[M+H]+= 743MS [M + H] + = 743
<실험예 1-1><Experimental Example 1-1>
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 화학식의 헥사아자트리페닐렌 헥사니트릴(hexaazatriphenylene hexanitrile; HAT-CN)를 500Å의 두께로 열 진공 증착하여 정공 주입층을 형성하였다. The hexaazatriphenylene hexanitrile (HAT-CN) of the following formula was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.
[HAT-CN][HAT-CN]
Figure PCTKR2017002763-appb-I000087
Figure PCTKR2017002763-appb-I000087
상기 정공 주입층 위에 정공을 수송하는 물질인 하기 화합물 4-4'-비스[N-(1-나프틸)-N-페닐아미노]비페닐(NPB)(300Å)를 진공 증착하여 정공 수송층을 형성하였다. Compound 4-4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (300 Pa), which is a substance for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. It was.
[NPB][NPB]
Figure PCTKR2017002763-appb-I000088
Figure PCTKR2017002763-appb-I000088
이어서, 상기 정공 수송층 위에 막 두께 100Å으로 하기 화합물 3을 진공 증착하여 전자 억제층을 형성하였다.Subsequently, the following compound 3 was vacuum-deposited to a film thickness of 100 kPa on the said hole transport layer, and the electron suppression layer was formed.
[화합물 3][Compound 3]
Figure PCTKR2017002763-appb-I000089
Figure PCTKR2017002763-appb-I000089
이어서, 상기 전자 억제층 위에 막 두께 300Å으로 아래와 같은 BH와 BD를 25:1의 중량비로 진공증착하여 발광층을 형성하였다. Subsequently, the following BH and BD were vacuum-deposited at a weight ratio of 25: 1 on the electron suppression layer with a film thickness of 300 Pa to form a light emitting layer.
[BH][BH]
Figure PCTKR2017002763-appb-I000090
Figure PCTKR2017002763-appb-I000090
[BD][BD]
Figure PCTKR2017002763-appb-I000091
Figure PCTKR2017002763-appb-I000091
[ET1][ET1]
Figure PCTKR2017002763-appb-I000092
Figure PCTKR2017002763-appb-I000092
[LiQ][LiQ]
Figure PCTKR2017002763-appb-I000093
Figure PCTKR2017002763-appb-I000093
상기 발광층 위에 상기 화합물 ET1과 상기 화합물 LiQ(Lithium Quinolate)를 1:1의 중량비로 진공증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å두께로 리튬플로라이드(LiF)와 2,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 kPa. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 12 kPa in order to form a cathode.
상기의 과정에서 유기물의 증착속도는 0.4~ 0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2 X 10-7 ~5 X 10-6 torr를 유지하여, 유기 발광 소자를 제작하였다.Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 10 2 X - The organic light emitting device was manufactured by maintaining 7 to 5 × 10 −6 torr.
<실험예 1-2><Experimental Example 1-2>
상기 실험예 1에서 화합물 3 대신 상기 화합물 5를 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 유기 발광 소자를 제작하였다.The organic light emitting device was manufactured by the same method as Experimental Example 1, except that compound 5 was used instead of compound 3 in Experimental Example 1.
<실험예 1-3><Experimental Example 1-3>
상기 실험예 1에서 화합물 3 대신 상기 화합물 6을 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 유기 발광 소자를 제작하였다.The organic light emitting device was manufactured by the same method as Experimental Example 1, except that compound 6 was used instead of compound 3 in Experimental Example 1.
<비교예 1>Comparative Example 1
상기 실험예 1에서 화합물 1 대신 하기 EB1의 화합물을 사용한 것을 제외하고는 상기 실험예 1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following EB1 compound instead of compound 1 in Experimental Example 1.
[EB1][EB1]
Figure PCTKR2017002763-appb-I000094
Figure PCTKR2017002763-appb-I000094
<< 비교예Comparative example 2> 2>
상기 실험예 1에서 화합물 1 대신 하기 EB2의 화합물을 사용한 것을 제외하고는 상기 실험예 1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following EB2 compound instead of compound 1 in Experimental Example 1.
[EB2][EB2]
Figure PCTKR2017002763-appb-I000095
Figure PCTKR2017002763-appb-I000095
<< 비교예Comparative example 3> 3>
상기 실험예 1에서 화합물 3 대신 하기 EB3의 화합물을 사용한 것을 제외하고는 상기 실험예 1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following EB3 compound instead of compound 3 in Experimental Example 1.
