WO2023229228A1 - Heterocyclic compound and organic light-emitting device including same - Google Patents

Heterocyclic compound and organic light-emitting device including same Download PDF

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WO2023229228A1
WO2023229228A1 PCT/KR2023/005090 KR2023005090W WO2023229228A1 WO 2023229228 A1 WO2023229228 A1 WO 2023229228A1 KR 2023005090 W KR2023005090 W KR 2023005090W WO 2023229228 A1 WO2023229228 A1 WO 2023229228A1
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이남진
정원장
김동준
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엘티소재주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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    • H10K50/00—Organic light-emitting devices
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Definitions

  • the present invention relates to heterocyclic compounds and organic light-emitting devices containing the same.
  • Organic light emitting devices are a type of self-emitting display devices and have the advantages of a wide viewing angle, excellent contrast, and fast response speed.
  • Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light emitting device with this structure, electrons and holes injected from two electrodes combine in the organic thin film to form a pair and then disappear, emitting light.
  • the organic thin film may be composed of a single layer or multiple layers, depending on need.
  • the material of the organic thin film may have a light-emitting function as needed.
  • a compound that can independently form a light-emitting layer may be used, or a compound that can act as a host or dopant of a host-dopant-based light-emitting layer may be used.
  • compounds that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.
  • Patent Document 1 U.S. Patent No. 4,356,429
  • the present invention seeks to provide a heterocyclic compound and an organic light-emitting device containing the same.
  • the present invention provides a heterocyclic compound represented by the following formula (1):
  • At least one of R2 to R12 is a group represented by the following formula (2),
  • R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; And a substituted or unsubstituted C2 to C60 heterocycloalkyl group; selected from the group consisting of,
  • L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;
  • Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group of C6 to C60; Or a substituted or unsubstituted C2 to C60 heteroaryl group;
  • n are the same as or different from each other and are each independently an integer from 0 to 3,
  • the present invention includes a first electrode; a second electrode provided opposite the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer contains a heterocyclic compound according to the present invention.
  • the heterocyclic compound according to one embodiment can be used as an organic layer material of an organic light-emitting device.
  • the heterocyclic compound may serve as a hole injection layer material, an electron blocking layer material, a hole transport layer material, a light emitting layer material, an electron transport layer material, a hole blocking layer material, an electron blocking layer material, an electron injection layer material, etc. in an organic light emitting device. You can.
  • the heterocyclic compound can be used as a hole transport layer material, a hole transport auxiliary layer material, or an electron blocking layer material of an organic light emitting device.
  • the driving voltage of the organic light-emitting device can be lowered, luminous efficiency can be improved, and lifespan characteristics can be improved.
  • 1 to 3 are diagrams schematically showing the stacked structure of an organic light-emitting device according to an embodiment of the present invention.
  • substitution means changing a hydrogen atom bonded to a carbon atom of a compound to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted. , when two or more substituents are substituted, the two or more substituents may be the same or different from each other.
  • the halogen may be fluorine, chlorine, bromine, or iodine.
  • the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent.
  • the carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20.
  • Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group,
  • the alkenyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent.
  • the alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms.
  • Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited thereto. .
  • the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent.
  • the carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.
  • the alkoxy group may be straight chain, branched chain, or ring chain.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms.
  • the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms and may be further substituted by another substituent.
  • polycyclic refers to a group in which a cycloalkyl group is directly connected to or condensed with another ring group.
  • the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group.
  • the carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20.
  • the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent.
  • polycyclic refers to a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group.
  • the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, or a heteroaryl group.
  • the carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.
  • the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent.
  • polycyclic refers to a group in which an aryl group is directly connected to or condensed with another ring group.
  • the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, heteroaryl group, etc.
  • the aryl group may include a spiro group.
  • the aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms.
  • aryl group examples include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, and pyrethyl group.
  • Nyl group tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed rings thereof etc., but is not limited to this.
  • the phosphine oxide group includes diphenylphosphine oxide group, dinaphthylphosphine oxide, etc., but is not limited thereto.
  • the silyl group is a substituent that contains Si and is directly connected to the Si atom as a radical, and is represented by -SiR101R102R103, and R101 to R103 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group.
  • silyl groups include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. It is not limited.
  • the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.
  • a spiro group is a group containing a spiro structure and may have 15 to 60 carbon atoms.
  • the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group.
  • the spiro group below may include any one of the groups of the structural formula below.
  • the heteroaryl group contains S, O, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent.
  • the polycyclic refers to a group in which a heteroaryl group is directly connected to or condensed with another ring group.
  • the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, or aryl group.
  • the carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25.
  • heteroaryl group examples include pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, and thiazolyl group.
  • isothiazolyl group triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group, Thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyryl group, naphthyridyl group, acridinyl group, phenanthridinyl group , imidazopyridinyl group, diazanaphthalenyl group, triazindenyl group, 2-indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzo
  • the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH 2 ; dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30.
  • amine group examples include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenyl fluorescein Examples include a nylamine group, phenyltriphenylenylamine group, and biphenyltriphenylenylamine group, but are not limited thereto.
  • an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group.
  • the description of the aryl group described above can be applied, except that each of these is a divalent group.
  • a heteroarylene group means that a heteroaryl group has two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.
  • an “adjacent” group may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the substituent in terms of structure, or another substituent substituted on the atom on which the substituent is substituted. You can. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as “adjacent” groups.
  • “when a substituent is not indicated in the chemical formula or compound structure” means that a hydrogen atom is bonded to a carbon atom.
  • deuterium 2H , Deuterium
  • some hydrogen atoms may be deuterium.
  • “when a substituent is not indicated in the chemical formula or compound structure” may mean that all positions that can appear as substituents are hydrogen or deuterium. That is, in the case of deuterium, it is an isotope of hydrogen, and some hydrogen atoms may be the isotope deuterium, and in this case, the content of deuterium may be 0% to 100%.
  • deuterium is one of the isotopes of hydrogen and is an element that has a deuteron consisting of one proton and one neutron as its nucleus.
  • Hydrogen- It can be expressed as 2, and the element symbol can also be written as D or 2 H.
  • isotopes refer to atoms having the same atomic number (Z) but different mass numbers (A). Isotopes have the same number of protons but do not contain neutrons. It can also be interpreted as an element with a different number of neutrons.
  • the deuterium content of 20% in the phenyl group represented by can mean that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and the number of deuteriums among them is 1 (T2 in the formula). . That is, it can be expressed by the following structural formula, which means that the deuterium content in the phenyl group is 20%.
  • a phenyl group with a deuterium content of 0% may mean a phenyl group that does not contain deuterium atoms, that is, has 5 hydrogen atoms.
  • the C6 to C60 aromatic hydrocarbon ring refers to a compound containing an aromatic ring consisting of C6 to C60 carbons and hydrogen, for example, benzene, biphenyl, terphenyl, triphenylene, naphthalene, Anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene, etc. may be mentioned, but are not limited to these, and aromatic hydrocarbon ring compounds known in the art that satisfy the above carbon number may be used. Includes all.
  • the present invention provides a heterocyclic compound represented by the following formula (1):
  • At least one of R2 to R12 is a group represented by the following formula (2),
  • R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; And a substituted or unsubstituted C2 to C60 heterocycloalkyl group; selected from the group consisting of,
  • L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;
  • Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group of C6 to C60; Or a substituted or unsubstituted C2 to C60 heteroaryl group;
  • n are the same as or different from each other and are each independently an integer from 0 to 3,
  • R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; Substituted or unsubstituted C2 to C20 heteroaryl group; and a group represented by the following formula (2), wherein at least one of R2 to R12 may be a group represented by the formula (2), wherein at least one
  • R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group;
  • R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.
  • R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.
  • R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
  • At least one of R2 to R8 may be a group represented by the following formula (2):
  • any one of R2 to R4 is a group represented by Formula 2, and R1 and R5 to R8 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; and a substituted or unsubstituted C2 to C30 heteroaryl group.
  • any one of R2 to R4 is a group represented by Formula 2, and R1 and R5 to R8 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group.
  • any one of R2 to R4 is a group represented by Formula 2, and R1 and R5 to R8 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
  • any one of R5 to R8 is a group represented by Formula 2, and R1 to R4 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; and a substituted or unsubstituted C2 to C30 heteroaryl group.
  • any one of R5 to R8 is a group represented by Formula 2, and R1 to R4 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group.
  • any one of R5 to R8 is a group represented by Formula 2, and R1 to R4 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
  • R13 and R14 are -CRaRbRc, and Ra to Rc are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; and a substituted or unsubstituted C2 to C30 heterocycloalkyl group.
  • R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C10 alkyl group; Substituted or unsubstituted C2 to C10 alkenyl group; Substituted or unsubstituted C2 to C10 alkynyl group; Substituted or unsubstituted C1 to C10 alkoxy group; Substituted or unsubstituted C3 to C10 cycloalkyl group; and a substituted or unsubstituted C2 to C10 heterocycloalkyl group.
  • R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; And cyano group; may be selected from the group consisting of.
  • L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C30 arylene group; Or it may be a substituted or unsubstituted C2 to C30 heteroarylene group.
  • L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C20 arylene group; Or a substituted or unsubstituted C2 to C20 heteroarylene group;
  • L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Or it may be a substituted or unsubstituted terphenylene group.
  • Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group;
  • Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.
  • Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted fluorenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
  • Ar1 and Ar2 are the same or different from each other, and the case where Ar1 or Ar2 is a 9,9-diphenylfluorenyl group may be excluded. More specifically, Ar1 or Ar2 is excluded to include a compound represented by any of the following compounds:
  • the compound represented by Formula 1 may not contain deuterium as a substituent, or the content of deuterium relative to the total number of hydrogen atoms and deuterium atoms may be, for example, greater than 0%, 1%. It may be 10% or more, 20% or more, 30% or more, 40% or more, or 50% or more, and may be 100% or less, 90% or less, 80% or less, 70% or less, and 60% or less.
  • the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 1% to 100%.
  • the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 20% to 90%.
  • the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 30% to 80%.
  • the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 40% to 70%.
  • the deuterium content is 0% or more, 1% or more, 5% or more, 10% or more, 15% or more, 20% or more. It can be more than 25%, more than 30%, more than 35%, more than 40%, more than 45%, or more than 50%, and less than 100%, less than 95%, less than 90%, less than 85%, less than 80%, 75 It may be % or less, 70% or less, 65% or less, or 60% or less.
  • the heterocyclic compound represented by Formula 1 may be any one selected from the group consisting of the following compounds:
  • a compound having the unique properties of the introduced substituent can be synthesized.
  • substituents mainly used in the hole injection layer material, hole transport layer material, hole transport auxiliary layer material, electron blocking layer material, light emitting layer material, electron transport layer material, hole blocking layer material, and electron injection layer material used in manufacturing organic light emitting devices By introducing into the core structure, a material that satisfies the conditions required for each organic layer can be synthesized.
  • the energy band gap can be finely adjusted, while the properties at the interface between organic materials can be improved and the uses of the material can be diversified.
  • Another embodiment of the present invention provides an organic light-emitting device including the heterocyclic compound represented by Formula 1 above.
  • the “organic light emitting device” may be expressed by terms such as “organic light emitting diode”, “OLED (Organic Light Emitting Diodes)”, “OLED device”, “organic electroluminescent device”, etc.
  • the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers includes a heterocyclic compound represented by Formula 1. do.
  • the first electrode may be an anode
  • the second electrode may be a cathode
  • the first electrode may be a cathode
  • the second electrode may be an anode
  • the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the red organic light-emitting device.
  • the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the green organic light-emitting device.
  • the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the blue organic light-emitting device.
  • the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the red organic light-emitting device.
  • the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the green organic light-emitting device.
  • the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the blue organic light-emitting device.
  • heterocyclic compound represented by Formula 1 Specific details about the heterocyclic compound represented by Formula 1 are the same as described above.
  • the organic light-emitting device of the present invention can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the heterocyclic compound described above.
  • the heterocyclic compound can form an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device.
  • the solution application method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may also have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, an electron injection layer, an electron transport layer, a battery blocking layer, a hole blocking layer, etc. as organic material layers.
  • the structure of the organic light emitting device is not limited to this and may include a smaller number of organic material layers.
  • the organic material layer includes a light-emitting layer
  • the light-emitting layer may include a heterocyclic compound represented by Formula 1 above.
  • the heterocyclic compound When the heterocyclic compound is used in the light-emitting layer, strong charge transfer is possible by spatially separating HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital), thereby driving the organic light-emitting device. Efficiency and lifespan can be improved.
  • the organic light-emitting device may include one or more organic material layers, the organic material layer may include a light-emitting layer, and the light-emitting layer may include a heterocyclic compound represented by Formula 1. there is.
  • the organic layer may include a light-emitting layer, the light-emitting layer may include a host material, and the host material may include the heterocyclic compound.
  • the organic light emitting device has one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. More may be included.
  • the organic light-emitting device may include one or more organic material layers, the organic material layer may include a hole transport layer, and the hole transport layer includes a heterocyclic compound represented by Formula 1. can do.
  • the organic light emitting device has one or two layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. It may include more than the above.
  • the organic light-emitting device may include one or more organic material layers, the organic material layer may include a hole transport auxiliary layer, and the hole transport auxiliary layer is a heterogeneous material represented by Formula 1. It may contain a ring compound.
  • the organic light emitting device has one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. More may be included.
  • the organic light-emitting device may include one or more organic material layers, the organic material layer may include an electron blocking layer, and the electron blocking layer is a heterocyclic compound represented by Formula 1. may include.
  • the organic light emitting device has one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, and a hole blocking layer. It may further include.
  • the organic material layer includes a heterocyclic compound represented by Formula 1, and can be used together with a phosphorescent dopant.
  • phosphorescent dopant material those known in the art can be used.
  • phosphorescent dopant materials represented by LL'MX', LL'L"M, LMX'X", L 2 MX' and L 3 M can be used, but the scope of the present invention is not limited by these examples. .
  • the M may be iridium, platinum, osmium, etc.
  • L is an anionic bidentate ligand coordinated to M by an sp 2 carbon and a hetero atom, and X may function to trap electrons or holes.
  • Non-limiting examples of L, L' and L" include 2-(1-naphthyl)benzoxazole, 2-phenylbenzoxazole, 2-phenylbenzothiazole, 7,8-benzoquinoline, phenylpyridine, benzothiazole Thiophenylpyridine, 3-methoxy-2-phenylpyridine, thiophenylpyridine, tolylpyridine, etc.
  • Non-limiting examples of X' and These include silidene, picolinate, and 8-hydroxyquinolinate.
  • the organic material layer includes a heterocyclic compound represented by Formula 1, and can be used together with an iridium-based dopant.
  • a green phosphorescent dopant or a red phosphorescent dopant may be Ir(ppy) 3 as the iridium-based dopant.
  • the content of the dopant may be 1% to 15%, preferably 2% to 10%, more preferably 3% to 7%, based on the total weight of the light emitting layer. .
  • the organic material layer includes a hole transport layer or a hole transport auxiliary layer, and the hole transport layer or the hole transport auxiliary layer may include a heterocyclic compound represented by Formula 1 above. .
  • the organic material layer includes an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer may include a heterocyclic compound represented by Formula 1 above.
  • the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include a heterocyclic compound represented by Formula 1 above. .
  • the organic material layer includes an electron transport layer, a light-emitting layer, or a hole blocking layer, and the electron transport layer, the light-emitting layer, or the hole blocking layer may include a heterocyclic compound represented by Formula 1. You can.
  • the organic material layer includes a light-emitting layer, and the light-emitting layer may include a heterocyclic compound represented by Formula 1 above.
  • the organic material layer includes a light-emitting layer
  • the light-emitting layer includes a host material
  • the host material may include a heterocyclic compound represented by Formula 1.
  • the light emitting layer may include two or more host materials, and at least one of the host materials may include a heterocyclic compound represented by Formula 1 above.
  • the light-emitting layer may be used by pre-mixing two or more host materials, and at least one of the two or more host materials is a heterogeneous compound represented by Formula 1. It may contain a ring compound.
  • the pre-mixed means that the light emitting layer first mixes two or more host materials into one container before depositing them on the organic layer.
  • the organic light emitting device may further include one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer. .
  • FIG. 1 to 3 illustrate the stacking order of electrodes and organic material layers of an organic light-emitting device according to an embodiment of the present invention.
  • the scope of the present application be limited by these drawings, and structures of organic light-emitting devices known in the art may also be applied to the present application.
  • an organic light emitting device is shown in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100.
  • an organic light-emitting device may be implemented in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate, as shown in FIG. 2.
  • FIG. 3 illustrates the case where the organic material layer is multi-layered.
  • the organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306.
  • the scope of the present application is not limited by this laminated structure, and if necessary, the remaining layers except the light-emitting layer may be omitted, and other necessary functional layers may be added.
  • the step of forming the organic layer may include pre-mixing the heterocyclic compound represented by Formula 1 and forming it using a thermal vacuum deposition method.
  • the pre-mixed means mixing the materials in one source before depositing the heterocyclic compound represented by Formula 1 on the organic layer.
  • the premixed material may be referred to as a heterocyclic compound according to an exemplary embodiment of the present application.
  • the organic material layer containing the heterocyclic compound represented by Formula 1 may further include other materials as needed.
  • anode material materials with a relatively large work function can be used, and transparent conductive oxides, metals, or conductive polymers can be used.
  • the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combination of metal and oxide such as ZnO:Al or SnO2:Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.
  • the cathode material materials with a relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used.
  • specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO 2 /Al.
  • hole injection layer material known hole injection layer materials may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or those described in Advanced Material, 6, p.677 (1994). Described starburst-type amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine ( m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate), Polyaniline/Camphor sulfonic acid, or Polyaniline/Poly(4-(4
  • hole transport layer material pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular or high molecular materials may also be used.
  • Electron transport layer materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone.
  • Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and not only low molecular substances but also high molecular substances may be used.
  • LiF is typically used as an electron injection layer material in the industry, but the present application is not limited thereto.
  • Red, green, or blue light-emitting materials can be used as the light-emitting layer material, and if necessary, two or more light-emitting materials can be mixed. At this time, two or more light emitting materials can be deposited and used from individual sources, or they can be premixed and deposited from a single source. Additionally, a fluorescent material may be used as the light-emitting layer material, but it may also be used as a phosphorescent material.
  • the light emitting layer material may be a material that emits light by combining holes and electrons injected from the anode and the cathode respectively, but may also be used as a host material and a dopant material that participates in light emission together.
  • hosts of the same series may be mixed and used, or hosts of different series may be mixed and used.
  • any two or more types of materials such as an n-type host material or a p-type host material, can be selected and used as the host material of the light-emitting layer.