[EB3][EB3]
Figure PCTKR2017002763-appb-I000096
Figure PCTKR2017002763-appb-I000096
실험예 1-1 내지 실험예 1-3, 비교예 1 내지 3에 의해 제작된 유기 발광 소자에 전류를 인가하였을 때, 표 1의 결과를 얻었다.When the electric current was applied to the organic light emitting element produced by Experimental Example 1-1 to Experimental Example 1-3 and Comparative Examples 1-3, the result of Table 1 was obtained.
화합물(전자 억제층)Compound (electron suppression layer) 전압(V@10mA/cm2)Voltage (V @ 10mA / cm 2 ) 효율(cd/A@10mA/cm2)Efficiency (cd / A @ 10mA / cm 2 ) 색좌표(x,y)Color coordinates (x, y)
실험예 1-1Experimental Example 1-1 화합물 3 Compound 3 3.743.74 6.496.49 (0.138, 0.126)(0.138, 0.126)
실험예 1-2Experimental Example 1-2 화합물 5Compound 5 3.523.52 6.716.71 (0.138, 0.127)(0.138, 0.127)
실험예 1-3Experimental Example 1-3 화합물 6 Compound 6 3.573.57 6.666.66 (0.138, 0.127)(0.138, 0.127)
비교예 1Comparative Example 1 EB1EB1 3.943.94 6.146.14 (0.136, 0.125)(0.136, 0.125)
비교예 2Comparative Example 2 EB2EB2 3.863.86 6.256.25 (0.135, 0.125)(0.135, 0.125)
비교예 3Comparative Example 3 EB3EB3 4.524.52 5.165.16 (0.133, 0.123)(0.133, 0.123)
상기 표 1에서 보는 바와 같이, 본원 발명의 화합물을 전자 억제층으로 사용하여 제조된 유기 발광 소자는 본원 발명의 코어의 다른 위치에 아민기가 연결된 비교예 1 및 비교예 2의 물질을 사용한 경우 및 아릴기만 치환된 비교예 3의 물질을 사용한 경우와 비교하였을 때 본원 발명의 화합물은 전자 억제역할을 하므로 유기 발광 소자의 효율, 구동전압 및/또는 안정성 면에서 우수한 특성을 나타낸다.As shown in Table 1, the organic light emitting device manufactured by using the compound of the present invention as an electron suppressing layer is a case of using the material of Comparative Example 1 and Comparative Example 2 in which the amine group is connected to another position of the core of the present invention and aryl Compared with the case of using the substance of Comparative Example 3, which is substituted with only a group, the compound of the present invention plays an electron suppressing role and thus exhibits excellent characteristics in terms of efficiency, driving voltage, and / or stability of the organic light emitting device.
실험예 1-1 내지 1-3은 비교예 1 내지 3보다 구동 전압은 10% ~ 12% 감소하며, 효율 또한 10% 이상 높은 특성을 보인다.Experimental Examples 1-1 to 1-3 have a driving voltage of 10% to 12% less than Comparative Examples 1 to 3, and show efficiency of 10% or more.
상기 표 1의 결과와 같이, 본 발명에 따른 화합물은 전자 억제 능력이 우수하여 유기 발광 소자에 적용 가능함을 확인할 수 있었다. As shown in Table 1, the compound according to the present invention was confirmed that the excellent electron suppression ability can be applied to the organic light emitting device.
<실험예 2-1 내지 2-3><Experimental Example 2-1 to 2-3>
상기 실험예 1-1 에서 전자 억제층으로 하기 EB4 물질을 사용하고, 상기 정공 수송층으로 NPB 대신 실험예 1-1 내지 1-3의 화합물들을 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the following EB4 material as the electron suppression layer in Experimental Example 1-1, and using the compounds of Experimental Examples 1-1 to 1-3 instead of NPB as the hole transport layer.
[EB4][EB4]
Figure PCTKR2017002763-appb-I000097
Figure PCTKR2017002763-appb-I000097
<비교예 3>Comparative Example 3
상기 실험예 2-1에서 화합물 3 대신 상기 EB1 의 화합물을 사용한 것을 제외하고는 상기 실험예 2과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Experimental Example 2 except for using the compound of EB1 instead of compound 3 in Experimental Example 2-1.
<비교예 4><Comparative Example 4>
상기 실험예 2-1에서 화합물 3 대신 상기 EB2의 화합물을 사용한 것을 제외하고는 상기 실험예 2과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Experimental Example 2 except for using the compound of EB2 instead of compound 3 in Experimental Example 2-1.
실험예 2-1 내지 실험예 2-3, 비교예 3 및 4에 의해 제작된 유기 발광 소자에 전류를 인가하였을 때, 표 2의 결과를 얻었다.When the electric current was applied to the organic light emitting element produced by Experimental Example 2-1 to Experimental Example 2-3, Comparative Example 3 and 4, the result of Table 2 was obtained.