  • the organic light emitting device may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.
  • the heterocyclic compound according to an embodiment of the present invention may function in organic electronic devices, including organic solar cells, organic photoreceptors, organic transistors, etc., on a principle similar to that applied to organic light-emitting devices.
  • reaction solution was extracted with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and the solvent was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain compound 001. 13g was obtained (yield 83%).
  • a glass substrate coated with a thin film of indium tinoxide (ITO) with a thickness of 1,500 ⁇ was washed with distilled water ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UV (Ultraviolet Ozone) for 5 minutes using UV light in a UV (Ultraviolet) cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to increase the work function of ITO and remove the remaining film, and then transferred to a thermal evaporation equipment for organic deposition.
  • ITO indium tinoxide
  • NPB N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine
  • a light-emitting layer was thermally vacuum deposited thereon as follows.
  • the emitting layer uses 9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'-bi-9 H -carbazole as a host.
  • the compound (9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'-Bi-9 H -carbazole) was deposited at 400 ⁇ .
  • the green phosphorescent dopant was deposited by doping 7% of Ir(ppy) 3 .
  • 60 ⁇ of bathocuproine (BCP) was deposited as a hole blocking layer, and 300 ⁇ of E1 was deposited on top of it as an electron transport layer.
  • lithium fluoride (LiF) was deposited to a thickness of 10 ⁇ on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200 ⁇ on the electron injection layer to form the cathode, thereby forming an organic A light emitting device was manufactured.
  • the electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using McScience's M7000, and the standard luminance was measured to be 20,000 cd using the measurement results using a lifespan measurement equipment (M6000) manufactured by McScience.
  • M6000 lifespan measurement equipment
  • the organic light-emitting devices (Examples 1 to 58) using the compound represented by Formula 1 of the present invention as the hole transport layer material were the organic light emitting devices using the compounds of Comparative Examples 1 to 4 as the hole transport layer material.
  • the driving voltage is lower, and the luminous efficiency and lifespan are significantly improved.
  • the compounds M1 to M3 used in Comparative Examples 2 to 4 are similar to the compounds of Formula 1 of the present invention in that they have a dimethylfluorenobenzofuran-type 5-ring skeleton, but in the case of the compounds M1 and M3, dimethylfluoreno An arylamine substituent is introduced at the 4th position of benzofuran, and the compound of the present invention is different in that an arylamine substituent is not introduced at the 4th position.
  • an arylamine group is introduced at position 4 of the dimethylfluorenobenzofuran, there is a disadvantage that hole mobility becomes slower compared to other positions.
  • the arylamine group was introduced at a position other than the 4th position of the parent nucleus, thereby improving the physical properties of hole mobility and improving device characteristics.
  • the compound M2 used in Comparative Example 3 is similar to the compound of Formula 1 of the present invention in that it has a dimethylfluorenobenzofuran-type 5-ring skeleton, but has a 2-substituted arylamine group structure.
  • the HOMO level increases.
  • the compound of Formula 1 of the present invention has a single arylamine substituent, so its HOMO level is lower than that of the compound M2 used in Comparative Example 3.
  • the HOMO level is lowered, the HOMO level difference between the hole transport layer and the light emitting layer is reduced, making hole transport easier, and for this reason, it was confirmed that the device characteristics are improved.
  • the transparent electrode ITO thin film obtained from OLED glass was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol before use.
  • the ITO substrate was installed in the substrate folder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine ( 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added.
  • the vacuum in the chamber was evacuated until it reached 10 -6 torr, and then a current was applied to the cell to evaporate 2-TNATA and a 600 ⁇ thick hole injection layer was deposited on the ITO substrate.
  • the following N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis( ⁇ -naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added and evaporated by applying a current to the cell to deposit a 1000 ⁇ thick hole transport layer on the hole injection layer.
  • a compound of the following structural formula M1 was deposited to a thickness of 100 ⁇ as an electron blocking layer thereon.
  • a blue light-emitting material with the following structure was deposited as a light-emitting layer thereon. Specifically, the compound of H1, a blue light-emitting host material, was vacuum deposited to a thickness of 300 ⁇ in one cell of the vacuum deposition equipment, and the compound of D1, a blue light-emitting dopant material, was doped at 5 wt% compared to the host material and deposited on it.
  • lithium fluoride (LiF) is deposited to a thickness of 10 ⁇ as an electron injection layer on the electron transport layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,000 ⁇ on the electron injection layer to form a cathode.
  • Al aluminum
  • the electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using McScience's M7000, and the standard luminance was measured to be 20,000 cd using the measurement results using a lifespan measurement equipment (M6000) manufactured by McScience.
  • M6000 lifespan measurement equipment
  • Examples 59 to 89 which are organic light-emitting devices using the compound represented by Formula 1 of the present invention as the electron blocking layer material, were obtained by using compounds M1 to M3 and NPB as the electron blocking layer material. Compared to Comparative Examples 5 to 8, which were organic light emitting devices, the driving voltage was lower, and the luminous efficiency and lifespan were significantly improved.

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Abstract

The present specification relates to a heterocyclic compound represented by chemical formula 1 and an organic light-emitting device including same.

Description

헤테로 고리 화합물 및 이를 포함하는 유기 발광 소자Heterocyclic compounds and organic light-emitting devices containing them
본 출원은 2022년 5월 27일자 한국 특허출원 제10-2022-0065252호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용을 본 명세서의 일부로서 포함한다.This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0065252, dated May 27, 2022, and includes all contents disclosed in the document of the Korean Patent Application as part of this specification.
본 발명은 헤테로 고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to heterocyclic compounds and organic light-emitting devices containing the same.
유기 발광 소자는 자체 발광형 표시 소자의 일종으로서, 시야각이 넓고, 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다.Organic light emitting devices are a type of self-emitting display devices and have the advantages of a wide viewing angle, excellent contrast, and fast response speed.
유기 발광 소자는 2개의 전극 사이에 유기 박막을 배치시킨 구조를 가지고 있다. 이와 같은 구조의 유기 발광 소자에 전압이 인가되면, 2개의 전극으로부터 주입된 전자와 정공이 유기 박막에서 결합하여 쌍을 이룬 후 소멸하면서 빛을 발하게 된다. 상기 유기 박막은 필요에 따라 단층 또는 다층으로 구성될 수 있다.Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light emitting device with this structure, electrons and holes injected from two electrodes combine in the organic thin film to form a pair and then disappear, emitting light. The organic thin film may be composed of a single layer or multiple layers, depending on need.
유기 박막의 재료는 필요에 따라 발광 기능을 가질 수 있다. 예컨대, 유기 박막 재료로는 그 자체가 단독으로 발광층을 구성할 수 있는 화합물이 사용될 수도 있고, 또는 호스트-도펀트계 발광층의 호스트 또는 도펀트 역할을 할 수 있는 화합물이 사용될 수도 있다. 그 외에도, 유기 박막의 재료로서, 정공 주입, 정공 수송, 전자 저지, 정공 저지, 전자 수송, 전자 주입 등의 역할을 수행할 수 있는 화합물이 사용될 수도 있다.The material of the organic thin film may have a light-emitting function as needed. For example, as an organic thin film material, a compound that can independently form a light-emitting layer may be used, or a compound that can act as a host or dopant of a host-dopant-based light-emitting layer may be used. In addition, as a material for the organic thin film, compounds that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.
유기 발광 소자의 성능, 수명 또는 효율을 향상시키기 위하여, 유기 박막의 재료의 개발이 지속적으로 요구되고 있다.In order to improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of organic thin film materials is continuously required.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Document]
(특허문헌 1) 미국 등록특허 제4,356,429호(Patent Document 1) U.S. Patent No. 4,356,429
본 발명은 헤테로 고리 화합물 및 이를 포함하는 유기 발광 소자를 제공하고자 한다.The present invention seeks to provide a heterocyclic compound and an organic light-emitting device containing the same.
본 발명은 하기 화학식 1로 표시되는 헤테로 고리 화합물을 제공한다:The present invention provides a heterocyclic compound represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2023005090-appb-img-000001
Figure PCTKR2023005090-appb-img-000001
상기 화학식 1에서,In Formula 1,
R1 내지 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; -P(=O)R101R102; -SiR101R102R103; 및 하기 화학식 2로 표시되는 기로 이루어진 군으로부터 선택되거나, 서로 인접하는 2 이상의 기가 서로 결합하여 치환 또는 비치환된 C6 내지 C60의 방향족 탄화수소 고리 또는 치환 또는 비치환된 C2 내지 C60의 헤테로 고리를 형성하고, 상기 R101, R102 및 R103은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이고, R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; And two or more groups selected from the group consisting of the following formula (2), or two or more adjacent groups are combined with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 hetero ring, , R101, R102 and R103 are the same or different from each other, and are each independently a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
R2 내지 R12 중 적어도 하나는 하기 화학식 2로 표시되는 기이고,At least one of R2 to R12 is a group represented by the following formula (2),
R13 및 R14는 -CRaRbRc이고, 상기 Ra 내지 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 및 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기;로 이루어진 군으로부터 선택되고,R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; And a substituted or unsubstituted C2 to C60 heterocycloalkyl group; selected from the group consisting of,
[화학식 2][Formula 2]
Figure PCTKR2023005090-appb-img-000002
Figure PCTKR2023005090-appb-img-000002
상기 화학식 2에서,In Formula 2,
L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 단일결합; 치환 또는 비치환된 C6 내지 C60의 아릴렌기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴렌기;이고,L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;
Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group of C6 to C60; Or a substituted or unsubstituted C2 to C60 heteroaryl group;
m 및 n은 서로 같거나 상이하고, 각각 독립적으로 0 내지 3의 정수이고,m and n are the same as or different from each other and are each independently an integer from 0 to 3,
*는 상기 화학식 1의 화합물과의 결합 사이트를 나타낸다.* represents the binding site with the compound of Formula 1 above.
또한, 본 발명은 제1 전극; 상기 제1전극과 대향하여 구비된 제2전극; 및 상기 제1전극과 제2전극 사이에 구비된 1층 이상의 유기물층;을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 본 발명에 따른 헤테로 고리 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, the present invention includes a first electrode; a second electrode provided opposite the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer contains a heterocyclic compound according to the present invention.
일 실시예에 따른 헤테로 고리 화합물은 유기 발광 소자의 유기물층 재료로서 사용할 수 있다. 상기 헤테로 고리 화합물은 유기 발광 소자에서 정공 주입층 재료, 전자 저지층 재료, 정공 수송층 재료, 발광층 재료, 전자 수송층 재료, 정공 저지층 재료, 전자 저지층 재료, 전자 주입층 재료 등의 역할을 수행할 수 있다. 특히, 상기 헤테로 고리 화합물이 유기 발광 소자의 정공 수송층 재료, 정공 수송 보조층 재료 또는 전자 저지층 재료로서 사용될 수 있다.The heterocyclic compound according to one embodiment can be used as an organic layer material of an organic light-emitting device. The heterocyclic compound may serve as a hole injection layer material, an electron blocking layer material, a hole transport layer material, a light emitting layer material, an electron transport layer material, a hole blocking layer material, an electron blocking layer material, an electron injection layer material, etc. in an organic light emitting device. You can. In particular, the heterocyclic compound can be used as a hole transport layer material, a hole transport auxiliary layer material, or an electron blocking layer material of an organic light emitting device.
상기 화학식 1로 표시되는 화합물을 유기물층에 사용하는 경우, 유기 발광 소자의 구동전압을 낮추고, 발광 효율을 향상시키며, 수명 특성을 향상시킬 수 있다.When the compound represented by Formula 1 is used in the organic material layer, the driving voltage of the organic light-emitting device can be lowered, luminous efficiency can be improved, and lifespan characteristics can be improved.
도 1 내지 3은 각각 본 발명의 일 실시형태에 따른 유기 발광 소자의 적층구조를 개략적으로 나타낸 도면이다.1 to 3 are diagrams schematically showing the stacked structure of an organic light-emitting device according to an embodiment of the present invention.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 명세서에 있어서, 상기 "치환"이라는 용어는, 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.In this specification, the term "substitution" means changing a hydrogen atom bonded to a carbon atom of a compound to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted. , when two or more substituents are substituted, the two or more substituents may be the same or different from each other.
본 명세서에 있어서, "치환 또는 비치환"이란, 중수소; 할로겐; 시아노기; C1 내지 C60의 직쇄 또는 분지쇄의 알킬기; C2 내지 C60의 직쇄 또는 분지쇄의 알케닐기; C2 내지 C60의 직쇄 또는 분지쇄의 알키닐기; C3 내지 C60의 단환 또는 다환의 시클로알킬기; C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬기; C6 내지 C60의 단환 또는 다환의 아릴기; C2 내지 C60의 단환 또는 다환의 헤테로아릴기; -SiRR'R"; -P(=O)RR'; C1 내지 C20의 알킬아민기; C6 내지 C60의 단환 또는 다환의 아릴아민기; 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중에서 선택된 2 이상의 치환기가 연결된 치환기로 치환 또는 비치환된 것을 의미한다.In this specification, “substituted or unsubstituted” means deuterium; halogen; Cyano group; C1 to C60 straight or branched alkyl group; C2 to C60 straight or branched alkenyl group; C2 to C60 straight or branched alkynyl group; C3 to C60 monocyclic or polycyclic cycloalkyl group; C2 to C60 monocyclic or polycyclic heterocycloalkyl group; C6 to C60 monocyclic or polycyclic aryl group; C2 to C60 monocyclic or polycyclic heteroaryl group; -SiRR'R"; -P(=O)RR'; a group consisting of a C1 to C20 alkylamine group; a C6 to C60 monocyclic or polycyclic arylamine group; and a C2 to C60 monocyclic or polycyclic heteroarylamine group. It means being substituted or unsubstituted with one or more substituents selected from, or substituted or unsubstituted with a substituent where two or more substituents selected from the above-exemplified substituents are connected.
본 명세서에 있어서, 상기 할로겐은 불소, 염소, 브롬 또는 요오드일 수 있다.In this specification, the halogen may be fluorine, chlorine, bromine, or iodine.
본 명세서에 있어서, 알킬기는 탄소수 1 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 상기 알킬기의 탄소수는 1 내지 60, 구체적으로 1 내지 40, 더욱 구체적으로, 1 내지 20일 수 있다. 구체적인 예로는 메틸기, 에틸기, 프로필기, n-프로필기, 이소프로필기, 부틸기, n-부틸기, 이소부틸기, tert-부틸기, sec-부틸기, 1-메틸-부틸기, 1-에틸-부틸기, 펜틸기, n-펜틸기, 이소펜틸기, 네오펜틸기, tert-펜틸기, 헥실기, n-헥실기, 1-메틸펜틸기, 2-메틸펜틸기, 4-메틸-2-펜틸기, 3,3-디메틸부틸기, 2-에틸부틸기, 헵틸기, n-헵틸기, 1-메틸헥실기, 시클로펜틸메틸기, 시클로헥실메틸기, 옥틸기, n-옥틸기, tert-옥틸기, 1-메틸헵틸기, 2-에틸헥실기, 2-프로필펜틸기, n-노닐기, 2,2-디메틸 헵틸기, 1-에틸-프로필기, 1,1-디메틸-프로필기, 이소헥실기, 4-메틸헥실기, 5-메틸헥실기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethyl heptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.
본 명세서에 있어서, 알케닐기는 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 상기 알케닐기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로, 2 내지 20일 수 있다. 구체적인 예로는 비닐기, 1-프로페닐기, 이소프로페닐기, 1-부테닐기, 2-부테닐기, 3-부테닐기, 1-펜테닐기, 2-펜테닐기, 3-펜테닐기, 3-메틸-1-부테닐기, 1,3-부타디에닐기, 알릴기, 1-페닐비닐-1-일기, 2-페닐비닐-1-일기, 2,2-디페닐비닐-1-일기, 2-페닐-2-(나프틸-1-일)비닐-1-일기, 2,2-비스(디페닐-1-일)비닐-1-일기, 스틸베닐기, 스티레닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkenyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited thereto. .
본 명세서에 있어서, 알키닐기는 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 상기 알키닐기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로, 2 내지 20일 수 있다.In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.
본 명세서에 있어서, 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 20인 것이 바람직하다. 구체적으로, 메톡시기, 에톡시기, n-프로폭시기, 이소프로폭시기, n-부톡시기, 이소부톡시기, tert-부톡시기, sec-부톡시기, n-펜틸옥시기, 네오펜틸옥시기, 이소펜틸옥시기, n-헥실옥시기, 3,3-디메틸부틸옥시기, 2-에틸부틸옥시기, n-옥틸옥시기, n-노닐옥시기, n-데실옥시기, 벤질옥시기, p-메틸벤질옥시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, Isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p -methylbenzyloxy group, etc., but is not limited thereto.
본 명세서에 있어서, 시클로알킬기는 탄소수 3 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 시클로알킬기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 시클로알킬기일 수도 있으나, 다른 종류의 고리기, 예컨대 헤테로시클로알킬기, 아릴기, 헤테로아릴기 등일 수도 있다. 상기 시클로알킬기의 탄소수는 3 내지 60, 구체적으로 3 내지 40, 더욱 구체적으로 5 내지 20일 수 있다. 구체적으로, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 3-메틸시클로펜틸기, 2,3-디메틸시클로펜틸기, 시클로헥실기, 3-메틸시클로헥실기, 4-메틸시클로헥실기, 2,3-디메틸시클로헥실기, 3,4,5-트리메틸시클로헥실기, 4-tert-부틸시클로헥실기, 시클로헵틸기, 시클로옥틸기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms and may be further substituted by another substituent. Here, polycyclic refers to a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 , 3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but is not limited thereto.
본 명세서에 있어서, 헤테로시클로알킬기는 헤테로 원자로서 O, S, Se, N 또는 Si를 포함하고, 탄소수 2 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 헤테로시클로알킬기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로시클로알킬기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬기, 아릴기, 헤테로아릴기 등일 수도 있다. 상기 헤테로시클로알킬기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로 3 내지 20일 수 있다.In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.
본 명세서에 있어서, 아릴기는 탄소수 6 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 아릴기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 아릴기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬기, 헤테로시클로알킬기, 헤테로아릴기 등일 수도 있다. 상기 아릴기는 스피로기를 포함할 수 있다. 상기 아릴기의 탄소수는 6 내지 60, 구체적으로 6 내지 40, 더욱 구체적으로 6 내지 25일 수 있다. 상기 아릴기의 구체적인 예로는 페닐기, 비페닐기, 터페닐기, 나프틸기, 안트릴기, 크라이세닐기, 페난트레닐기, 페릴레닐기, 플루오란테닐기, 트리페닐레닐기, 페날레닐기, 파이레닐기, 테트라세닐기, 펜타세닐기, 플루오레닐기, 인데닐기, 아세나프틸레닐기, 벤조플루오레닐기, 스피로비플루오레닐기, 2,3-디히드로-1H-인데닐기, 이들의 축합고리기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which an aryl group is directly connected to or condensed with another ring group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, heteroaryl group, etc. The aryl group may include a spiro group. The aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms. Specific examples of the aryl group include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, and pyrethyl group. Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed rings thereof etc., but is not limited to this.