화합물(정공 수송층)Compound (hole transport layer) 전압(V@10mA/cm2)Voltage (V @ 10mA / cm 2 ) 효율(cd/A@10mA/cm2)Efficiency (cd / A @ 10mA / cm 2 ) 색좌표(x,y)Color coordinates (x, y)
실험예 2-1Experimental Example 2-1 화합물 3 Compound 3 4.684.68 5.375.37 (0.138, 0.127)(0.138, 0.127)
실험예 2-2Experimental Example 2-2 화합물 5Compound 5 4.774.77 5.295.29 (0.138, 0.127)(0.138, 0.127)
실험예 2-3Experimental Example 2-3 화합물 6 Compound 6 4.724.72 5.265.26 (0.138, 0.127)(0.138, 0.127)
비교예 3Comparative Example 3 EB1EB1 5.065.06 4.914.91 (0.136, 0.126)(0.136, 0.126)
비교예 4Comparative Example 4 EB2EB2 5.185.18 4.824.82 (0.135, 0.126)(0.135, 0.126)
상기 표 2에서 보는 바와 같이, 본원 발명의 화합물을 정공 수송층으로 사용하여 제조된 유기 발광 소자의 본원 발명의 코어의 다른 위치에 아민기가 연결된 비교예 3 및 비교예 4의 물질을 사용한 경우와 비교하였을 때 본원 발명의 화합물은 정공 수송 역할을 하므로 유기 발광 소자의 효율, 구동전압 및/또는 안정성 면에서 우수한 특성을 나타낸다.As shown in Table 2, the organic light emitting device manufactured by using the compound of the present invention as a hole transport layer compared with the case of using the material of Comparative Example 3 and Comparative Example 4 in which the amine group is connected to another position of the core of the present invention When the compound of the present invention plays a role of hole transport, it shows excellent properties in terms of efficiency, driving voltage and / or stability of the organic light emitting device.
구체적으로 실험예 2-1 내지 2-3은 이러한 비교예보다 구동 전압은 5% ~ 8% 이상 감소하고, 효율 또한 7~10% 이상 높은 특성을 보인다.Specifically, Experimental Examples 2-1 to 2-3 show a driving voltage of 5% to 8% or more, and an efficiency of 7 to 10% or more than the comparative example.
상기 표 1 및 표 2의 결과와 같이, 본 발명에 다른 화합물은 전자 억제 능력 뿐만 아니라 정공 수송 능력이 우수하여 유기 발광 소자에 적용 가능함을 확인할 수 있었다.As shown in Table 1 and Table 2, it was confirmed that the compound according to the present invention is not only excellent in electron suppression ability but also in hole transport ability, and thus can be applied to an organic light emitting device.
<비교예 5>Comparative Example 5
상기 합성예에서 합성된 화합물들을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기와 같은 방법으로 녹색 유기 발광 소자를 제조하였다.After the compounds synthesized in the synthesis example was subjected to high purity sublimation purification by a commonly known method, a green organic light emitting device was manufactured by the following method.
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 CBP을 호스트로 이용하여, m-MTDATA(60nm) / TCTA(80 nm) / CBP + 10 % Ir(ppy)3(300nm)/ BCP(10 nm) / Alq3(30 nm) / LiF(1 nm) / Al (200nm) 순으로 발광 소자를 구성하여 유기 발광 소자를 제조하였다.Using CBP as a host on the prepared ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / CBP + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq 3 (30 nm) The organic light emitting device was manufactured by constructing the light emitting device in the order of) / LiF (1 nm) / Al (200nm).
m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 각각 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP, and BCP are as follows.
Figure PCTKR2017002763-appb-I000098
Figure PCTKR2017002763-appb-I000098
<실험예 3-1>Experimental Example 3-1
상기 비교예 5에서 CBP 대신 상기 화합물 8을 사용한 것을 제외하고는 실험예 2과 동일한 방법으로 유기 발광 소자를 제작하였다.The organic light emitting device was manufactured by the same method as Experimental Example 2, except that compound 8 was used instead of CBP in Comparative Example 5.
<실험예 3-2> Experimental Example 3-2
상기 비교예 5에서 화합물 CBP 대신 상기 화합물 9를 사용한 것을 제외하고는 비교예 5와 동일한 방법으로 유기 발광 소자를 제작하였다. An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 9 was used instead of Compound CBP in Comparative Example 5.
<실험예 3-3>Experimental Example 3-3
상기 비교예 5에서 화합물 CBP 대신 상기 화합물 10을 사용한 것을 제외하고는 비교예 5와 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 10 was used instead of Compound CBP in Comparative Example 5.
<실험예 3-4>Experimental Example 3-4
상기 비교예 5에서 화합물 CBP 대신 상기 화합물 11을 사용한 것을 제외하고는 비교예 5와 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 11 was used instead of Compound CBP in Comparative Example 5.
<실험예 3-5><Experimental Example 3-5>
상기 비교예 5에서 화합물 CBP 대신 상기 화합물 12를 사용한 것을 제외하고는 비교예 5와 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that Compound 12 was used instead of Compound CBP in Comparative Example 5.
<비교예 6>Comparative Example 6
상기 비교예 5에서 화합물 CBP 대신 하기 GH1의 화합물을 사용한 것을 제외하고는 상기 비교예 5와 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting device was manufactured in the same manner as in Comparative Example 5, except that the following compound of GH1 was used instead of the compound CBP in Comparative Example 5.
[GH1][GH1]
Figure PCTKR2017002763-appb-I000099
Figure PCTKR2017002763-appb-I000099
<< 비교예Comparative example 7> 7>
상기 비교예 5에서 화합물 CBP 대신 하기 GH2의 화합물을 사용한 것을 제외하고는 상기 비교예 5와 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 5, except that the following compound of GH2 was used instead of the compound CBP in Comparative Example 5.
[GH2][GH2]
Figure PCTKR2017002763-appb-I000100
Figure PCTKR2017002763-appb-I000100
비교예 5, 실험예 3-1 내지 3-5, 비교예 6 및 7에 의해 제작된 유기 발광 소자에 전류를 인가하였을 때, 표 3의 결과를 얻었다.When the electric current was applied to the organic light emitting element produced by Comparative Example 5, Experimental Examples 3-1 to 3-5, and Comparative Examples 6 and 7, the results of Table 3 were obtained.
화합물(호스트)Compound (Host) 전압(V@10mA/cm2)Voltage (V @ 10mA / cm 2 ) 효율(cd/A@10mA/cm2)Efficiency (cd / A @ 10mA / cm 2 ) EL 피크(nm)EL peak (nm)
비교예 5Comparative Example 5 CBPCBP 7.457.45 38.6238.62 516516
실험예 3-1Experimental Example 3-1 화합물 8Compound 8 6.826.82 43.8943.89 517517
실험예 3-2Experimental Example 3-2 화합물 9Compound 9 6.916.91 42.4742.47 516516
실험예 3-3Experimental Example 3-3 화합물 10Compound 10 6.756.75 44.1544.15 517517
실험예 3-4Experimental Example 3-4 화합물 11Compound 11 6.886.88 43.8243.82 517517
실험예 3-5Experimental Example 3-5 화합물 12Compound 12 6.816.81 43.9543.95 517517
비교예 6Comparative Example 6 GH1GH1 7.067.06 41.2541.25 516516
비교예 7Comparative Example 7 GH2GH2 7.127.12 40.7640.76 516516
실험 결과, 본 발명의 화합물을 녹색 발광층의 호스트 물질로 사용하는 실험예 3-1 내지 3-5의 녹색 유기 발광 소자는 종래 CBP를 사용하는 비교예 5 및 본원발명의 코어와 비슷한 구조인 비교예 6 및 7의 화합물을 녹색 호스트 물질로 사용하여 제조된 유기 발광 소자보다 전류효율 및 구동전압 면에서 우수한 성능을 나타내는 것을 확인할 수 있었다. As a result, the green organic light emitting device of Experimental Examples 3-1 to 3-5 using the compound of the present invention as a host material of the green light emitting layer is Comparative Example 5 using the conventional CBP and Comparative Example having a structure similar to the core of the present invention. It was confirmed that the organic light emitting device manufactured by using the compounds of 6 and 7 as the green host material showed superior performance in terms of current efficiency and driving voltage.
이상을 통해 본 발명의 바람직한 실시예(전자 억제층, 정공 수송층, 녹색 발광층)에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 발명의 범주에 속한다.Although preferred embodiments of the present invention (electron suppression layer, hole transport layer, green light emitting layer) have been described above, the present invention is not limited thereto, and various modifications are made within the scope of the claims and the detailed description of the invention. It is possible to do this and this also belongs to the scope of the invention.