본 명세서에 있어서, 포스핀옥사이드기는 -P(=O)R101R102로 표시되고, R101 및 R102는 서로 동일하거나 상이하며, 각각 독립적으로 수소; 중수소; 할로겐기; 알킬기; 알케닐기; 알콕시기; 시클로알킬기; 아릴기; 및 헤테로 고리기 중 적어도 하나로 이루어진 치환기일 수 있다. 구체적으로 아릴기로 치환될 수 있으며, 상기 아릴기는 전술한 예시가 적용될 수 있다. 예컨대, 포스핀옥사이드기는 디페닐포스핀옥사이드기, 디나프틸포스핀옥사이드 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the phosphine oxide group is represented by -P(=O)R101R102, and R101 and R102 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specifically, it may be substituted with an aryl group, and the examples described above may be applied to the aryl group. For example, the phosphine oxide group includes diphenylphosphine oxide group, dinaphthylphosphine oxide, etc., but is not limited thereto.
본 명세서에 있어서, 실릴기는 Si를 포함하고 상기 Si 원자가 라디칼로서 직접 연결되는 치환기이며, -SiR101R102R103로 표시되고, R101 내지 R103은 서로 동일하거나 상이하며, 각각 독립적으로 수소; 중수소; 할로겐기; 알킬기; 알케닐기; 알콕시기; 시클로알킬기; 아릴기; 및 헤테로 고리기 중 적어도 하나로 이루어진 치환기일수 있다. 실릴기의 구체적인 예로는 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the silyl group is a substituent that contains Si and is directly connected to the Si atom as a radical, and is represented by -SiR101R102R103, and R101 to R103 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of silyl groups include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. It is not limited.
본 명세서에 있어서, 상기 플루오레닐기는 치환될 수 있으며, 인접한 치환기들이 서로 결합하여 고리를 형성할 수 있다.In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.
상기 플루오레닐기가 치환되는 경우, When the fluorenyl group is substituted,
Figure PCTKR2023005090-appb-img-000003
등이 될 수 있으나, 이에 한정되는 것은 아니다.
Figure PCTKR2023005090-appb-img-000003
It may be, but is not limited to this.
본 명세서에 있어서, 스피로기는 스피로 구조를 포함하는 기로서, 탄소수 15 내지 60일 수 있다. 예컨대, 상기 스피로기는 플루오레닐기에 2,3-디히드로-1H-인덴기 또는 시클로헥산기가 스피로 결합된 구조를 포함할 수 있다. 구체적으로, 하기 스피로기는 하기 구조식의 기 중 어느 하나를 포함할 수 있다.In the present specification, a spiro group is a group containing a spiro structure and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the spiro group below may include any one of the groups of the structural formula below.
Figure PCTKR2023005090-appb-img-000004
Figure PCTKR2023005090-appb-img-000004
본 명세서에 있어서, 헤테로아릴기는 헤테로 원자로서 S, O, Se, N 또는 Si를 포함하고, 탄소수 2 내지 60인 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 상기 다환이란 헤테로아릴기가 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로아릴기일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬기, 헤테로시클로알킬기, 아릴기 등일 수도 있다. 상기 헤테로아릴기의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로 3 내지 25일 수 있다. 상기 헤테로아릴기의 구체적인 예로는 피리딜기, 피롤릴기, 피리미딜기, 피리다지닐기, 푸라닐기, 티오페닐기, 이미다졸릴기, 피라졸릴기, 옥사졸릴기, 이속사졸릴기, 티아졸릴기, 이소티아졸릴기, 트리아졸릴기, 푸라자닐기, 옥사디아졸릴기, 티아디아졸릴기, 디티아졸릴기, 테트라졸릴기, 파이라닐기, 티오파이라닐기, 디아지닐기, 옥사지닐기, 티아지닐기, 디옥시닐기, 트리아지닐기, 테트라지닐기, 퀴놀릴기, 이소퀴놀릴기, 퀴나졸리닐기, 이소퀴나졸리닐기, 퀴노졸리릴기, 나프티리딜기, 아크리디닐기, 페난트리디닐기, 이미다조피리디닐기, 디아자나프탈레닐기, 트리아자인데닐기, 2-인돌릴기, 인돌리지닐기, 벤조티아졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티오페닐기, 벤조퓨라닐기, 디벤조티오페닐기, 디벤조퓨라닐기, 카바졸릴기, 벤조카바졸릴기, 디벤조카바졸릴기, 페나지닐기, 디벤조실롤기, 스피로비(디벤조실롤)기, 디히드로페나지닐기, 페녹사지닐기, 페난트리딜기, 티에닐기, 인돌로[2,3-a]카바졸릴기, 인돌로[2,3-b]카바졸릴기, 인돌리닐기, 10,11-디히드로-디벤조[b,f]아제피닐기, 9,10-디히드로아크리디닐기, 페난트라지닐기, 페노티아지닐기, 프탈라지닐기, 나프틸리디닐기, 페난트롤리닐기, 벤조[c][1,2,5]티아디아졸릴기, 5,10-디히드로디벤조[b,e][1,4]아자실리닐기, 피라졸로[1,5-c]퀴나졸리닐기, 피리도[1,2-b]인다졸릴기, 피리도[1,2-a]이미다조[1,2-e]인돌리닐기, 5,11-디히드로인데노[1,2-b]카바졸릴기 등을 들 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the heteroaryl group contains S, O, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, or aryl group. The carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, and thiazolyl group. , isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group, Thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyryl group, naphthyridyl group, acridinyl group, phenanthridinyl group , imidazopyridinyl group, diazanaphthalenyl group, triazindenyl group, 2-indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophenyl group, benzofura Nyl group, dibenzothiophenyl group, dibenzofuranyl group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol) group, dihydrophenazinyl group , phenoxazinyl group, phenanthridyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10,11-dihydro- Dibenzo[b,f]azepinyl group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, benzo[c][ 1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azacylinyl group, pyrazolo[1,5-c]quinazolinyl group, pyrido[1 ,2-b]indazolyl group, pyrido[1,2-a]imidazo[1,2-e]indolinyl group, 5,11-dihydroindeno[1,2-b]carbazolyl group, etc. Examples include, but are not limited to.
본 명세서에 있어서, 아민기는 모노알킬아민기; 모노아릴아민기; 모노헤테로아릴아민기; -NH2; 디알킬아민기; 디아릴아민기; 디헤테로아릴아민기; 알킬아릴아민기; 알킬헤테로아릴아민기; 및 아릴헤테로아릴아민기로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 1 내지 30인 것이 바람직하다. 상기 아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 비페닐아민기, 디비페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, 페닐나프틸아민기, 디톨릴아민기, 페닐톨릴아민기, 트리페닐아민기, 비페닐나프틸아민기, 페닐비페닐아민기, 비페닐플루오레닐아민기, 페닐트리페닐레닐아민기, 비페닐트리페닐레닐아민기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH 2 ; dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenyl fluorescein Examples include a nylamine group, phenyltriphenylenylamine group, and biphenyltriphenylenylamine group, but are not limited thereto.
본 명세서에 있어서, 아릴렌기는 아릴기에 결합 위치가 두 개 있는 것, 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 아릴기의 설명이 적용될 수 있다. 또한, 헤테로아릴렌기는 헤테로아릴기에 결합 위치가 두 개 있는 것, 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 헤테로아릴기의 설명이 적용될 수 있다.In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group. In addition, a heteroarylene group means that a heteroaryl group has two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.
본 명세서에 있어서, "인접한" 기는 해당 치환기가 치환된 원자와 직접 연결된 원자에 치환된 치환기, 해당 치환기와 입체구조적으로 가장 가깝게 위치한 치환기, 또는 해당 치환기가 치환된 원자에 치환된 다른 치환기를 의미할 수 있다. 예컨대, 벤젠고리에서 오쏘(ortho)위치로 치환된 2개의 치환기 및 지방족 고리에서 동일 탄소에 치환된 2개의 치환기는 서로 “인접한”기로 해석될 수 있다.As used herein, an “adjacent” group may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the substituent in terms of structure, or another substituent substituted on the atom on which the substituent is substituted. You can. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as “adjacent” groups.
본 발명에 있어서, "화학식 또는 화합물 구조에 치환기가 표시되지 않은 경우"는 탄소 원자에 수소 원자가 결합된 것을 의미한다. 다만, 중수소(2H, Deuterium)는 수소의 동위원소이므로, 일부 수소 원자는 중수소일 수 있다.In the present invention, “when a substituent is not indicated in the chemical formula or compound structure” means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( 2H , Deuterium) is an isotope of hydrogen, some hydrogen atoms may be deuterium.
본 발명의 일 실시형태에 있어서, “화학식 또는 화합물 구조에 치환기가 표시되지 않은 경우”는 치환기로 올 수 있는 위치가 모두 수소 또는 중수소인 것을 의미할 수 있다. 즉, 중수소의 경우 수소의 동위원소로, 일부의 수소 원자는 동위원소인 중수소일 수 있으며, 이 때 중수소의 함량은 0% 내지 100%일 수 있다.In one embodiment of the present invention, “when a substituent is not indicated in the chemical formula or compound structure” may mean that all positions that can appear as substituents are hydrogen or deuterium. That is, in the case of deuterium, it is an isotope of hydrogen, and some hydrogen atoms may be the isotope deuterium, and in this case, the content of deuterium may be 0% to 100%.
본 발명의 일 실시형태에 있어서, "화학식 또는 화합물 구조에 치환기가 표시되지 않은 경우"에 있어서, "중수소의 함량이 0%", "수소의 함량이 100%", "치환기는 모두 수소" 등 중수소를 명시적으로 배제하지 않는 경우에는 수소와 중수소는 화합물에 있어 혼재되어 사용될 수 있다.In one embodiment of the present invention, in “cases where substituents are not indicated in the chemical formula or compound structure,” “the content of deuterium is 0%,” “the content of hydrogen is 100%,” “all substituents are hydrogen,” etc. If deuterium is not explicitly excluded, hydrogen and deuterium can be used together in a compound.
본 발명의 일 실시형태에 있어서, 중수소는 수소의 동위원소(isotope) 중 하나로 양성자(proton) 1개와 중성자(neutron) 1개로 이루어진 중양성자(deuteron)를 원자핵(nucleus)으로 가지는 원소로서, 수소-2로 표현될 수 있으며, 원소기호는 D 또는 2H로 쓸 수도 있다.In one embodiment of the present invention, deuterium is one of the isotopes of hydrogen and is an element that has a deuteron consisting of one proton and one neutron as its nucleus. Hydrogen- It can be expressed as 2, and the element symbol can also be written as D or 2 H.
본 발명의 일 실시형태에 있어서, 동위원소는 원자 번호(atomic number, Z)는 같지만, 질량수(mass number, A)가 다른 원자를 의미하는 동위원소는 같은 수의 양성자(proton)를 갖지만, 중성자(neutron)의 수가 다른 원소로도 해석할 수 있다.In one embodiment of the present invention, isotopes refer to atoms having the same atomic number (Z) but different mass numbers (A). Isotopes have the same number of protons but do not contain neutrons. It can also be interpreted as an element with a different number of neutrons.
본 발명의 일 실시형태에 있어서, 특정 치환기의 함량 T%의 의미는 기본이 되는 화합물이 가질 수 있는 치환기의 총 개수를 T1으로 정의하고, 그 중 특정의 치환기의 개수를 T2로 정의하는 경우 T2/T1×100 = T%로 정의할 수 있다.In one embodiment of the present invention, the meaning of the content T% of a specific substituent means that the total number of substituents that the basic compound can have is defined as T1, and the number of specific substituents among them is defined as T2. It can be defined as /T1×100 = T%.
즉, 일 예시에 있어서,
Figure PCTKR2023005090-appb-img-000005
로 표시되는 페닐기에 있어서 중수소의 함량 20%라는 것은 페닐기가 가질 수 있는 치환기의 총 개수는 5(식 중 T1)개이고, 그 중 중수소의 개수가 1(식 중 T2)인 경우를 의미할 수 있다. 즉, 페닐기에 있어서 중수소의 함량 20%라는 것인 하기 구조식으로 표시될 수 있다.That is, in one example,
Figure PCTKR2023005090-appb-img-000005
The deuterium content of 20% in the phenyl group represented by can mean that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and the number of deuteriums among them is 1 (T2 in the formula). . That is, it can be expressed by the following structural formula, which means that the deuterium content in the phenyl group is 20%.
Figure PCTKR2023005090-appb-img-000006
Figure PCTKR2023005090-appb-img-000006
또한, 본 발명의 일 실시형태에 있어서, “중수소의 함량이 0%인 페닐기”의 경우 중수소 원자가 포함되지 않은, 즉 수소 원자 5개를 갖는 페닐기를 의미할 수 있다.Additionally, in one embodiment of the present invention, “a phenyl group with a deuterium content of 0%” may mean a phenyl group that does not contain deuterium atoms, that is, has 5 hydrogen atoms.
본 발명에 있어서, C6 내지 C60의 방향족 탄화수소 고리는 C6 내지 C60개의 탄소와 수소로 이루어진 방향족 고리를 포함하는 화합물을 의미하며, 예를 들어, 벤젠, 비페닐, 터페닐, 트리페닐렌, 나프탈렌, 안트라센, 페날렌, 페난트렌, 플루오렌, 피렌, 크리센, 페릴렌, 아줄렌 등을 들 수 있으나, 이들로 한정되는 것은 아니며, 상기 탄소수를 충족하는 것으로서 이 분야에 공지된 방향족 탄화수소 고리 화합물을 모두 포함한다.In the present invention, the C6 to C60 aromatic hydrocarbon ring refers to a compound containing an aromatic ring consisting of C6 to C60 carbons and hydrogen, for example, benzene, biphenyl, terphenyl, triphenylene, naphthalene, Anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene, etc. may be mentioned, but are not limited to these, and aromatic hydrocarbon ring compounds known in the art that satisfy the above carbon number may be used. Includes all.
본 발명은 하기 화학식 1로 표시되는 헤테로 고리 화합물을 제공한다:The present invention provides a heterocyclic compound represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2023005090-appb-img-000007
Figure PCTKR2023005090-appb-img-000007
상기 화학식 1에서,In Formula 1,
R1 내지 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; -P(=O)R101R102; -SiR101R102R103; 및 하기 화학식 2로 표시되는 기로 이루어진 군으로부터 선택되거나, 서로 인접하는 2 이상의 기가 서로 결합하여 치환 또는 비치환된 C6 내지 C60의 방향족 탄화수소 고리 또는 치환 또는 비치환된 C2 내지 C60의 헤테로 고리를 형성하고, 상기 R101, R102 및 R103은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이고, R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; And two or more groups selected from the group consisting of the following formula (2), or two or more adjacent groups are combined with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 hetero ring, , R101, R102 and R103 are the same or different from each other, and are each independently a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
R2 내지 R12 중 적어도 하나는 하기 화학식 2로 표시되는 기이고,At least one of R2 to R12 is a group represented by the following formula (2),
R13 및 R14는 -CRaRbRc이고, 상기 Ra 내지 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 및 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기;로 이루어진 군으로부터 선택되고,R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; And a substituted or unsubstituted C2 to C60 heterocycloalkyl group; selected from the group consisting of,
[화학식 2][Formula 2]
Figure PCTKR2023005090-appb-img-000008
Figure PCTKR2023005090-appb-img-000008
상기 화학식 2에서,In Formula 2,
L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 단일결합; 치환 또는 비치환된 C6 내지 C60의 아릴렌기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴렌기;이고,L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;
Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group of C6 to C60; Or a substituted or unsubstituted C2 to C60 heteroaryl group;
m 및 n은 서로 같거나 상이하고, 각각 독립적으로 0 내지 3의 정수이고,m and n are the same as or different from each other and are each independently an integer from 0 to 3,
*는 상기 화학식 1의 화합물과의 결합 사이트를 나타낸다.* represents the binding site with the compound of Formula 1 above.
본 발명의 일 실시형태에 있어서, R1 내지 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C30의 알킬기; 치환 또는 비치환된 C2 내지 C30의 알케닐기; 치환 또는 비치환된 C2 내지 C30의 알키닐기; 치환 또는 비치환된 C1 내지 C30의 알콕시기; 치환 또는 비치환된 C3 내지 C30의 시클로알킬기; 치환 또는 비치환된 C2 내지 C30의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C30의 아릴기; 치환 또는 비치환된 C2 내지 C30의 헤테로아릴기; -P(=O)R101R102; -SiR101R102R103; 및 하기 화학식 2로 표시되는 기로 이루어진 군으로부터 선택되거나, 서로 인접하는 2 이상의 기가 서로 결합하여 치환 또는 비치환된 C6 내지 C30의 방향족 탄화수소 고리 또는 치환 또는 비치환된 C2 내지 C30의 헤테로 고리를 형성하고, 상기 R101, R102 및 R103은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C30의 알킬기; 치환 또는 비치환된 C6 내지 C30의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이고, 상기 R2 내지 R12 중 적어도 하나는 하기 화학식 2로 표시되는 기일 수 있다.In one embodiment of the present invention, R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; Substituted or unsubstituted C2 to C30 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; And two or more groups selected from the group consisting of the following formula (2), or two or more adjacent groups are combined with each other to form a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C30 hetero ring, , R101, R102 and R103 are the same or different from each other, and are each independently a substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, and at least one of R2 to R12 may be a group represented by the following formula (2).
본 발명의 다른 실시형태에 있어서, R1 내지 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C20의 알킬기; 치환 또는 비치환된 C2 내지 C20의 알케닐기; 치환 또는 비치환된 C2 내지 C20의 알키닐기; 치환 또는 비치환된 C1 내지 C20의 알콕시기; 치환 또는 비치환된 C3 내지 C20의 시클로알킬기; 치환 또는 비치환된 C2 내지 C20의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기; -P(=O)R101R102; -SiR101R102R103; 및 하기 화학식 2로 표시되는 기로 이루어진 군으로부터 선택되거나, 서로 인접하는 2 이상의 기가 서로 결합하여 치환 또는 비치환된 C6 내지 C20의 방향족 탄화수소 고리 또는 치환 또는 비치환된 C2 내지 C20의 헤테로 고리를 형성하고, 상기 R101, R102 및 R103은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C20의 알킬기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 또는 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기이고, 상기 R2 내지 R12 중 적어도 하나는 하기 화학식 2로 표시되는 기일 수 있다.In another embodiment of the present invention, R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; Substituted or unsubstituted C2 to C20 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; And two or more groups selected from the group consisting of the following formula (2), or two or more adjacent groups are combined with each other to form a substituted or unsubstituted C6 to C20 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C20 hetero ring, , R101, R102 and R103 are the same or different from each other, and are each independently a substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group, and at least one of R2 to R12 may be a group represented by the following formula (2).