Claims (12)

  1. 하기 화학식 1로 표시되는 화합물: Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2017002763-appb-I000101
    Figure PCTKR2017002763-appb-I000101
    상기 화학식 1에 있어서,In Chemical Formula 1,
    R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이거나, R1 및 R2가 서로 결합하여 치환 또는 비치환된 고리를 형성하며,R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R 1 and R 2 combine with each other to form a substituted or unsubstituted ring,
    L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이며,L 1 and L 2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
    m 및 n은 서로 같거나 상이하고, 각각 독립적으로 0 내지 5의 정수이며,m and n are the same as or different from each other, and each independently an integer of 0 to 5,
    m이 2 이상인 경우에 L1은 서로 같거나 상이하고,when m is 2 or more, L 1 is the same as or different from each other,
    n이 2 이상인 경우에 L2는 서로 같거나 상이하며,when n is 2 or more, L 2 is the same as or different from each other,
    Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 아릴아민기; 치환 또는 비치환된 헤테로고리기; 또는 치환 또는 비치환된 포스핀옥사이드기이며,Ar 1 and Ar 2 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted heterocyclic group; Or a substituted or unsubstituted phosphine oxide group,
    R, R' 및 R"는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 아르알킬기; 치환 또는 비치환된 알킬아릴기; 치환 또는 비치환된 알킬아민기; 치환 또는 비치환된 아랄킬아민기; 치환 또는 비치환된 헤테로아릴아민기; 치환 또는 비치환된 아릴아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기이며,R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; substituted or unsubstituted silyl group Substituted or unsubstituted boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkenyl group; substituted or unsubstituted aralkyl group; substituted or unsubstituted alkylaryl group; substituted or unsubstituted alkylamine group; substituted or unsubstituted aralkylamine group; substituted or unsubstituted hetero Arylamine groups; substituted or unsubstituted arylamine groups; substituted or unsubstituted arylphosphine groups; substituted or unsubstituted phosphine oxide groups; substituted or unsubstituted aryl groups; substituted or unsubstituted heterocyclic groups And
    a 및 b는 서로 같거나 상이하고, 각각 독립적으로 0 내지 4의 정수이며,a and b are the same as or different from each other, and each independently an integer of 0 to 4,
    a가 2 이상인 경우에 R'는 서로 같거나 상이하고,when a is 2 or more, R 'is the same as or different from each other,
    b가 2 이상인 경우에 R"는 서로 같거나 상이하다.R "is the same as or different from each other when b is two or more.
  2. 청구항 1에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 A 또는 화학식 B로 표시되는 것인 화합물:The compound of claim 1, wherein the compound represented by Chemical Formula 1 is represented by the following Chemical Formula A or Chemical Formula B:
    [화학식 A][Formula A]
    Figure PCTKR2017002763-appb-I000102
    Figure PCTKR2017002763-appb-I000102
    [화학식 B][Formula B]
    Figure PCTKR2017002763-appb-I000103
    Figure PCTKR2017002763-appb-I000103
    상기 화학식 A 및 화학식 B에 있어서, In Chemical Formula A and Chemical Formula B,
    R1, R2, L1, L2, m, n, Ar1, Ar2, R, R', R", a 및 b의 정의는 화학식 1에서와 같다.The definitions of R 1 , R 2 , L 1 , L 2 , m, n, Ar 1 , Ar 2 , R, R ′, R ″, a and b are as in Chemical Formula 1.
  3. 청구항 1에 있어서, 상기 Ar1은 페닐기; 나프틸기; 피리딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리딘기; 피리미딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리미딘기; 트리아진기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 트리아진기; 카바졸기; 또는 페닐기, 바이페닐기 및 나프틸기로 이루어진 군에서 선택된 1 이상으로 치환된 카바졸기인 것인 화합물.The method according to claim 1, Ar 1 is a phenyl group; Naphthyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Carbazole groups; Or a carbazole group substituted with at least one selected from the group consisting of a phenyl group, a biphenyl group and a naphthyl group.
  4. 청구항 1에 있어서, 상기 Ar2는 수소; 페닐기; 페닐기, 피리딘기, 퀴놀린기 및 퀴나졸린기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 페닐기; 바이페닐기; 안트라세닐기; 페닐기로 치환된 안트라세닐기; 피리딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리딘기; 피리미딘기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 피리미딘기; 트리아진기; 페닐기 및 바이페닐기로 이루어진 군에서 선택된 1 이상의 치환기로 치환된 트리아진기; 벤즈이미다졸기; 페닐기로 치환된 벤즈이미다졸기; 퀴놀린기; 페닐기로 치환된 퀴놀린기; 퀴나졸린기; 페닐기로 치환된 퀴나졸린기; 카바졸기; 페닐기로 치환된 카바졸기; 디벤조퓨란기; 디벤조티오펜기; 또는 페닐기로 치환된 포스핀옥사이드기인 것인 화합물.The method according to claim 1, wherein Ar 2 is hydrogen; Phenyl group; A phenyl group substituted with at least one substituent selected from the group consisting of a phenyl group, a pyridine group, a quinoline group and a quinazoline group; Biphenyl group; Anthracenyl group; Anthracenyl group substituted with a phenyl group; Pyridine group; A pyridine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Pyrimidine groups; A pyrimidine group substituted with at least one substituent selected from the group consisting of a phenyl group and a biphenyl group; Triazine group; Triazine groups substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Benzimidazole groups; Benzimidazole groups substituted with phenyl groups; Quinoline groups; Quinoline groups substituted with phenyl groups; Quinazoline group; A quinazoline group substituted with a phenyl group; Carbazole groups; Carbazole groups substituted with phenyl groups; Dibenzofuran group; Dibenzothiophene group; Or a phosphine oxide group substituted with a phenyl group.
  5. 청구항 1에 있어서, L1은 직접결합; 또는 아래의 군으로부터 선택되는 어느 하나의 연결기인 것인 화합물:The method according to claim 1, L 1 is a direct bond; Or any one linking group selected from the group below:
    Figure PCTKR2017002763-appb-I000104
    .
    Figure PCTKR2017002763-appb-I000104
    .
  6. 청구항 1에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 메틸기 또는 페닐기인 것인 화합물.The compound of claim 1, wherein R 1 and R 2 are the same as or different from each other, and are each independently a methyl group or a phenyl group.
  7. 청구항 1에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 구조들 중에서 선택되는 어느 하나인 것인 화합물:The compound of claim 1, wherein the compound represented by Formula 1 is any one selected from the following structures:
    Figure PCTKR2017002763-appb-I000105
    Figure PCTKR2017002763-appb-I000105
    Figure PCTKR2017002763-appb-I000106
    Figure PCTKR2017002763-appb-I000106
    Figure PCTKR2017002763-appb-I000107
    Figure PCTKR2017002763-appb-I000107
    Figure PCTKR2017002763-appb-I000108
    Figure PCTKR2017002763-appb-I000108
    Figure PCTKR2017002763-appb-I000109
    Figure PCTKR2017002763-appb-I000109
    Figure PCTKR2017002763-appb-I000110
    Figure PCTKR2017002763-appb-I000110
    Figure PCTKR2017002763-appb-I000111
    Figure PCTKR2017002763-appb-I000111
    Figure PCTKR2017002763-appb-I000112
    Figure PCTKR2017002763-appb-I000112
    Figure PCTKR2017002763-appb-I000113
    Figure PCTKR2017002763-appb-I000113
    Figure PCTKR2017002763-appb-I000114
    Figure PCTKR2017002763-appb-I000114
    Figure PCTKR2017002763-appb-I000115
    Figure PCTKR2017002763-appb-I000115
    Figure PCTKR2017002763-appb-I000116
    Figure PCTKR2017002763-appb-I000116
    Figure PCTKR2017002763-appb-I000117
    Figure PCTKR2017002763-appb-I000117
    Figure PCTKR2017002763-appb-I000118
    .
    Figure PCTKR2017002763-appb-I000118
    .
  8. 제1 전극, 제2 전극, 및 상기 제1 전극과 제2 전극 사이에 배치된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 청구항 1 내지 7 중 어느 하나의 항에 따른 화합물을 포함하는 것을 특징으로 하는 유기 발광 소자.An organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one layer of the organic layer is any one of claims 1 to 7. An organic light-emitting device comprising a compound according to.
  9. 청구항 8에 있어서 상기 유기물층은 전자 수송층, 전자 주입층, 및 전자 수송과 전자 주입을 동시에 하는 층 중 1층 이상을 포함하고, 상기 층들 중 1층 이상이 상기 화합물을 포함하는 것을 특징으로 하는 유기 발광 소자. The organic light emitting diode of claim 8, wherein the organic material layer comprises at least one of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting electrons and injecting electrons, and at least one of the layers includes the compound. device.
  10. 청구항 8에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층이 상기 화합물을 발광층의 호스트로서 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 8, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound as a host of the light emitting layer.
  11. 청구항 8에 있어서, 상기 유기물층은 정공 주입층, 전자 억제층, 정공 수송층, 및 정공 주입과 정공 수송을 동시에 하는 층 중 1층 이상의 층을 포함하고, 상기 층들 중 1층 이상이 상기 화합물을 포함하는 것을 특징으로 하는 유기 발광 소자.The method of claim 8, wherein the organic material layer comprises a hole injection layer, an electron suppression layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, at least one of the layers comprises the compound An organic light emitting device, characterized in that.
  12. 청구항 8에 있어서, 상기 유기물층은 상기 화합물을 호스트로서 포함하고, 다른 유기 화합물, 금속 또는 금속 화합물을 도펀트로 포함하는 것인 유기 발광 소자. The organic light emitting device of claim 8, wherein the organic material layer includes the compound as a host and another organic compound, a metal, or a metal compound as a dopant.
PCT/KR2017/002763 2016-03-14 2017-03-14 Heterocyclic compound and organic light emitting diode comprising same WO2017160068A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2018544457A JP6628066B2 (en) 2016-03-14 2017-03-14 Heterocyclic compound and organic light emitting device containing the same
CN201780017673.XA CN108779072B (en) 2016-03-14 2017-03-14 Heterocyclic compound and organic light-emitting element comprising same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20160030406 2016-03-14
KR10-2016-0030406 2016-03-14