본 발명의 다른 실시형태에 있어서, R1 내지 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C20의 알킬기; 치환 또는 비치환된 C2 내지 C20의 알케닐기; 치환 또는 비치환된 C2 내지 C20의 알키닐기; 치환 또는 비치환된 C1 내지 C20의 알콕시기; 치환 또는 비치환된 C3 내지 C20의 시클로알킬기; 치환 또는 비치환된 C2 내지 C20의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기; 및 하기 화학식 2로 표시되는 기로 이루어진 군으로부터 선택되고, 상기 R2 내지 R12 중 적어도 하나는 하기 화학식 2로 표시되는 기일 수 있다.In another embodiment of the present invention, R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; Substituted or unsubstituted C2 to C20 heteroaryl group; and a group represented by the following formula (2), wherein at least one of R2 to R12 may be a group represented by the formula (2).
본 발명의 일 실시형태에 있어서, R1은 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C30의 알킬기; 치환 또는 비치환된 C2 내지 C30의 알케닐기; 치환 또는 비치환된 C2 내지 C30의 알키닐기; 치환 또는 비치환된 C1 내지 C30의 알콕시기; 치환 또는 비치환된 C3 내지 C30의 시클로알킬기; 치환 또는 비치환된 C2 내지 C30의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C30의 아릴기; 또는 치환 또는 비치환된 C2 내지 C30의 헤테로아릴기;일 수 있다.In one embodiment of the invention, R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group;
본 발명의 다른 실시형태에 있어서, R1은 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C20의 알킬기; 치환 또는 비치환된 C2 내지 C20의 알케닐기; 치환 또는 비치환된 C2 내지 C20의 알키닐기; 치환 또는 비치환된 C1 내지 C20의 알콕시기; 치환 또는 비치환된 C3 내지 C20의 시클로알킬기; 치환 또는 비치환된 C2 내지 C20의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 또는 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기;일 수 있다.In another embodiment of the invention, R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.
본 발명의 다른 실시형태에 있어서, R1은 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 또는 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기;일 수 있다.In another embodiment of the invention, R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.
본 발명의 다른 실시형태에 있어서, R1은 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 디벤조퓨라닐기; 치환 또는 비치환된 디벤조티오페닐기; 또는 치환 또는 비치환된 디벤조카바졸릴기;일 수 있다.In another embodiment of the invention, R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
본 발명의 일 실시형태에 있어서, 상기 R2 내지 R8 중 적어도 하나는 하기 화학식 2로 표시되는 기일 수 있다:In one embodiment of the present invention, at least one of R2 to R8 may be a group represented by the following formula (2):
[화학식 2][Formula 2]
Figure PCTKR2023005090-appb-img-000009
Figure PCTKR2023005090-appb-img-000009
상기 화학식 2는 앞서 정의된 바와 같다.Formula 2 is as previously defined.
본 발명의 다른 실시형태에 있어서, 상기 R2 내지 R4 중 어느 하나가 상기 화학식 2로 표시되는 기이고, 상기 R1 및 R5 내지 R8은 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C30의 알킬기; 치환 또는 비치환된 C2 내지 C30의 알케닐기; 치환 또는 비치환된 C2 내지 C30의 알키닐기; 치환 또는 비치환된 C1 내지 C30의 알콕시기; 치환 또는 비치환된 C3 내지 C30의 시클로알킬기; 치환 또는 비치환된 C2 내지 C30의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C30의 아릴기; 및 치환 또는 비치환된 C2 내지 C30의 헤테로아릴기;로 이루어진 군으로부터 선택될 수 있다.In another embodiment of the present invention, any one of R2 to R4 is a group represented by Formula 2, and R1 and R5 to R8 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; and a substituted or unsubstituted C2 to C30 heteroaryl group.
본 발명의 다른 실시형태에 있어서, 상기 R2 내지 R4 중 어느 하나가 상기 화학식 2로 표시되는 기이고, 상기 R1 및 R5 내지 R8은 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C20의 알킬기; 치환 또는 비치환된 C2 내지 C20의 알케닐기; 치환 또는 비치환된 C2 내지 C20의 알키닐기; 치환 또는 비치환된 C1 내지 C20의 알콕시기; 치환 또는 비치환된 C3 내지 C20의 시클로알킬기; 치환 또는 비치환된 C2 내지 C20의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 및 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기;로 이루어진 군으로부터 선택될 수 있다.In another embodiment of the present invention, any one of R2 to R4 is a group represented by Formula 2, and R1 and R5 to R8 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group.
본 발명의 다른 실시형태에 있어서, 상기 R2 내지 R4 중 어느 하나가 상기 화학식 2로 표시되는 기이고, 상기 R1 및 R5 내지 R8은 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 페난트레닐기; 치환 또는 비치환된 트리페닐레닐기; 치환 또는 비치환된 디벤조퓨라닐기; 치환 또는 비치환된 디벤조티오페닐기; 또는 치환 또는 비치환된 디벤조카바졸릴기;일 수 있다.In another embodiment of the present invention, any one of R2 to R4 is a group represented by Formula 2, and R1 and R5 to R8 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
본 발명의 다른 실시형태에 있어서, 상기 R5 내지 R8 중 어느 하나가 상기 화학식 2로 표시되는 기이고, 상기 R1 내지 R4는 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C30의 알킬기; 치환 또는 비치환된 C2 내지 C30의 알케닐기; 치환 또는 비치환된 C2 내지 C30의 알키닐기; 치환 또는 비치환된 C1 내지 C30의 알콕시기; 치환 또는 비치환된 C3 내지 C30의 시클로알킬기; 치환 또는 비치환된 C2 내지 C30의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C30의 아릴기; 및 치환 또는 비치환된 C2 내지 C30의 헤테로아릴기;로 이루어진 군으로부터 선택될 수 있다.In another embodiment of the present invention, any one of R5 to R8 is a group represented by Formula 2, and R1 to R4 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; Substituted or unsubstituted C2 to C30 heterocycloalkyl group; Substituted or unsubstituted C6 to C30 aryl group; and a substituted or unsubstituted C2 to C30 heteroaryl group.
본 발명의 다른 실시형태에 있어서, 상기 R5 내지 R8 중 어느 하나가 상기 화학식 2로 표시되는 기이고, 상기 R1 내지 R4는 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C20의 알킬기; 치환 또는 비치환된 C2 내지 C20의 알케닐기; 치환 또는 비치환된 C2 내지 C20의 알키닐기; 치환 또는 비치환된 C1 내지 C20의 알콕시기; 치환 또는 비치환된 C3 내지 C20의 시클로알킬기; 치환 또는 비치환된 C2 내지 C20의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C20의 아릴기; 및 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기;로 이루어진 군으로부터 선택될 수 있다.In another embodiment of the present invention, any one of R5 to R8 is a group represented by Formula 2, and R1 to R4 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C2 to C20 alkenyl group; Substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group.
본 발명의 다른 실시형태에 있어서, 상기 R5 내지 R8 중 어느 하나가 상기 화학식 2로 표시되는 기이고, 상기 R1 내지 R4는 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 페난트레닐기; 치환 또는 비치환된 트리페닐레닐기; 치환 또는 비치환된 디벤조퓨라닐기; 치환 또는 비치환된 디벤조티오페닐기; 또는 치환 또는 비치환된 디벤조카바졸릴기;일 수 있다.In another embodiment of the present invention, any one of R5 to R8 is a group represented by Formula 2, and R1 to R4 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
본 발명의 일 실시형태에 있어서, R13 및 R14는 -CRaRbRc이고, 상기 Ra 내지 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C30의 알킬기; 치환 또는 비치환된 C2 내지 C30의 알케닐기; 치환 또는 비치환된 C2 내지 C30의 알키닐기; 치환 또는 비치환된 C1 내지 C30의 알콕시기; 치환 또는 비치환된 C3 내지 C30의 시클로알킬기; 및 치환 또는 비치환된 C2 내지 C30의 헤테로시클로알킬기;로 이루어진 군으로부터 선택될 수 있다.In one embodiment of the present invention, R13 and R14 are -CRaRbRc, and Ra to Rc are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C30 alkyl group; Substituted or unsubstituted C2 to C30 alkenyl group; Substituted or unsubstituted C2 to C30 alkynyl group; Substituted or unsubstituted C1 to C30 alkoxy group; Substituted or unsubstituted C3 to C30 cycloalkyl group; and a substituted or unsubstituted C2 to C30 heterocycloalkyl group.
본 발명의 다른 실시형태에 있어서, R13 및 R14는 -CRaRbRc이고, 상기 Ra 내지 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C10의 알킬기; 치환 또는 비치환된 C2 내지 C10의 알케닐기; 치환 또는 비치환된 C2 내지 C10의 알키닐기; 치환 또는 비치환된 C1 내지 C10의 알콕시기; 치환 또는 비치환된 C3 내지 C10의 시클로알킬기; 및 치환 또는 비치환된 C2 내지 C10의 헤테로시클로알킬기;로 이루어진 군으로부터 선택될 수 있다.In another embodiment of the present invention, R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C10 alkyl group; Substituted or unsubstituted C2 to C10 alkenyl group; Substituted or unsubstituted C2 to C10 alkynyl group; Substituted or unsubstituted C1 to C10 alkoxy group; Substituted or unsubstituted C3 to C10 cycloalkyl group; and a substituted or unsubstituted C2 to C10 heterocycloalkyl group.
본 발명의 다른 실시형태에 있어서, R13 및 R14는 -CRaRbRc이고, 상기 Ra 내지 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 및 시아노기;로 이루어진 군으로부터 선택될 수 있다.In another embodiment of the present invention, R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; And cyano group; may be selected from the group consisting of.
본 발명의 일 실시형태에 있어서, L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 단일결합; 치환 또는 비치환된 C6 내지 C30의 아릴렌기; 또는 치환 또는 비치환된 C2 내지 C30의 헤테로아릴렌기;일 수 있다.In one embodiment of the present invention, L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C30 arylene group; Or it may be a substituted or unsubstituted C2 to C30 heteroarylene group.
본 발명의 다른 실시형태에 있어서, L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 단일결합; 치환 또는 비치환된 C6 내지 C20의 아릴렌기; 또는 치환 또는 비치환된 C2 내지 C20의 헤테로아릴렌기;일 수 있다.In another embodiment of the present invention, L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C20 arylene group; Or a substituted or unsubstituted C2 to C20 heteroarylene group;
본 발명의 다른 실시형태에 있어서, L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 단일결합; 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 비페닐렌기; 또는 치환 또는 비치환된 터페닐렌기;일 수 있다.In another embodiment of the present invention, L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Or it may be a substituted or unsubstituted terphenylene group.
본 발명의 일 실시형태에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C30의 아릴기; 또는 치환 또는 비치환된 C2 내지 C30의 헤테로아릴기;일 수 있다.In one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group;
본 발명의 다른 실시형태에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C20의 아릴기; 또는 치환 또는 비치환된 C2 내지 C20의 헤테로아릴기;일 수 있다.In another embodiment of the present invention, Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.
본 발명의 다른 실시형태에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 페난트레닐기; 치환 또는 비치환된 트리페닐레닐기; 치환 또는 비치환된 플루오레닐기; 치환 또는 비치환된 디벤조퓨라닐기; 치환 또는 비치환된 디벤조티오페닐기; 또는 치환 또는 비치환된 디벤조카바졸릴기;일 수 있다.In another embodiment of the present invention, Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted fluorenyl group; Substituted or unsubstituted dibenzofuranyl group; Substituted or unsubstituted dibenzothiophenyl group; Or it may be a substituted or unsubstituted dibenzocarbazolyl group.
본 발명의 다른 실시형태에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 상기 Ar1 또는 Ar2가 9,9-디페닐플루오레닐기인 경우는 제외될 수 있다. 보다 구체적으로, Ar1 또는 Ar2는 하기 화합물들 중 어느 하나로 표시되는 화합물을 포함하는 것이 제외된다:In another embodiment of the present invention, Ar1 and Ar2 are the same or different from each other, and the case where Ar1 or Ar2 is a 9,9-diphenylfluorenyl group may be excluded. More specifically, Ar1 or Ar2 is excluded to include a compound represented by any of the following compounds:
Figure PCTKR2023005090-appb-img-000010
Figure PCTKR2023005090-appb-img-000010
본 발명의 일 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 치환기로서 중수소를 포함하지 않을 수 있거나, 수소 원자와 중수소 원자의 총수에 대한 중수소의 함량은 예를 들면, 0% 초과, 1% 이상, 10% 이상, 20% 이상, 30% 이상, 40% 이상 또는 50% 이상일 수 있고, 100% 이하, 90% 이하, 80% 이하, 70% 이하, 60% 이하일 수 있다.In one embodiment of the present invention, the compound represented by Formula 1 may not contain deuterium as a substituent, or the content of deuterium relative to the total number of hydrogen atoms and deuterium atoms may be, for example, greater than 0%, 1%. It may be 10% or more, 20% or more, 30% or more, 40% or more, or 50% or more, and may be 100% or less, 90% or less, 80% or less, 70% or less, and 60% or less.
본 발명의 다른 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 중수소를 포함하지 않을 수 있거나, 수소 원자와 중수소 원자의 총수에 대한 중수소의 함량은 1% 내지 100%일 수 있다.In another embodiment of the present invention, the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 1% to 100%.
본 발명의 다른 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 중수소를 포함하지 않을 수 있거나, 수소 원자와 중수소 원자의 총수에 대한 중수소의 함량은 20% 내지 90%일 수 있다.In another embodiment of the present invention, the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 20% to 90%.
본 발명의 다른 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 중수소를 포함하지 않을 수 있거나, 수소 원자와 중수소 원자의 총수에 대한 중수소의 함량은 30% 내지 80%일 수 있다.In another embodiment of the present invention, the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 30% to 80%.
본 발명의 다른 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 중수소를 포함하지 않을 수 있거나, 수소 원자와 중수소 원자의 총수에 대한 중수소의 함량은 40% 내지 70%일 수 있다.In another embodiment of the present invention, the compound represented by Formula 1 may not contain deuterium, or the content of deuterium relative to the total number of hydrogen and deuterium atoms may be 40% to 70%.
예를 들면, 상기 화학식 1로 표시되는 헤테로 고리 화합물 중 수소 원자와 중수소 원자의 총수를 기준으로 중수소의 함량이 0% 이상, 1% 이상, 5% 이상, 10% 이상, 15% 이상, 20% 이상, 25% 이상, 30% 이상, 35% 이상, 40% 이상, 45% 이상, 또는 50% 이상일 수 있고, 100% 이하, 95% 이하, 90% 이하, 85% 이하, 80% 이하, 75% 이하, 70% 이하, 65% 이하 또는 60% 이하일 수 있다.For example, based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1, the deuterium content is 0% or more, 1% or more, 5% or more, 10% or more, 15% or more, 20% or more. It can be more than 25%, more than 30%, more than 35%, more than 40%, more than 45%, or more than 50%, and less than 100%, less than 95%, less than 90%, less than 85%, less than 80%, 75 It may be % or less, 70% or less, 65% or less, or 60% or less.
본 발명의 일 실시형태에 있어서, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 하기 화합물들로 구성된 군으로부터 선택되는 어느 하나인 것일 수 있다:In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one selected from the group consisting of the following compounds:
Figure PCTKR2023005090-appb-img-000011
Figure PCTKR2023005090-appb-img-000011
Figure PCTKR2023005090-appb-img-000012
Figure PCTKR2023005090-appb-img-000012
Figure PCTKR2023005090-appb-img-000013
Figure PCTKR2023005090-appb-img-000013
Figure PCTKR2023005090-appb-img-000014
Figure PCTKR2023005090-appb-img-000014
Figure PCTKR2023005090-appb-img-000015
Figure PCTKR2023005090-appb-img-000015
Figure PCTKR2023005090-appb-img-000016
Figure PCTKR2023005090-appb-img-000016
Figure PCTKR2023005090-appb-img-000017
Figure PCTKR2023005090-appb-img-000017
Figure PCTKR2023005090-appb-img-000018
Figure PCTKR2023005090-appb-img-000018
Figure PCTKR2023005090-appb-img-000019
Figure PCTKR2023005090-appb-img-000019
Figure PCTKR2023005090-appb-img-000020
Figure PCTKR2023005090-appb-img-000020
Figure PCTKR2023005090-appb-img-000021
Figure PCTKR2023005090-appb-img-000021
Figure PCTKR2023005090-appb-img-000022
Figure PCTKR2023005090-appb-img-000022
Figure PCTKR2023005090-appb-img-000023
Figure PCTKR2023005090-appb-img-000023
Figure PCTKR2023005090-appb-img-000024
Figure PCTKR2023005090-appb-img-000024
Figure PCTKR2023005090-appb-img-000025
Figure PCTKR2023005090-appb-img-000025
Figure PCTKR2023005090-appb-img-000026
Figure PCTKR2023005090-appb-img-000026
Figure PCTKR2023005090-appb-img-000027
Figure PCTKR2023005090-appb-img-000027
Figure PCTKR2023005090-appb-img-000028
Figure PCTKR2023005090-appb-img-000028
Figure PCTKR2023005090-appb-img-000029
Figure PCTKR2023005090-appb-img-000029
Figure PCTKR2023005090-appb-img-000030
Figure PCTKR2023005090-appb-img-000030
Figure PCTKR2023005090-appb-img-000031
Figure PCTKR2023005090-appb-img-000031
Figure PCTKR2023005090-appb-img-000032
Figure PCTKR2023005090-appb-img-000032
Figure PCTKR2023005090-appb-img-000033
Figure PCTKR2023005090-appb-img-000033
Figure PCTKR2023005090-appb-img-000034
Figure PCTKR2023005090-appb-img-000034
Figure PCTKR2023005090-appb-img-000035
Figure PCTKR2023005090-appb-img-000035
Figure PCTKR2023005090-appb-img-000036
Figure PCTKR2023005090-appb-img-000036
Figure PCTKR2023005090-appb-img-000037
Figure PCTKR2023005090-appb-img-000037
Figure PCTKR2023005090-appb-img-000038
Figure PCTKR2023005090-appb-img-000038
Figure PCTKR2023005090-appb-img-000039
Figure PCTKR2023005090-appb-img-000039
Figure PCTKR2023005090-appb-img-000040
Figure PCTKR2023005090-appb-img-000040
또한, 상기 화학식 1의 구조에 다양한 치환기를 도입함으로써 도입된 치환기의 고유 특성을 갖는 화합물을 합성할 수 있다. 예컨대, 유기 발광 소자 제조시 사용되는 정공 주입층 물질, 정공 수송층 물질, 정공 수송 보조층 물질, 전자 저지층 물질, 발광층 물질, 전자 수송층 물질, 정공 저지층 물질 및 전자 주입층 물질에 주로 사용되는 치환기를 상기 코어 구조에 도입함으로써 각 유기물층에서 요구하는 조건들을 충족시키는 물질을 합성할 수 있다.Additionally, by introducing various substituents into the structure of Formula 1, a compound having the unique properties of the introduced substituent can be synthesized. For example, substituents mainly used in the hole injection layer material, hole transport layer material, hole transport auxiliary layer material, electron blocking layer material, light emitting layer material, electron transport layer material, hole blocking layer material, and electron injection layer material used in manufacturing organic light emitting devices. By introducing into the core structure, a material that satisfies the conditions required for each organic layer can be synthesized.
또한, 상기 화학식 1의 구조에 다양한 치환기를 도입함으로써 에너지 밴드갭을 미세하게 조절이 가능하게 하며, 한편으로 유기물 사이에서의 계면에서의 특성을 향상되게 하며 물질의 용도를 다양하게 할 수 있다.In addition, by introducing various substituents into the structure of Formula 1, the energy band gap can be finely adjusted, while the properties at the interface between organic materials can be improved and the uses of the material can be diversified.
본 발명의 다른 실시형태는, 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함하는 유기 발광 소자를 제공한다. 상기 "유기 발광 소자"는 "유기발광다이오드”, "OLED(Organic Light Emitting Diodes)", "OLED 소자", "유기 전계 발광 소자" 등의 용어로 표현될 수 있다.Another embodiment of the present invention provides an organic light-emitting device including the heterocyclic compound represented by Formula 1 above. The “organic light emitting device” may be expressed by terms such as “organic light emitting diode”, “OLED (Organic Light Emitting Diodes)”, “OLED device”, “organic electroluminescent device”, etc.
또한, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층;을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers includes a heterocyclic compound represented by Formula 1. do.
본 발명의 일 실시형태에 있어서, 상기 제1 전극은 양극일 수 있고, 상기 제2 전극은 음극일 수 있다. In one embodiment of the present invention, the first electrode may be an anode, and the second electrode may be a cathode.
본 발명의 다른 일 실시형태에 있어서, 상기 제1 전극은 음극일 수 있고, 상기 제2 전극은 양극일 수 있다.In another embodiment of the present invention, the first electrode may be a cathode, and the second electrode may be an anode.
본 발명의 일 실시형태에 있어서, 상기 유기 발광 소자는 적색 유기 발광 소자일 수 있으며, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 적색 유기 발광 소자의 재료로 사용될 수 있다.In one embodiment of the present invention, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the red organic light-emitting device.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 녹색 유기 발광 소자일 수 있으며, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 녹색 유기 발광 소자의 재료로 사용될 수 있다.In another embodiment of the present invention, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the green organic light-emitting device.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 청색 유기 발광 소자일 수 있으며, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 청색 유기 발광 소자의 재료로 사용될 수 있다.In another embodiment of the present invention, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the blue organic light-emitting device.
본 발명의 일 실시형태에 있어서, 상기 유기 발광 소자는 적색 유기 발광 소자일 수 있으며, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 적색 유기 발광 소자의 발광층 재료로 사용될 수 있다.In one embodiment of the present invention, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the red organic light-emitting device.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 녹색 유기 발광 소자일 수 있으며, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 녹색 유기 발광 소자의 발광층 재료로 사용될 수 있다.In another embodiment of the present invention, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the green organic light-emitting device.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 청색 유기 발광 소자일 수 있으며, 상기 화학식 1로 표시되는 헤테로 고리 화합물은 청색 유기 발광 소자의 발광층 재료로 사용될 수 있다.In another embodiment of the present invention, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the blue organic light-emitting device.
상기 화학식 1로 표시되는 헤테로 고리 화합물에 대한 구체적인 내용은 전술한 바와 동일하다.Specific details about the heterocyclic compound represented by Formula 1 are the same as described above.
본 발명의 유기 발광 소자는 전술한 헤테로 고리 화합물을 이용하여 1 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 can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the heterocyclic compound described above.
상기 헤테로 고리 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층을 형성할 수 있다. 여기서, 용액 도포법은 스핀 코팅, 딥 코팅, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.The heterocyclic compound can form an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution application method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
본 발명의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수도 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물층으로 정공주입층, 정공수송층, 정공수송보조층, 발광층, 전자주입층, 전자수송층, 전지저지층, 정공저지층 등을 포함하는 구조를 가질 수 있다. 그러나, 상기 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 also have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, an electron injection layer, an electron transport layer, a battery blocking layer, a hole blocking layer, etc. as organic material layers. However, the structure of the organic light emitting device is not limited to this and may include a smaller number of organic material layers.
본 발명의 유기 발광 소자에서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다. 상기 헤테로 고리 화합물이 발광층에 사용될 경우, 호모(HOMO, Highest Occupied Molecular Orbital) 및 루모(LUMO, Lowest Unoccupied Molecular Orbital)를 공간적으로 분리하여 강한 전하이동(charge transfer)이 가능하기 때문에 유기 발광 소자의 구동 효율 및 수명이 우수해질 수 있다.In the organic light-emitting device of the present invention, the organic material layer includes a light-emitting layer, and the light-emitting layer may include a heterocyclic compound represented by Formula 1 above. When the heterocyclic compound is used in the light-emitting layer, strong charge transfer is possible by spatially separating HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital), thereby driving the organic light-emitting device. Efficiency and lifespan can be improved.
본 발명의 일 실시형태에 있어서, 상기 유기 발광 소자는 1층 이상의 유기물층을 포함할 수 있고, 상기 유기물층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In one embodiment of the present invention, the organic light-emitting device may include one or more organic material layers, the organic material layer may include a light-emitting layer, and the light-emitting layer may include a heterocyclic compound represented by Formula 1. there is.
본 발명의 다른 실시형태에 있어서, 상기 유기물층은 발광층을 포함할 수 있고, 상기 발광층은 호스트 물질을 포함할 수 있으며, 상기 호스트 물질은 상기 헤테로 고리 화합물을 포함할 수 있다.In another embodiment of the present invention, the organic layer may include a light-emitting layer, the light-emitting layer may include a host material, and the host material may include the heterocyclic compound.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 발광층, 정공주입층, 정공수송층, 전자주입층, 전자수송층, 전지저지층 및 정공저지층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함할 수 있다.In another embodiment of the present invention, the organic light emitting device has one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. More may be included.
본 발명의 일 실시형태에 있어서, 상기 유기 발광 소자는 1층 이상의 유기물층을 포함할 수 있고, 상기 유기물층은 정공수송층을 포함할 수 있고, 상기 정공수송층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In one embodiment of the present invention, the organic light-emitting device may include one or more organic material layers, the organic material layer may include a hole transport layer, and the hole transport layer includes a heterocyclic compound represented by Formula 1. can do.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 발광층, 정공주입층, 정공수송보조층, 전자주입층, 전자수송층, 전지저지층 및 정공저지층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함할 수 있다.In another embodiment of the present invention, the organic light emitting device has one or two layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. It may include more than the above.
본 발명의 일 실시형태에 있어서, 상기 유기 발광 소자는 1층 이상의 유기물층을 포함할 수 있고, 상기 유기물층은 정공수송보조층을 포함할 수 있고, 상기 정공수송보조층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In one embodiment of the present invention, the organic light-emitting device may include one or more organic material layers, the organic material layer may include a hole transport auxiliary layer, and the hole transport auxiliary layer is a heterogeneous material represented by Formula 1. It may contain a ring compound.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 발광층, 정공주입층, 정공수송층, 전자주입층, 전자수송층, 전지저지층 및 정공저지층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함할 수 있다.In another embodiment of the present invention, the organic light emitting device has one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. More may be included.
본 발명의 일 실시형태에 있어서, 상기 유기 발광 소자는 1층 이상의 유기물층을 포함할 수 있고, 상기 유기물층은 전자저지층을 포함할 수 있고, 상기 전자저지층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In one embodiment of the present invention, the organic light-emitting device may include one or more organic material layers, the organic material layer may include an electron blocking layer, and the electron blocking layer is a heterocyclic compound represented by Formula 1. may include.
본 발명의 다른 실시형태에 있어서, 상기 유기 발광 소자는 발광층, 정공주입층, 정공수송층, 정공수송보조층, 전자주입층, 전자수송층 및 정공저지층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함할 수 있다.In another embodiment of the present invention, the organic light emitting device has one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, and a hole blocking layer. It may further include.
본 발명의 일 실시형태에 있어서, 상기 유기물층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함하고, 인광 도펀트와 함께 사용할 수 있다.In one embodiment of the present invention, the organic material layer includes a heterocyclic compound represented by Formula 1, and can be used together with a phosphorescent dopant.
상기 인광 도펀트 재료로는 당 기술분야에 알려져 있는 것들을 사용할 수 있다. 예컨대, LL'MX', LL'L"M, LMX'X", L2MX' 및 L3M로 표시되는 인광 도펀트 재료를 사용할 수 있으나, 이들 예에 의하여 본 발명의 범위가 한정되는 것은 아니다.As the phosphorescent dopant material, those known in the art can be used. For example, phosphorescent dopant materials represented by LL'MX', LL'L"M, LMX'X", L 2 MX' and L 3 M can be used, but the scope of the present invention is not limited by these examples. .
상기 M은 이리듐, 백금, 오스뮴 등이 될 수 있다.The M may be iridium, platinum, osmium, etc.
상기 L은 sp2 탄소 및 헤테로 원자에 의하여 상기 M에 배위되는 음이온성 2좌 배위자이고, X는 전자 또는 정공을 트랩하는 기능을 수행할 수 있다. L, L' 및 L"의 비한정적인 예로는 2-(1-나프틸)벤조옥사졸, 2-페닐벤조옥사졸, 2-페닐벤조티아졸, 7,8-벤조퀴놀린, 페닐피리딘, 벤조티오페닐피리딘, 3-메톡시-2-페닐피리딘, 티오페닐피리딘, 톨릴피리딘 등이 있다. X' 및 X"의 비한정적인 예로는 아세틸아세토네이트(acac), 헥사플루오로아세틸아세토네이트, 살리실리덴, 피콜리네이트, 8-히드록시퀴놀리네이트 등이 있다.L is an anionic bidentate ligand coordinated to M by an sp 2 carbon and a hetero atom, and X may function to trap electrons or holes. Non-limiting examples of L, L' and L" include 2-(1-naphthyl)benzoxazole, 2-phenylbenzoxazole, 2-phenylbenzothiazole, 7,8-benzoquinoline, phenylpyridine, benzothiazole Thiophenylpyridine, 3-methoxy-2-phenylpyridine, thiophenylpyridine, tolylpyridine, etc. Non-limiting examples of X' and These include silidene, picolinate, and 8-hydroxyquinolinate.
상기 인광 도펀트의 구체적인 예를 하기에 표시하나, 이들 예로만 한정되는 것은 아니다:Specific examples of the phosphorescent dopant are shown below, but are not limited to these examples:
Figure PCTKR2023005090-appb-img-000041
Figure PCTKR2023005090-appb-img-000041
본 발명의 일 실시형태에 있어서, 상기 유기물층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함하고, 이리듐계 도펀트와 함께 사용할 수 있다.In one embodiment of the present invention, the organic material layer includes a heterocyclic compound represented by Formula 1, and can be used together with an iridium-based dopant.
본 발명의 일 실시형태에 있어서, 상기 이리듐계 도펀트로는 녹색 인광 도펀트 또는 적색 인광 도펀트는 Ir(ppy)3가 사용될 수 있다.In one embodiment of the present invention, a green phosphorescent dopant or a red phosphorescent dopant may be Ir(ppy) 3 as the iridium-based dopant.
본 발명의 일 실시형태에 있어서, 상기 도펀트의 함량은 발광층 전체 중량을 기준으로 1% 내지 15%, 바람직하게는 2% 내지 10%, 보다 바람직하게는 3% 내지 7%의 함량을 가질 수 있다.In one embodiment of the present invention, the content of the dopant may be 1% to 15%, preferably 2% to 10%, more preferably 3% to 7%, based on the total weight of the light emitting layer. .
본 발명의 일 실시형태에 따른 유기 발광 소자에서, 상기 유기물층은 정공 수송층 또는 정공 수송 보조층을 포함하고, 상기 정공 수송층 또는 정공 수송 보조층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In the organic light emitting device according to an embodiment of the present invention, the organic material layer includes a hole transport layer or a hole transport auxiliary layer, and the hole transport layer or the hole transport auxiliary layer may include a heterocyclic compound represented by Formula 1 above. .
본 발명의 다른 실시형태에 따른 유기 발광 소자에서, 상기 유기물층은 전자 주입층 또는 전자 수송층을 포함하고, 상기 전자 주입층 또는 전자 수송층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light emitting device according to another embodiment of the present invention, the organic material layer includes an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer may include a heterocyclic compound represented by Formula 1 above.
본 발명의 다른 실시형태에 따른 유기 발광 소자에서, 상기 유기물층은 전자 저지층 또는 정공 저지층을 포함하고, 상기 전자 저지층 또는 정공 저지층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light emitting device according to another embodiment of the present invention, the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include a heterocyclic compound represented by Formula 1 above. .
본 발명의 다른 실시형태에 따른 유기 발광 소자에서, 상기 유기물층은 전자 수송층, 발광층 또는 정공 저지층을 포함하고, 상기 전자 수송층, 발광층 또는 정공 저지층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light-emitting device according to another embodiment of the present invention, the organic material layer includes an electron transport layer, a light-emitting layer, or a hole blocking layer, and the electron transport layer, the light-emitting layer, or the hole blocking layer may include a heterocyclic compound represented by Formula 1. You can.
본 발명의 다른 실시형태에 따른 유기 발광 소자에서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light-emitting device according to another embodiment of the present invention, the organic material layer includes a light-emitting layer, and the light-emitting layer may include a heterocyclic compound represented by Formula 1 above.
본 발명의 다른 실시형태에 따른 유기 발광 소자에서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 호스트 물질을 포함하며, 상기 호스트 물질은 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light-emitting device according to another embodiment of the present invention, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host material, and the host material may include a heterocyclic compound represented by Formula 1.
또 다른 실시형태에 따른 유기 발광 소자에서, 상기 발광층은 2개 이상의 호스트 물질을 포함할 수 있으며, 상기 호스트 물질 중 적어도 1개는 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light emitting device according to another embodiment, the light emitting layer may include two or more host materials, and at least one of the host materials may include a heterocyclic compound represented by Formula 1 above.
또 다른 실시형태에 따른 유기 발광 소자에서, 상기 발광층은 2개 이상의 호스트 물질을 예비 혼합(pre-mixed)하여 사용할 수 있으며, 상기 2개 이상의 호스트 물질 중 적어도 1개는 상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함할 수 있다.In an organic light-emitting device according to another embodiment, the light-emitting layer may be used by pre-mixing two or more host materials, and at least one of the two or more host materials is a heterogeneous compound represented by Formula 1. It may contain a ring compound.
상기 예비 혼합(pre-mixed)은 상기 발광층은 2개 이상의 호스트 물질을 유기물층에 증착하기 전에 먼저 재료를 섞어서 하나의 공원에 담아 혼합하는 것을 의미한다.The pre-mixed means that the light emitting layer first mixes two or more host materials into one container before depositing them on the organic layer.
본 발명의 일 실시형태에 따른 유기 발광 소자는 발광층, 정공 주입층, 정공 수송층, 전자 주입층, 전자 저지층 및 정공 저지층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함할 수 있다.The organic light emitting device according to an embodiment of the present invention may further include one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer. .
도 1 내지 도 3에 본 발명의 일 실시형태에 따른 유기 발광 소자의 전극과 유기물층의 적층 순서를 예시하였다. 그러나, 이들 도면에 의하여 본 출원의 범위가 한정될 것을 의도한 것은 아니며, 당 기술분야에 알려져 있는 유기 발광 소자의 구조가 본 출원에도 적용될 수 있다.1 to 3 illustrate the stacking order of electrodes and organic material layers of an organic light-emitting device according to an embodiment of the present invention. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light-emitting devices known in the art may also be applied to the present application.
도 1에 따르면, 기판(100) 상에 양극(200), 유기물층(300) 및 음극(400)이 순차적으로 적층된 유기 발광 소자가 도시된다. 그러나, 이와 같은 구조에만 한정되는 것은 아니고, 도 2와 같이, 기판 상에 음극, 유기물층 및 양극이 순차적으로 적층된 유기 발광 소자가 구현될 수도 있다.According to Figure 1, an organic light emitting device is shown in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100. However, it is not limited to this structure, and an organic light-emitting device may be implemented in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate, as shown in FIG. 2.
도 3은 유기물층이 다층인 경우를 예시한 것이다. 도 3에 따른 유기 발광 소자는 정공 주입층(301), 정공 수송층(302), 발광층(303), 정공 저지층(304), 전자 수송층(305) 및 전자 주입층(306)을 포함한다. 그러나, 이와 같은 적층 구조에 의하여 본 출원의 범위가 한정되는 것은 아니며, 필요에 따라 발광층을 제외한 나머지 층은 생략될 수도 있고, 필요한 다른 기능층이 더 추가될 수 있다.Figure 3 illustrates the case where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by this laminated structure, and if necessary, the remaining layers except the light-emitting layer may be omitted, and other necessary functional layers may be added.
본 발명의 일 실시형태에 있어서, 기판을 준비하는 단계; 상기 기판 상에 제1 전극을 형성하는 단계; 상기 제1 전극 상에 1층 이상의 유기물층을 형성하는 단계; 및 상기 유기물층 상에 제2 전극을 형성하는 단계를 포함하는 유기 발광 소자의 제조 방법으로서, 상기 유기물층을 형성하는 단계가 본 발명의 일 실시형태에 따른 헤테로 고리 화합물을 이용하여 1층 이상의 유기물층을 형성하는 단계를 포함하는 것인 유기 발광 소자의 제조 방법을 제공한다.In one embodiment of the present invention, preparing a substrate; forming a first electrode on the substrate; Forming one or more organic layers on the first electrode; and forming a second electrode on the organic layer, wherein the step of forming the organic layer includes forming one or more organic layers using a heterocyclic compound according to an embodiment of the present invention. It provides a method for manufacturing an organic light-emitting device comprising the step of:
본 발명의 일 실시형태에 있어서, 상기 유기물층을 형성하는 단계는 상기 화학식 1로 표시되는 헤테로 고리 화합물을 예비 혼합(pre-mixed)하고, 열 진공 증착 방법을 이용하여 형성하는 것일 수 있다.In one embodiment of the present invention, the step of forming the organic layer may include pre-mixing the heterocyclic compound represented by Formula 1 and forming it using a thermal vacuum deposition method.