Publications (1)

Publication Number Publication Date
WO2017160068A1 true WO2017160068A1 (en) 2017-09-21

Family

ID=59850764

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/002763 WO2017160068A1 (en) 2016-03-14 2017-03-14 Heterocyclic compound and organic light emitting diode comprising same

Country Status (4)

Country Link
JP (1) JP6628066B2 (en)
KR (1) KR20170106935A (en)
CN (1) CN108779072B (en)
WO (1) WO2017160068A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102611419B1 (en) * 2018-10-01 2023-12-07 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102453982B1 (en) * 2019-02-01 2022-10-14 주식회사 엘지화학 Multicyclic compound and organic light emitting device comprising same
CN112778283B (en) * 2019-11-08 2023-02-03 北京夏禾科技有限公司 Organic electroluminescent material and device thereof
CN117337283A (en) * 2020-02-26 2024-01-02 保土谷化学工业株式会社 Arylamine compound and electronic device using the same
US20230331639A1 (en) * 2020-04-17 2023-10-19 Lg Chem, Ltd. Method for preparing deuterated compound
CN113943279A (en) * 2021-10-21 2022-01-18 上海八亿时空先进材料有限公司 Carbazole derivative, organic electroluminescent element, display device, and lighting device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110132721A (en) * 2010-06-03 2011-12-09 다우어드밴스드디스플레이머티리얼 유한회사 Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20150017605A (en) * 2013-08-07 2015-02-17 제일모직주식회사 Compound, light emitting diode, organic optoelectric device, and display device
KR101555680B1 (en) * 2015-03-03 2015-09-25 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof
KR20160011582A (en) * 2014-07-22 2016-02-01 롬엔드하스전자재료코리아유한회사 Organic Electroluminescence Device
WO2016015810A1 (en) * 2014-07-29 2016-02-04 Merck Patent Gmbh Materials for organic electroluminescent devices