상기 예비 혼합(pre-mixed)은, 상기 화학식 1로 표시되는 헤테로 고리 화합물을 유기물층에 증착하기 전 먼저 재료를 섞어서 하나의 공급원에 담아 혼합하는 것을 의미한다.The pre-mixed means mixing the materials in one source before depositing the heterocyclic compound represented by Formula 1 on the organic layer.
예비 혼합된 재료는 본 출원의 일 실시상태에 따른 헤테로 고리 화합물로 언급될 수 있다.The premixed material may be referred to as a heterocyclic compound according to an exemplary embodiment of the present application.
상기 화학식 1로 표시되는 헤테로 고리 화합물을 포함하는 유기물층은, 필요에 따라 다른 물질을 추가로 포함할 수 있다.The organic material layer containing the heterocyclic compound represented by Formula 1 may further include other materials as needed.
본 발명의 일 실시형태에 따른 유기 발광 소자에 있어서, 상기 화학식 1로 표시되는 헤테로 고리 화합물 이외의 재료를 하기에 예시하지만, 이들은 예시를 위한 것일 뿐 본 출원의 범위를 한정하기 위한 것은 아니며, 당 기술분야에 공지된 재료들로 대체될 수 있다.In the organic light emitting device according to an embodiment of the present invention, materials other than the heterocyclic compound represented by Formula 1 are illustrated below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. It can be replaced by materials known in the art.
양극 재료로는 비교적 일함수가 큰 재료들을 이용할 수 있으며, 투명 전도성 산화물, 금속 또는 전도성 고분자 등을 사용할 수 있다. 상기 양극 재료의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO : Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.As the anode material, materials with a relatively large work function can be used, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combination of metal and oxide such as ZnO:Al or SnO2:Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.
음극 재료로는 비교적 일함수가 낮은 재료들을 이용할 수 있으며, 금속, 금속 산화물 또는 전도성 고분자 등을 사용할 수 있다. 상기 음극 재료의 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.As the cathode material, materials with a relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO 2 /Al.
정공 주입층 재료로는 공지된 정공 주입층 재료를 이용할 수도 있는데, 예를들면, 미국 특허 제4,356,429호에 개시된 구리프탈로시아닌 등의 프탈로시아닌 화합물 또는 문헌 [Advanced Material, 6, p.677 (1994)]에 기재되어 있는 스타버스트형 아민 유도체류, 예컨대 트리스(4-카바조일-9-일페닐)아민(TCTA), 4,4',4"-트리[페닐(m-톨릴)아미노]트리페닐아민(m-MTDATA), 1,3,5-트리스[4-(3-메틸페닐페닐아미노)페닐]벤젠(m-MTDAPB), 용해성이 있는 전도성 고분자인 폴리아닐린/도데실벤젠술폰산(Polyaniline/Dodecylbenzenesulfonic acid) 또는 폴리(3,4-에틸렌디옥시티오펜)/폴리(4-스티렌술포네이트)(Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), 폴리아닐린/캠퍼술폰산(Polyaniline/Camphor sulfonic acid) 또는 폴리아닐린/폴리(4-스티렌술포네이트)(Polyaniline/Poly(4-styrenesulfonate)) 등을 사용할 수 있다.As the hole injection layer material, known hole injection layer materials may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or those described in Advanced Material, 6, p.677 (1994). Described starburst-type amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine ( m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate), Polyaniline/Camphor sulfonic acid, or Polyaniline/Poly(4-styrenesulfonate), etc. can be used.
정공 수송층 재료로는 피라졸린 유도체, 아릴아민계 유도체, 스틸벤 유도체, 트리페닐디아민 유도체 등이 사용될 수 있으며, 저분자 또는 고분자 재료가 사용될 수도 있다.As the hole transport layer material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular or high molecular materials may also be used.
전자 수송층 재료로는 옥사디아졸 유도체, 안트라퀴노디메탄 및 이의 유도체, 벤조퀴논 및 이의 유도체, 나프토퀴논 및 이의 유도체, 안트라퀴논 및 이의 유도체, 테트라시아노안트라퀴노디메탄 및 이의 유도체, 플루오레논 유도체, 디페닐디시아노에틸렌 및 이의 유도체, 디페노퀴논 유도체, 8-히드록시퀴놀린 및 이의 유도체의 금속 착체 등이 사용될 수 있으며, 저분자 물질뿐만 아니라 고분자 물질이 사용될 수도 있다.Electron transport layer materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and not only low molecular substances but also high molecular substances may be used.
전자 주입층 재료로는 예를 들어, LiF가 당업계 대표적으로 사용되나, 본 출원이 이에 한정되는 것은 아니다.For example, LiF is typically used as an electron injection layer material in the industry, but the present application is not limited thereto.
발광층 재료로는 적색, 녹색 또는 청색 발광재료가 사용될 수 있으며, 필요한 경우, 2 이상의 발광 재료를 혼합하여 사용할 수 있다. 이 때, 2 이상의 발광 재료를 개별적인 공급원으로 증착하여 사용하거나, 예비혼합하여 하나의 공급원으로 증착하여 사용할 수 있다. 또한, 발광층 재료로서 형광 재료를 사용할 수도 있으나, 인광 재료로서 사용할 수도 있다. 발광층 재료로는 단독으로서 양극과 음극으로부터 각각 주입된 정공과 전자를 결합하여 발광시키는 재료가 사용될 수도 있으나, 호스트 재료와 도펀트 재료가 함께 발광에 관여하는 재료들이 사용될 수도 있다.Red, green, or blue light-emitting materials can be used as the light-emitting layer material, and if necessary, two or more light-emitting materials can be mixed. At this time, two or more light emitting materials can be deposited and used from individual sources, or they can be premixed and deposited from a single source. Additionally, a fluorescent material may be used as the light-emitting layer material, but it may also be used as a phosphorescent material. The light emitting layer material may be a material that emits light by combining holes and electrons injected from the anode and the cathode respectively, but may also be used as a host material and a dopant material that participates in light emission together.
발광층 재료의 호스트를 혼합하여 사용하는 경우에는, 동일 계열의 호스트를 혼합하여 사용할 수도 있고, 다른 계열의 호스트를 혼합하여 사용할 수도 있다. 예를 들어, n 타입 호스트 재료 또는 p 타입 호스트 재료 중 어느 두 종류 이상의 재료를 선택하여 발광층의 호스트 재료로 사용할 수 있다.When using a mixture of hosts of the light emitting layer material, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, any two or more types of materials, such as an n-type host material or a p-type host material, can be selected and used as the host material of the light-emitting layer.
본 발명의 일 실시형태에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to an embodiment of the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.
본 발명의 일 실시형태에 따른 헤테로 고리 화합물은 유기 태양 전지, 유기 감광체, 유기 트랜지스터 등을 비롯한 유기 전자 소자에서도 유기 발광 소자에 적용되는 것과 유사한 원리로 작용할 수 있다.The heterocyclic compound according to an embodiment of the present invention may function in organic electronic devices, including organic solar cells, organic photoreceptors, organic transistors, etc., on a principle similar to that applied to organic light-emitting devices.
이하, 본 발명의 이해를 돕기 위해 바람직한 실시예를 제시하지만, 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 이에 한정되는 것은 아니다.Hereinafter, preferred examples are presented to aid understanding of the present invention, but the following examples are provided to facilitate understanding of the present invention and do not limit the present invention thereto.
<제조예><Manufacturing example>
제조예 1: 화합물 001의 제조Preparation Example 1: Preparation of Compound 001
Figure PCTKR2023005090-appb-img-000042
Figure PCTKR2023005090-appb-img-000042
1) 화합물 001-P5의 제조1) Preparation of compound 001-P5
1-브로모나프탈렌-2-올(1-bromonaphthalen-2-ol) (50g, 224.14mmol)과 (5-클로로-2-플루오로페닐)보론산((5-chloro-2-fluorophenyl)boronic acid) (42.99g, 246.56mmol)을 1,4-디옥세인(1,4-Dioxane) (500ml) 및 증류수 (100ml)에 넣고 녹인 후, 테트라키스(트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine)palladium, Pd(PPh3)4) (12.95g, 11.21mmol)과 탄산칼륨 (potassium carbonate, K2CO3) (77.45g, 560.36mmol)을 넣고, 12시간 동안 환류 교반하였다. 반응 완료 후 반응액을 디클로로메탄 (dichloromethane, DCM)과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후, 디클로로메탄과 헥산(hexane)을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 001-P5를 45g 얻었다(수율 74%).1-bromonaphthalen-2-ol (50g, 224.14mmol) and (5-chloro-2-fluorophenyl)boronic acid ) (42.99g, 246.56mmol) was dissolved in 1,4-Dioxane (500ml) and distilled water (100ml), then tetrakis(triphenylphosphine)palladium , Pd(PPh 3 ) 4 ) (12.95g, 11.21mmol) and potassium carbonate (K 2 CO 3 ) (77.45g, 560.36mmol) were added, and the mixture was refluxed and stirred for 12 hours. After completion of the reaction, the reaction solution was extracted with dichloromethane (DCM) and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and dichloromethane and hexane were used as developing solvents. Purified by column chromatography, 45 g of compound 001-P5 was obtained (yield 74%).
2) 화합물 001-P4의 제조2) Preparation of compound 001-P4
화합물 001-P5 (45g, 165.02mmol)와 N-브로모숙신이미드(N-bromosuccinimide) (32.31g, 181.52mmol)를 디메틸포름아마이드(dimethylformamide) (1000ml)에 넣고, 12시간 동안 상온에서 교반하였다. 반응 완료 후 반응액에 증류수 1000ml를 넣고 30분 교반시킨 후 생성된 고체를 여과하여 화합물 001-P4를 53g 얻었다(수율 91%).Compound 001-P5 (45g, 165.02mmol) and N-bromosuccinimide (32.31g, 181.52mmol) were added to dimethylformamide (1000ml) and stirred at room temperature for 12 hours. . After completion of the reaction, 1000 ml of distilled water was added to the reaction solution, stirred for 30 minutes, and the resulting solid was filtered to obtain 53 g of compound 001-P4 (yield 91%).
3) 화합물 001-P3의 제조3) Preparation of compound 001-P3
화합물 001-P4 (53g, 150.74mmol)를 N,N-디메틸아세트아마이드(N,N-Dimethylacetamide) (600ml)에 넣고 용해시킨 후, 150℃로 가열한 후 탄산세슘 (cesium carbonate, Cs2CO3) (147.34g, 452.22mmol)을 넣고 30분 동안 환류 교반하였다. 반응 완료 후 디클로로메탄과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼크로마토그래피로 정제하여 화합물 001-P3을 42g 얻었다(수율 84%).Compound 001-P4 (53g, 150.74mmol) was dissolved in N,N-Dimethylacetamide (600ml), heated to 150°C, and dissolved in cesium carbonate (Cs 2 CO 3) . ) (147.34g, 452.22mmol) was added and stirred under reflux for 30 minutes. After completion of the reaction, extraction was performed with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as developing solvents to obtain 42 g of compound 001-P3. obtained (yield 84%).
4) 화합물 001-P2의 제조4) Preparation of Compound 001-P2
화합물 001-P3 (42g, 126.66mmol) 및 (2-메톡시카보닐)페닐)보론산 ((2-(methoxycarbonyl)phenyl)boronic acid) (25.07g, 139.33mmol)을 1,4-디옥세인(1,4-Dioxane) (500ml) 및 증류수 100ml에 넣고 녹인 후, 테트라키스(트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine)palladium, Pd(PPh3)4) (7.32g, 6.33mmol)과 탄산칼륨 (potassium carbonate, K2CO3) (43.77g, 316.66mmol)을 넣고 12시간 동안 환류 교반하였다. 반응 완료 후 반응액을 디클로로메탄 (dichloromethane, DCM)과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 001-P2를 40g 얻었다(수율 82%).Compound 001-P3 (42g, 126.66mmol) and (2-(methoxycarbonyl)phenyl)boronic acid) (25.07g, 139.33mmol) were mixed with 1,4-dioxane ( After dissolving in 1,4-Dioxane (500ml) and distilled water (100ml), tetrakis(triphenylphosphine)palladium, Pd(PPh 3 ) 4 ) (7.32g, 6.33mmol) and potassium carbonate (K 2 CO 3 ) (43.77g, 316.66mmol) was added and stirred under reflux for 12 hours. After completion of the reaction, the reaction solution was extracted with dichloromethane (DCM) and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then subjected to column chromatography using dichloromethane and hexane as developing solvents. By purification, 40g of compound 001-P2 was obtained (yield 82%).
5) 화합물 001-P1의 제조5) Preparation of Compound 001-P1
화합물 001-P2 (40g, 103.40mmol)을 테트라하이드로퓨란(tetrahydrofuran) (400ml)에 넣고 녹인 후, 0℃에서 메틸마그네슘 브로마이드 (methylmagnesium bromide) (3M solution in ether, 103ml, 310.21mmol)를 천천히 첨가한 후 60℃에서 6시간 동안 교반하였다. 반응 종료 후 반응액에 물을 첨가하여 종결시킨 후 디클로로메탄과 증류수를 이용하여 추출하고, 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거하였고, 그 후 디클로로메탄에 녹인 후 반응물에 보론 트리플루오라이드 디에틸 이더레이트 (boron trifluoride diethyl ehterate)를 추가 후 상온에서 4시간 동안 교반하였다. 반응 종료 후 디클로로메탄과 헥산을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 001-P1을 27g 얻었다(수율 70%).Compound 001-P2 (40g, 103.40mmol) was dissolved in tetrahydrofuran (400ml), and then methylmagnesium bromide (3M solution in ether, 103ml, 310.21mmol) was slowly added at 0°C. Afterwards, it was stirred at 60°C for 6 hours. After the reaction was terminated by adding water to the reaction solution, extraction was performed using dichloromethane and distilled water. The organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then the solution was dissolved in dichloromethane. After adding boron trifluoride diethyl etherate to the reaction, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, dichloromethane and hexane were purified by column chromatography using a developing solvent to obtain 27 g of compound 001-P1 (yield 70%).
6) 화합물 001의 제조6) Preparation of Compound 001
화합물 001-P1 (10g, 27.11mmol)과 N-페닐-[1,1’-비페닐]-4-아민(N-phenyl-[1,1'-biphenyl]-4-amine) (6.98g, 28.47mmol)을 톨루엔(Toluene) (100ml)에 넣고 녹인 후, 트리스(디벤질리덴아세톤)디팔라듐 (tris(dibenzylideneacetone)dipalladium, Pd2(dba)3) (1.24g, 1.36mmol), 디사이클로헥실(2',4',6'-트리아이소프로필-[1,1'-바이페닐]-2-일)포스핀(Dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine, Xphos) (1.29g, 2.71mmol) 및 소듐 터트-부톡사이드 (sodium tert-butoxide, t-BuONa) (5.21g, 54.22mmol)을 넣고 2시간 동안 환류 교반하였다. 반응 완료 후 반응액을 디클로로메탄과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼크로마토그래피로 정제하여 화합물 001을 13g 얻었다(수율 83%).Compound 001-P1 (10g, 27.11mmol) and N-phenyl-[1,1'-biphenyl]-4-amine (6.98g, After dissolving 28.47mmol) in toluene (100ml), tris(dibenzylideneacetone)dipalladium, Pd 2 (dba) 3 ) (1.24g, 1.36mmol), dicyclohexyl (2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Dicyclohexyl(2',4', 6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine, Xphos) (1.29g, 2.71mmol) and sodium tert-butoxide (t-BuONa) (5.21g, 54.22mmol) was added and stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was extracted with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and the solvent was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain compound 001. 13g was obtained (yield 83%).
상기 제조예 1에서, (5-클로로-2-플루오로페닐)보론산((5-chloro-2-fluorophenyl)boronic acid) 대신, 하기 표 1의 화합물 A를 사용하고, (2-메톡시카보닐)페닐)보론산 ((2-(methoxycarbonyl)phenyl)boronic acid) 대신, 하기 표 1의 화합물 B를 사용하고, N-페닐-[1,1’-비페닐]-4-아민(N-phenyl-[1,1'-biphenyl]-4-amine) 대신, 하기 표 1의 화합물 C를 사용한 것을 제외하고, 상기 제조예와 동일한 방법으로 목적화합물을 합성하였다.In Preparation Example 1, instead of (5-chloro-2-fluorophenyl)boronic acid ((5-chloro-2-fluorophenyl)boronic acid), Compound A of Table 1 below was used, and (2-methoxycarbo Instead of (2-(methoxycarbonyl)phenyl)boronic acid), Compound B of Table 1 below was used, and N-phenyl-[1,1'-biphenyl]-4-amine (N- The target compound was synthesized in the same manner as in the above preparation example, except that compound C of Table 1 below was used instead of phenyl-[1,1'-biphenyl]-4-amine).
[표 1][Table 1]
Figure PCTKR2023005090-appb-img-000043
Figure PCTKR2023005090-appb-img-000043
Figure PCTKR2023005090-appb-img-000044
Figure PCTKR2023005090-appb-img-000044
Figure PCTKR2023005090-appb-img-000045
Figure PCTKR2023005090-appb-img-000045
제조예 2: 화합물 141의 제조Preparation Example 2: Preparation of Compound 141
Figure PCTKR2023005090-appb-img-000046
Figure PCTKR2023005090-appb-img-000046
1) 화합물 141-P5의 제조1) Preparation of compound 141-P5
1-브로모나프탈렌-2-올(1-bromonaphthalen-2-ol) (50g, 224.14mmol)과 (5-클로로-2-플루오로페닐)보론산((5-chloro-2-fluorophenyl)boronic acid) (42.99g, 246.56mmol)을 1,4-디옥세인(1,4-Dioxane) (500ml) 및 증류수 (100ml)에 넣고 녹인 후, 테트라키스(트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine)palladium, Pd(PPh3)4) (12.95g, 11.21mmol)과 탄산칼륨 (potassium carbonate, K2CO3) (77.45g, 560.36mmol)을 넣고, 12시간 동안 환류 교반하였다. 반응 완료 후 반응액을 디클로로메탄 (dichloromethane, DCM)과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후, 디클로로메탄과 헥산을 전개용매로 컬럼크로마토그래피로 정제하여 화합물 141-P5를 45g 얻었다(수율 74%).1-bromonaphthalen-2-ol (50g, 224.14mmol) and (5-chloro-2-fluorophenyl)boronic acid ) (42.99g, 246.56mmol) was dissolved in 1,4-Dioxane (500ml) and distilled water (100ml), then tetrakis(triphenylphosphine)palladium , Pd(PPh 3 ) 4 ) (12.95 g, 11.21 mmol) and potassium carbonate (K 2 CO 3 ) (77.45 g, 560.36 mmol) were added, and refluxed and stirred for 12 hours. After completion of the reaction, the reaction solution was extracted with dichloromethane (DCM) and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then subjected to column chromatography using dichloromethane and hexane as developing solvents. After purification, 45 g of compound 141-P5 was obtained (yield 74%).
2) 화합물 141-P4의 제조2) Preparation of compound 141-P4
화합물 141-P5 (45g, 165.02mmol)와 N-브로모숙신이미드(N-bromosuccinimide) (32.31g, 181.52mmol)를 디메틸포름아마이드(dimethylformamide) (1000ml)에 넣고 12시간 동안 상온 교반하였다. 반응 완료 후 반응액에 증류수 1000ml를 넣고 30분 교반시킨 후 생성된 고체를 여과하여 화합물 141-P4를 53g 얻었다(수율 91%).Compound 141-P5 (45g, 165.02mmol) and N-bromosuccinimide (32.31g, 181.52mmol) were added to dimethylformamide (1000ml) and stirred at room temperature for 12 hours. After completion of the reaction, 1000 ml of distilled water was added to the reaction solution, stirred for 30 minutes, and the resulting solid was filtered to obtain 53 g of compound 141-P4 (yield 91%).
3) 화합물 141-P3의 제조3) Preparation of compound 141-P3
화합물 141-P4 (53g, 150.74mmol)을 N,N-디메틸아세트아마이드(N,N-Dimethylacetamide) (600ml)에 넣고 용해시킨 후, 150℃로 가열한 후 탄산세슘 (cesium carbonate, Cs2CO3) (147.34g, 452.22mmol)을 넣고 30분 동안 환류 교반하였다. 반응 완료 후 디클로로메탄과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼크로마토그래피로 정제하여 화합물 141-P3을 42g 얻었다(수율 84%).Compound 141-P4 (53g, 150.74mmol) was dissolved in N,N-Dimethylacetamide (600ml), heated to 150°C, and dissolved in cesium carbonate (Cs 2 CO 3 ) . ) (147.34g, 452.22mmol) was added and stirred under reflux for 30 minutes. After completion of the reaction, extraction was performed with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as developing solvents to yield 42 g of compound 141-P3. obtained (yield 84%).
4) 화합물 141-P2의 제조4) Preparation of compound 141-P2
화합물 141-P3 (42g, 126.66mmol)과 메틸 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤란-2-일)-[1,1'-비페닐]-3-카르복실레이트 (methyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-carboxylate) (47.12g, 139.33mmol)을 1,4-디옥세인(1,4-Dioxane) (500ml) 및 증류수 (100ml)에 넣고 녹인 후, 테트라키스(트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine)palladium, Pd(PPh3)4) (7.32g, 6.33mmol)과 탄산칼륨 (potassium carbonate, K2CO3) (43.77g, 316.66mmol)을 넣고, 12시간 동안 환류 교반하였다. 반응 완료 후 반응액을 디클로로메탄과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 141-P2를 45g 얻었다(수율 77%).Compound 141-P3 (42g, 126.66mmol) and methyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl ]-3-carboxylate (methyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-carboxylate) (47.12 g, 139.33mmol) was dissolved in 1,4-Dioxane (500ml) and distilled water (100ml), then tetrakis(triphenylphosphine)palladium, Pd( PPh 3 ) 4 ) (7.32g, 6.33mmol) and potassium carbonate (K 2 CO 3 ) (43.77g, 316.66mmol) was added and stirred under reflux for 12 hours. After completion of the reaction, the reaction solution was extracted with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then dichloromethane and hexane were used as developing solvents and purified by column chromatography to obtain compound 141- 45g of P2 was obtained (yield 77%).
5) 화합물 141-P1의 제조5) Preparation of compound 141-P1
화합물 141-P2 (45g, 97.21mmol)을 테트라하이드로퓨란(tetrahydrofuran) (500ml)에 넣고 녹인 후, 0℃에서 메틸마그네슘 브로마이드 (methylmagnesium bromide) (3M solution in ether, 97ml, 291.63mmol)를 천천히 첨가한 후 60℃에서 6시간 동안 교반하였다. 반응 종료 후 반응액에 물을 첨가하여 종결시킨 후 디클로로메탄과 증류수를 이용하여 추출하고, 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거하였고, 그 후 디클로로메탄에 녹인 후 반응물에 보론 트리플루오라이드 디에틸 이더레이트 (boron trifluoride diethyl ehterate)를 추가 후 상온에서 4시간 동안 교반하였다. 반응 종료 후 디클로로메탄과 헥산을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 141-P1을 30g 얻었다(수율 69%).Compound 141-P2 (45g, 97.21mmol) was dissolved in tetrahydrofuran (500ml), and then methylmagnesium bromide (3M solution in ether, 97ml, 291.63mmol) was slowly added at 0°C. Afterwards, it was stirred at 60°C for 6 hours. After the reaction was terminated by adding water to the reaction solution, extraction was performed using dichloromethane and distilled water. The organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then the solution was dissolved in dichloromethane. After adding boron trifluoride diethyl etherate to the reaction, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, dichloromethane and hexane were purified by column chromatography using a developing solvent to obtain 30 g of compound 141-P1 (yield 69%).
6) 화합물 141의 제조6) Preparation of Compound 141
화합물 141-P1 (10g, 22.47mmol)과 디([1,1'-비페닐]-4-일)아민 (di([1,1'-biphenyl]-4-yl)amine) (7.58g, 23.60mmol)을 톨루엔(Toluene) (100ml)에 넣고 녹인 후, 트리스(디벤질리덴아세톤)디팔라듐 (tris(dibenzylideneacetone)dipalladium, Pd2(dba)3) (1.03g, 1.12mmol), 디사이클로헥실(2',4',6'-트리아이소프로필-[1,1'-바이페닐]-2-일)포스핀(Dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine, Xphos) (1.07g, 2.25mmol) 및 소듐 터트-부톡사이드 (sodium tert-butoxide, t-BuONa) (4.32g, 44.95mmol)을 넣고 2시간 동안 환류 교반하였다. 반응 완료 후 반응액을 디클로로메탄과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 141을 13g 얻었다(수율 79%).Compound 141-P1 (10g, 22.47mmol) and di([1,1'-biphenyl]-4-yl)amine) (7.58g, After dissolving 23.60mmol) in toluene (100ml), tris(dibenzylideneacetone)dipalladium, Pd 2 (dba) 3 ) (1.03g, 1.12mmol), Dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Dicyclohexyl(2',4', 6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine, Xphos) (1.07g, 2.25mmol) and sodium tert-butoxide (t-BuONa) (4.32g, 44.95mmol) was added and stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was extracted with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and the solvent was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain Compound 141. 13g was obtained (yield 79%).
상기 제조예 2에서, (5-클로로-2-플루오로페닐)보론산((5-chloro-2-fluorophenyl)boronic acid) 대신, 하기 표 2의 화합물 D를 사용하고, 메틸 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤란-2-일)-[1,1'-비페닐]-3-카르복실레이트 (methyl 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-carboxylate) 대신, 하기 표2의 화합물 E를 사용하고, 디([1,1'-비페닐]-4-일)아민 (di([1,1'-biphenyl]-4-yl)amine) 대신, 하기 표 2의 화합물 F를 사용한 것을 제외하고, 상기 제조예와 동일한 방법으로 목적화합물을 합성하였다.In Preparation Example 2, instead of (5-chloro-2-fluorophenyl)boronic acid, compound D of Table 2 below was used, and methyl 2-(4, 4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-carboxylate (methyl 2-(4,4,5 Instead of ,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-3-carboxylate), use compound E of Table 2 below, and use di([1,1' -Biphenyl]-4-yl)amine (di([1,1'-biphenyl]-4-yl)amine) was used in the same manner as in the above production example, except that compound F of Table 2 below was used. The compound was synthesized.
[표 2][Table 2]
Figure PCTKR2023005090-appb-img-000047
Figure PCTKR2023005090-appb-img-000047
Figure PCTKR2023005090-appb-img-000048
Figure PCTKR2023005090-appb-img-000048
Figure PCTKR2023005090-appb-img-000049
Figure PCTKR2023005090-appb-img-000049
Figure PCTKR2023005090-appb-img-000050
Figure PCTKR2023005090-appb-img-000050
Figure PCTKR2023005090-appb-img-000051
Figure PCTKR2023005090-appb-img-000051
Figure PCTKR2023005090-appb-img-000052
Figure PCTKR2023005090-appb-img-000052
Figure PCTKR2023005090-appb-img-000053
Figure PCTKR2023005090-appb-img-000053
Figure PCTKR2023005090-appb-img-000054
Figure PCTKR2023005090-appb-img-000054
제조예 3 : 화합물 584의 제조Preparation Example 3: Preparation of Compound 584
Figure PCTKR2023005090-appb-img-000055
Figure PCTKR2023005090-appb-img-000055
화합물 113 (10g, 16.45mmol), 트리플루오로메탄설폰산(Trifluoromethanesulfonic acid) (3.70g, 24.68mmol) 및 D6-벤젠(D6-benzene) (100ml)을 반응 플라스크에 넣은 후, 5시간 동안 환류 교반하였다. 반응 완료 후 물을 넣어 반응을 종결시킨 후 디클로로메탄과 증류수로 추출하고 유기층을 무수 황산 마그네슘 (MgSO4)으로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 컬럼 크로마토그래피로 정제하여 화합물 584를 9g 얻었다(수율 87%).Compound 113 (10g, 16.45mmol), trifluoromethanesulfonic acid (3.70g, 24.68mmol), and D6-benzene (100ml) were added to the reaction flask, and then refluxed and stirred for 5 hours. did. After completion of the reaction, water was added to terminate the reaction, extracted with dichloromethane and distilled water, the organic layer was dried with anhydrous magnesium sulfate (MgSO 4 ), the solvent was removed using a rotary evaporator, and then subjected to column chromatography using dichloromethane and hexane as developing solvents. By purification, 9g of compound 584 was obtained (yield 87%).
상기 제조예 1 내지 제조예 3에 기재된 화합물 이외의 나머지 화합물도 전술한 제조예에 기재된 방법과 동일한 방법으로 제조하였고, 하기 표 3 및 표 4에 합성 결과를 나타내었다. 하기 표 3은 화합물의 1H NMR(CDCl3, 300Mz)의 측정값이고, 하기 표 4는 FD-질량분석계(FD-MS: Field desorption mass spectrometry)의 측정값이다.The remaining compounds other than those described in Preparation Examples 1 to 3 were also prepared in the same manner as described in the above Preparation Examples, and the synthesis results are shown in Tables 3 and 4 below. Table 3 below shows the measured values of 1 H NMR (CDCl 3 , 300Mz) of the compound, and Table 4 below shows the measured values of Field desorption mass spectrometry (FD-MS) of the compound.
[표 3][Table 3]
Figure PCTKR2023005090-appb-img-000056
Figure PCTKR2023005090-appb-img-000056
Figure PCTKR2023005090-appb-img-000057
Figure PCTKR2023005090-appb-img-000057
Figure PCTKR2023005090-appb-img-000058
Figure PCTKR2023005090-appb-img-000058
Figure PCTKR2023005090-appb-img-000059
Figure PCTKR2023005090-appb-img-000059
Figure PCTKR2023005090-appb-img-000060
Figure PCTKR2023005090-appb-img-000060
[표 4][Table 4]
Figure PCTKR2023005090-appb-img-000061
Figure PCTKR2023005090-appb-img-000061
<실험예><Experimental example>
실험예 1Experimental Example 1
(1) 유기 발광 소자의 제작(1) Fabrication of organic light emitting devices
1,500Å의 두께로 인듐틴옥사이드(ITO, Indium Tinoxide)가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 아세톤, 메탄올, 이소프로필 알코올 등의 용제로 초음파 세척을 실시하고, 건조시킨 후, UV(Ultraviolet) 세정기에서 UV를 이용하여 5분간 UVO (Ultraviolet Ozone)처리를 하였다. 이후 기판을 플라즈마 세정기(PT)로 이송시킨 후, ITO의 일함수 증대 및 잔막 제거를 위해 진공상태에서 플라즈마 처리를 하여, 유기증착용 열증착 장비로 이송하였다.A glass substrate coated with a thin film of indium tinoxide (ITO) with a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UV (Ultraviolet Ozone) for 5 minutes using UV light in a UV (Ultraviolet) cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to increase the work function of ITO and remove the remaining film, and then transferred to a thermal evaporation equipment for organic deposition.
이어서 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 4,4',4"-트리스[2-나프틸(페닐)아미노] 트리페닐아민 (4,4',4"-Tris[2-naphthyl(phenyl)amino] triphenylamine: 2-TNATA)를 증발시켜 ITO 기판 상에 600Å 두께의 정공 주입층을 증착하였다. 진공 증착 장비 내의 다른 셀에 하기 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 넣고, 셀에 전류를 인가하여 증발시켜 정공 주입층 위에 1000Å 두께의 정공 수송층을 증착하였다. Subsequently, the vacuum in the chamber was evacuated until it reached 10 -6 torr, and then a current was applied to the cell to produce 4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine (4,4 ',4"-Tris[2-naphthyl(phenyl)amino] triphenylamine: 2-TNATA) was evaporated to deposit a 600Å thick hole injection layer on the ITO substrate. In another cell in the vacuum deposition equipment, the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added and evaporated by applying a current to the cell to deposit a 1000Å thick hole transport layer on the hole injection layer.
Figure PCTKR2023005090-appb-img-000062
Figure PCTKR2023005090-appb-img-000063
Figure PCTKR2023005090-appb-img-000062
Figure PCTKR2023005090-appb-img-000063
이와 같이 정공 주입층 및 정공 수송층을 형성시킨 후, 그 위에 발광층을 다음과 같이 열 진공 증착시켰다. 발광층은 호스트로 9-[4-(4,6-디페닐-1,3,5-트리아진-2-일)페닐]-9'-페닐-3,3'-비-9H-카바졸 (9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'-Bi-9H-carbazole)의 화합물을 400Å 증착하였고, 녹색 인광 도펀트는 Ir(ppy)3를 7% 도핑하여 증착하였다. 이후 정공 저지층으로 바토큐프로인 (bathocuproine, BCP)를 60Å 증착하였으며, 그 위에 전자 수송층으로 E1을 300Å 증착하였다.After forming the hole injection layer and the hole transport layer in this way, a light-emitting layer was thermally vacuum deposited thereon as follows. The emitting layer uses 9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'-bi-9 H -carbazole as a host. The compound (9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9'-phenyl-3,3'-Bi-9 H -carbazole) was deposited at 400 Å. And the green phosphorescent dopant was deposited by doping 7% of Ir(ppy) 3 . Afterwards, 60Å of bathocuproine (BCP) was deposited as a hole blocking layer, and 300Å of E1 was deposited on top of it as an electron transport layer.
Figure PCTKR2023005090-appb-img-000064
Figure PCTKR2023005090-appb-img-000065
Figure PCTKR2023005090-appb-img-000064
Figure PCTKR2023005090-appb-img-000065
마지막으로 전자 수송층 위에 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하여 전자 주입층을 형성한 후, 전자 주입층 위에 알루미늄(Al) 음극을 1,200Å의 두께로 증착하여 음극을 형성함으로써 유기 발광 소자를 제조하였다.Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic A light emitting device was manufactured.
한편, 유기 발광 소자의 제조에 필요한 모든 유기 화합물은 재료 별로 각각 10-6~10-8torr 하에서 진공 승화 정제하여 유기 발광 소자의 제조에 사용하였다.Meanwhile, all organic compounds required for the production of organic light-emitting devices were purified by vacuum sublimation under 10 -6 to 10 -8 torr for each material and used in the production of organic light-emitting devices.
상기 실험예 1에서 정공 수송층 형성 시 사용된 화합물 NPB 대신, 하기 표 5에 표시되어 있는 화합물을 사용하는 것을 제외하고는, 실험예 1에 따른 유기 발광 소자의 구동 전압 및 발광 효율은 하기와 같다.Except that the compound shown in Table 5 below was used instead of the compound NPB used to form the hole transport layer in Experimental Example 1, the driving voltage and luminous efficiency of the organic light-emitting device according to Experimental Example 1 are as follows.
이때, NPB를 제외한 비교예 2 내지 4의 화합물은 하기와 같다.At this time, the compounds of Comparative Examples 2 to 4 excluding NPB are as follows.
Figure PCTKR2023005090-appb-img-000066
Figure PCTKR2023005090-appb-img-000066
(2) 유기 발광 소자의 구동 전압 및 발광 효율(2) Driving voltage and luminous efficiency of organic light-emitting devices
상기와 같이 제작된 유기 발광 소자에 대하여 맥사이언스사의 M7000으로 전계 발광(EL)특성을 측정하였으며, 그 측정 결과를 가지고 맥사이언스사에서 제조된 수명장비측정장비(M6000)를 통해 기준 휘도가 20,000 cd/m2 일 때, 초기 휘도 대비 95%가 되는 시간인 수명 T95 (단위: h, 시간)를 측정하였다.The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using McScience's M7000, and the standard luminance was measured to be 20,000 cd using the measurement results using a lifespan measurement equipment (M6000) manufactured by McScience. When /m 2 , the lifespan T 95 (unit: h, time), which is the time for 95% of the initial luminance, was measured.
본 발명에 따라 제조된 유기 발광 소자의 구동전압, 발광효율 및 수명을 측정한 결과는 하기 표 5와 같았다.The results of measuring the driving voltage, luminous efficiency, and lifespan of the organic light-emitting device manufactured according to the present invention are shown in Table 5 below.
[표 5][Table 5]
Figure PCTKR2023005090-appb-img-000067
Figure PCTKR2023005090-appb-img-000067
Figure PCTKR2023005090-appb-img-000068
Figure PCTKR2023005090-appb-img-000068
상기 표 5의 결과로부터 알 수 있듯이, 본 발명의 화학식 1로 표시되는 화합물을 정공 수송층 재료로 이용한 유기 발광 소자(실시예 1 내지 58)는 비교예 1 내지 4의 화합물을 정공 수송층 재료로 이용한 유기 발광 소자에 비해 구동 전압이 낮고, 발광효율 및 수명이 현저히 개선되었다. As can be seen from the results in Table 5, the organic light-emitting devices (Examples 1 to 58) using the compound represented by Formula 1 of the present invention as the hole transport layer material were the organic light emitting devices using the compounds of Comparative Examples 1 to 4 as the hole transport layer material. Compared to light-emitting devices, the driving voltage is lower, and the luminous efficiency and lifespan are significantly improved.