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101174088B1 (en) * 2009-06-25 2012-08-14 제일모직주식회사 Compounds?for organic photoelectric?device and organic photoelectric?device containing the same
KR101531904B1 (en) * 2010-10-13 2015-06-29 롬엔드하스전자재료코리아유한회사 Novel compounds for organic electronic material and organic electroluminescent device using the same
KR20120052879A (en) * 2010-11-16 2012-05-24 롬엔드하스전자재료코리아유한회사 Novel compound for organic electronic material and organic electroluminescent device using the same
WO2013017189A1 (en) * 2011-07-29 2013-02-07 Merck Patent Gmbh Compounds for electronic devices
JP6342419B2 (en) * 2012-12-21 2018-06-13 メルク パテント ゲーエムベーハー Materials for organic electroluminescent devices
WO2015165563A1 (en) * 2014-04-30 2015-11-05 Merck Patent Gmbh Materials for electronic devices
US11107994B2 (en) * 2014-06-18 2021-08-31 Merck Patent Gmbh Materials for organic electroluminescent devices
WO2016013875A1 (en) * 2014-07-22 2016-01-28 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent device
JP5920432B2 (en) * 2014-09-24 2016-05-18 Jnc株式会社 Fused pyrrole polycyclic compound, material for light emitting layer, and organic electroluminescent device using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110132721A (en) * 2010-06-03 2011-12-09 다우어드밴스드디스플레이머티리얼 유한회사 Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20150017605A (en) * 2013-08-07 2015-02-17 제일모직주식회사 Compound, light emitting diode, organic optoelectric device, and display device
KR20160011582A (en) * 2014-07-22 2016-02-01 롬엔드하스전자재료코리아유한회사 Organic Electroluminescence Device
WO2016015810A1 (en) * 2014-07-29 2016-02-04 Merck Patent Gmbh Materials for organic electroluminescent devices
KR101555680B1 (en) * 2015-03-03 2015-09-25 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof

Also Published As

Publication number Publication date
JP6628066B2 (en) 2020-01-08
JP2019508427A (en) 2019-03-28
CN108779072A (en) 2018-11-09
KR20170106935A (en) 2017-09-22
CN108779072B (en) 2021-12-14

Similar Documents

Publication Publication Date Title
WO2017150859A1 (en) Nitrogen-containing compound and organic light emitting device comprising same
WO2019168367A1 (en) Organic light emitting diode
WO2014208829A1 (en) Hetero ring compound and organic light emitting diode comprising same
WO2014010824A1 (en) Heterocyclic compound and organic electronic element containing same
WO2015046988A1 (en) Heterocyclic compound and organic light-emitting element using same
WO2017073932A1 (en) Amine compound and organic light emitting element comprising same
WO2015046835A1 (en) Heterocyclic compound and organic light-emtting element including same
WO2017160068A1 (en) Heterocyclic compound and organic light emitting diode comprising same
WO2017047977A1 (en) Heterocyclic compound and organic light emitting diode comprising same
WO2019190223A1 (en) Compound and organic light-emitting device comprising same
WO2017086713A1 (en) Compound and organic electronic element comprising same
WO2017052138A2 (en) Amine-based compound and organic light-emitting element comprising same
WO2017146522A1 (en) Heterocyclic compound and organic light emitting diode containing same
WO2017039388A1 (en) Amine-based compound and organic light emitting device comprising same
WO2019004791A1 (en) Heterocyclic compound and organic light emitting element including same
WO2021125813A1 (en) Compound and organic light-emitting device comprising same
WO2016068478A2 (en) Cyclic compound and organic light-emitting element comprising same
WO2019108033A1 (en) Compound and organic light emitting element comprising same
WO2018056773A1 (en) Amine-based compound and organic light emitting device comprising same
WO2022102992A1 (en) Novel compound and organic light-emitting device using same
WO2017074018A2 (en) Heterocyclic compound and organic light emitting element comprising same
WO2017052221A1 (en) Novel compound and organic light-emitting element comprising same
WO2018074881A1 (en) Polycyclic compound and organic light emitting element comprising same
WO2017099471A1 (en) Heterocyclic compound and organic light emitting element comprising same
WO2017048060A1 (en) Heterocyclic compound and organic light emitting element comprising same

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018544457

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17766969

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17766969

Country of ref document: EP

Kind code of ref document: A1