비교예 2 내지 4에 사용된 M1 내지 M3의 화합물은 디메틸플루오레노벤조퓨란 타입의 5환 골격을 가지고 있는 점에서 본 발명의 화학식 1의 화합물과 유사하나, M1 및 M3의 화합물의 경우 디메틸플루오레노벤조퓨란의 4번 위치에 아릴아민 치환기가 도입되었고, 본 발명의 화합물은 4번 위치에 아릴아민 치환기가 도입되어 있지 않다는 점에서 차이가 있다. 상기 디메틸플루오레노벤조퓨란의 4번 위치에 아릴아민기가 도입이 되었을 경우, 다른 위치에 비해 정공이동도가 느려지는 단점이 있다. 본 발명의 화합물의 경우 상기 모핵의 4번 위치가 아닌 다른 위치에 아릴아민기가 도입됨으로써 정공이동도의 물성이 우수해져서 소자 특성이 우수해짐을 확인하였다.The compounds M1 to M3 used in Comparative Examples 2 to 4 are similar to the compounds of Formula 1 of the present invention in that they have a dimethylfluorenobenzofuran-type 5-ring skeleton, but in the case of the compounds M1 and M3, dimethylfluoreno An arylamine substituent is introduced at the 4th position of benzofuran, and the compound of the present invention is different in that an arylamine substituent is not introduced at the 4th position. When an arylamine group is introduced at position 4 of the dimethylfluorenobenzofuran, there is a disadvantage that hole mobility becomes slower compared to other positions. In the case of the compound of the present invention, it was confirmed that the arylamine group was introduced at a position other than the 4th position of the parent nucleus, thereby improving the physical properties of hole mobility and improving device characteristics.
비교예 3에 사용된 M2의 화합물의 경우 디메틸플루오레노벤조퓨란 타입의 5환 골격을 가지고 있는 점에서, 본 발명의 화학식 1의 화합물과 유사하나, 아릴아민기의 2치환 구조를 가지고 있다. 상기 디메틸플루오레노벤조퓨란 타입의 골격 구조에 디아릴아민기로 2치환 구조를 가지고 있을 경우, HOMO 준위가 높아지게 된다. 본 발명의 화학식 1의 화합물은 단일 아릴아민 치환기를 가짐으로써 HOMO 준위가 비교예 3에 사용된 M2의 화합물보다 낮다. HOMO 준위가 낮아짐으로써 정공수송층과 발광층 사이의 HOMO 준위 차이가 적어져 정공수송이 더 용이해지게 되고, 이러한 이유로 소자 특성이 우수해짐을 확인하였다.The compound M2 used in Comparative Example 3 is similar to the compound of Formula 1 of the present invention in that it has a dimethylfluorenobenzofuran-type 5-ring skeleton, but has a 2-substituted arylamine group structure. When the dimethylfluorenobenzofuran type skeletal structure has a 2-substituted diarylamine group, the HOMO level increases. The compound of Formula 1 of the present invention has a single arylamine substituent, so its HOMO level is lower than that of the compound M2 used in Comparative Example 3. As the HOMO level is lowered, the HOMO level difference between the hole transport layer and the light emitting layer is reduced, making hole transport easier, and for this reason, it was confirmed that the device characteristics are improved.
<실험예 2><Experimental Example 2>
(1) 유기 발광 소자의 제작(1) Fabrication of organic light emitting devices
OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막을 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 각 5분간 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. 다음으로 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 하기 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐 아민 (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA)을 넣었다.The transparent electrode ITO thin film obtained from OLED glass (manufactured by Samsung-Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol before use. Next, the ITO substrate was installed in the substrate folder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine ( 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added.
Figure PCTKR2023005090-appb-img-000069
Figure PCTKR2023005090-appb-img-000069
이어서 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 600Å 두께의 정공 주입층을 증착하였다. 진공 증착 장비 내의 다른 셀에 하기 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 넣고, 셀에 전류를 인가하여 증발시켜 정공 주입층 위에 1000Å 두께의 정공 수송층을 증착하였다.Subsequently, the vacuum in the chamber was evacuated until it reached 10 -6 torr, and then a current was applied to the cell to evaporate 2-TNATA and a 600Å thick hole injection layer was deposited on the ITO substrate. In another cell in the vacuum deposition equipment, the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added and evaporated by applying a current to the cell to deposit a 1000 Å thick hole transport layer on the hole injection layer.
Figure PCTKR2023005090-appb-img-000070
Figure PCTKR2023005090-appb-img-000070
이와 같이 정공 주입층 및 정공 수송층을 형성시킨 후, 그 위에 전자저지층으로, 하기 구조식 M1의 화합물을 100Å 두께로 증착하였다.After forming the hole injection layer and the hole transport layer in this way, a compound of the following structural formula M1 was deposited to a thickness of 100 Å as an electron blocking layer thereon.
Figure PCTKR2023005090-appb-img-000071
Figure PCTKR2023005090-appb-img-000071
그 위에 발광층으로서 다음과 같은 구조의 청색 발광 재료를 증착시켰다. 구체적으로, 진공 증착 장비 내의 한쪽 셀에 청색 발광 호스트 재료인 H1의 화합물을 300Å 두께로 진공 증착시키고, 그 위에 청색 발광 도펀트 재료인 D1의 화합물을 호스트 재료 대비 5 wt% 도핑하여 증착시켰다.A blue light-emitting material with the following structure was deposited as a light-emitting layer thereon. Specifically, the compound of H1, a blue light-emitting host material, was vacuum deposited to a thickness of 300 Å in one cell of the vacuum deposition equipment, and the compound of D1, a blue light-emitting dopant material, was doped at 5 wt% compared to the host material and deposited on it.
Figure PCTKR2023005090-appb-img-000072
Figure PCTKR2023005090-appb-img-000073
Figure PCTKR2023005090-appb-img-000072
Figure PCTKR2023005090-appb-img-000073
이어서 전자 수송층으로서 하기 구조식 E1의 화합물을 300Å 두께로 증착하였다.Next, a compound of the following structural formula E1 was deposited to a thickness of 300 Å as an electron transport layer.
Figure PCTKR2023005090-appb-img-000074
Figure PCTKR2023005090-appb-img-000074
마지막으로, 상기 전자 수송층 위에 전자 주입층으로 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착한 후, 상기 전자 주입층 위에 알루미늄(Al) 음극을 1,000Å의 두께로 증착하여 음극을 형성함으로써 유기 발광 소자를 제조하였다. Finally, lithium fluoride (LiF) is deposited to a thickness of 10 Å as an electron injection layer on the electron transport layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,000 Å on the electron injection layer to form a cathode. An organic light emitting device was manufactured.
한편, 유기 발광 소자의 제조에 필요한 모든 유기 화합물은 재료 별로 각각 10-6~10-8torr 하에서 진공 승화 정제하여 유기 발광 소자의 제조에 사용하였다.Meanwhile, all organic compounds required for the production of organic light-emitting devices were purified by vacuum sublimation under 10 -6 to 10 -8 torr for each material and used in the production of organic light-emitting devices.
상기 실험예 2에서 전자 저지층 형성 시 사용된 화합물 M1 대신, 하기 표 6에 표시되어 있는 화합물을 사용하는 것을 제외하고는, 실험예 2에 따른 유기 발광 소자의 구동 전압 및 발광 효율은 하기와 같다.Except that the compound shown in Table 6 below was used instead of compound M1 used in forming the electron blocking layer in Experimental Example 2, the driving voltage and luminous efficiency of the organic light-emitting device according to Experimental Example 2 are as follows. .
이때, NPB를 제외한 비교예 5 내지 7의 화합물은 하기와 같다.At this time, the compounds of Comparative Examples 5 to 7 excluding NPB are as follows.
Figure PCTKR2023005090-appb-img-000075
Figure PCTKR2023005090-appb-img-000075
(2) 유기 발광 소자의 구동 전압 및 발광 효율(2) Driving voltage and luminous efficiency of organic light-emitting devices
상기와 같이 제작된 유기 발광 소자에 대하여 맥사이언스사의 M7000으로 전계 발광(EL)특성을 측정하였으며, 그 측정 결과를 가지고 맥사이언스사에서 제조된 수명장비측정장비(M6000)를 통해 기준 휘도가 20,000 cd/m2 일 때, 초기 휘도 대비 95%가 되는 시간인 수명 T95 (단위: h, 시간)를 측정하였다.The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using McScience's M7000, and the standard luminance was measured to be 20,000 cd using the measurement results using a lifespan measurement equipment (M6000) manufactured by McScience. When /m 2 , the lifespan T 95 (unit: h, time), which is the time for 95% of the initial luminance, was measured.
본 발명에 따라 제조된 유기 발광 소자의 구동전압, 발광효율 및 수명을 측정한 결과는 하기 표 6과 같았다.The results of measuring the driving voltage, luminous efficiency, and lifespan of the organic light-emitting device manufactured according to the present invention are shown in Table 6 below.
[표 6][Table 6]
Figure PCTKR2023005090-appb-img-000076
Figure PCTKR2023005090-appb-img-000076
상기 표 6의 결과로부터 알 수 있듯이, 본 발명의 화학식 1로 표시되는 화합물을 전자 저지층 재료로 이용한 유기 발광 소자인 실시예 59 내지 89은, M1 내지 M3 및 NPB 화합물을 전자 저지층 재료로 이용한 유기 발광 소자인 비교예 5 내지 8에 비해 구동 전압이 낮고, 발광효율 및 수명이 현저히 개선되었다.As can be seen from the results in Table 6, Examples 59 to 89, which are organic light-emitting devices using the compound represented by Formula 1 of the present invention as the electron blocking layer material, were obtained by using compounds M1 to M3 and NPB as the electron blocking layer material. Compared to Comparative Examples 5 to 8, which were organic light emitting devices, the driving voltage was lower, and the luminous efficiency and lifespan were significantly improved.
[부호의 설명][Explanation of symbols]
100: 기판100: substrate
200: 양극200: anode
300: 유기물층300: Organic layer
301: 정공 주입층301: hole injection layer
302: 정공 수송층302: hole transport layer
303: 발광층303: light emitting layer
304: 정공 저지층304: hole blocking layer
305: 전자 수송층305: electron transport layer
306: 전자 주입층306: electron injection layer
400: 음극400: cathode

Claims (12)

  1. 하기 화학식 1로 표시되는 헤테로 고리 화합물:Heterocyclic compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2023005090-appb-img-000077
    Figure PCTKR2023005090-appb-img-000077
    상기 화학식 1에서,In Formula 1,
    R1 내지 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기; -P(=O)R101R102; -SiR101R102R103; 및 하기 화학식 2로 표시되는 기로 이루어진 군으로부터 선택되거나, 서로 인접하는 2 이상의 기가 서로 결합하여 치환 또는 비치환된 C6 내지 C60의 방향족 탄화수소 고리 또는 치환 또는 비치환된 C2 내지 C60의 헤테로 고리를 형성하고, 상기 R101, R102 및 R103은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기이고, R1 to R12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; And two or more groups selected from the group consisting of the following formula (2), or two or more adjacent groups are combined with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 hetero ring, , R101, R102 and R103 are the same or different from each other, and are each independently a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
    R2 내지 R12 중 적어도 하나는 하기 화학식 2로 표시되는 기이고,At least one of R2 to R12 is a group represented by the following formula (2),
    R13 및 R14는 -CRaRbRc이고, 상기 Ra 내지 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 및 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기;로 이루어진 군으로부터 선택되고,R13 and R14 are -CRaRbRc, and Ra to Rc are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; And a substituted or unsubstituted C2 to C60 heterocycloalkyl group; selected from the group consisting of,
    [화학식 2][Formula 2]
    Figure PCTKR2023005090-appb-img-000078
    Figure PCTKR2023005090-appb-img-000078
    상기 화학식 2에서,In Formula 2,
    L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 단일결합; 치환 또는 비치환된 C6 내지 C60의 아릴렌기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴렌기;이고,L1 and L2 are the same or different from each other and are each independently a single bond; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;
    Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C60의 아릴기; 또는 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기;이고,Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group of C6 to C60; Or a substituted or unsubstituted C2 to C60 heteroaryl group;
    m 및 n은 서로 같거나 상이하고, 각각 독립적으로 0 내지 3의 정수이고,m and n are the same as or different from each other and are each independently an integer from 0 to 3,
    *는 상기 화학식 1의 화합물과의 결합 사이트를 나타낸다.* represents the binding site with the compound of Formula 1 above.
  2. 제1항에 있어서, According to paragraph 1,
    상기 R2 내지 R8 중 적어도 하나는 하기 화학식 2로 표시되는 기인 것인, 헤테로 고리 화합물:At least one of R2 to R8 is a heterocyclic compound represented by the following formula (2):
    [화학식 2][Formula 2]
    Figure PCTKR2023005090-appb-img-000079
    Figure PCTKR2023005090-appb-img-000079
    상기 화학식 2는 상기 청구항 1에서 정의된 바와 같다.Formula 2 is as defined in claim 1 above.
  3. 제1항에 있어서,According to paragraph 1,
    상기 R1은 수소; 중수소; 할로겐; 시아노기; 치환 또는 비치환된 C1 내지 C60의 알킬기; 치환 또는 비치환된 C2 내지 C60의 알케닐기; 치환 또는 비치환된 C2 내지 C60의 알키닐기; 치환 또는 비치환된 C1 내지 C60의 알콕시기; 치환 또는 비치환된 C3 내지 C60의 시클로알킬기; 치환 또는 비치환된 C2 내지 C60의 헤테로시클로알킬기; 치환 또는 비치환된 C6 내지 C60의 아릴기; 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴기;로 이루어진 군으로부터 선택되는 것인, 헤테로 고리 화합물.R1 is hydrogen; heavy hydrogen; halogen; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted C1 to C60 alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; a heterocyclic compound selected from the group consisting of.
  4. 제1항에 있어서,According to paragraph 1,
    상기 Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6 내지 C30의 아릴기; 또는 치환 또는 비치환된 C2 내지 C30의 헤테로아릴기;이되, 단, Ar1 또는 Ar2가 9,9-디페닐플루오레닐기인 것은 제외되는 것인, 헤테로 고리 화합물.Ar1 and Ar2 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group; However, the heterocyclic compound excludes Ar1 or Ar2 being a 9,9-diphenylfluorenyl group.
  5. 제1항에 있어서,According to paragraph 1,
    상기 화학식 1로 표시되는 헤테로 고리 화합물이 치환기로서 중수소를 포함하지 않거나, 수소 원자와 중수소 원자의 총수를 기준으로 중수소의 함량이 1% 내지 100%인, 헤테로 고리 화합물. A heterocyclic compound represented by Formula 1 does not contain deuterium as a substituent, or has a deuterium content of 1% to 100% based on the total number of hydrogen atoms and deuterium atoms.
  6. 제1항에 있어서,According to paragraph 1,
    상기 화학식 1로 표시되는 헤테로 고리 화합물은 하기 화합물들로 구성된 군으로부터 선택되는 어느 하나인 것인, 헤테로 고리 화합물:The heterocyclic compound represented by Formula 1 is any one selected from the group consisting of the following compounds:
    Figure PCTKR2023005090-appb-img-000080
    Figure PCTKR2023005090-appb-img-000080
    Figure PCTKR2023005090-appb-img-000081
    Figure PCTKR2023005090-appb-img-000081
    Figure PCTKR2023005090-appb-img-000082
    Figure PCTKR2023005090-appb-img-000082
    Figure PCTKR2023005090-appb-img-000083
    Figure PCTKR2023005090-appb-img-000083
    Figure PCTKR2023005090-appb-img-000084
    Figure PCTKR2023005090-appb-img-000084
    Figure PCTKR2023005090-appb-img-000085
    Figure PCTKR2023005090-appb-img-000085
    Figure PCTKR2023005090-appb-img-000086
    Figure PCTKR2023005090-appb-img-000086
    Figure PCTKR2023005090-appb-img-000087
    Figure PCTKR2023005090-appb-img-000087
    Figure PCTKR2023005090-appb-img-000088
    Figure PCTKR2023005090-appb-img-000088
    Figure PCTKR2023005090-appb-img-000089
    Figure PCTKR2023005090-appb-img-000089
    Figure PCTKR2023005090-appb-img-000090
    Figure PCTKR2023005090-appb-img-000090
    Figure PCTKR2023005090-appb-img-000091
    Figure PCTKR2023005090-appb-img-000091
    Figure PCTKR2023005090-appb-img-000092
    Figure PCTKR2023005090-appb-img-000092
    Figure PCTKR2023005090-appb-img-000093
    Figure PCTKR2023005090-appb-img-000093
    Figure PCTKR2023005090-appb-img-000094
    Figure PCTKR2023005090-appb-img-000094
    Figure PCTKR2023005090-appb-img-000095
    Figure PCTKR2023005090-appb-img-000095
    Figure PCTKR2023005090-appb-img-000096
    Figure PCTKR2023005090-appb-img-000096
    Figure PCTKR2023005090-appb-img-000097
    Figure PCTKR2023005090-appb-img-000097
    Figure PCTKR2023005090-appb-img-000098
    Figure PCTKR2023005090-appb-img-000098
    Figure PCTKR2023005090-appb-img-000099
    Figure PCTKR2023005090-appb-img-000099
    Figure PCTKR2023005090-appb-img-000100
    Figure PCTKR2023005090-appb-img-000100
    Figure PCTKR2023005090-appb-img-000101
    Figure PCTKR2023005090-appb-img-000101
    Figure PCTKR2023005090-appb-img-000102
    Figure PCTKR2023005090-appb-img-000102
    Figure PCTKR2023005090-appb-img-000103
    Figure PCTKR2023005090-appb-img-000103
    Figure PCTKR2023005090-appb-img-000104
    Figure PCTKR2023005090-appb-img-000104
    Figure PCTKR2023005090-appb-img-000105
    Figure PCTKR2023005090-appb-img-000105
    Figure PCTKR2023005090-appb-img-000106
    Figure PCTKR2023005090-appb-img-000106
    Figure PCTKR2023005090-appb-img-000107
    Figure PCTKR2023005090-appb-img-000107
    Figure PCTKR2023005090-appb-img-000108
    Figure PCTKR2023005090-appb-img-000108
    Figure PCTKR2023005090-appb-img-000109
    Figure PCTKR2023005090-appb-img-000109
  7. 제1 전극;first electrode;
    상기 제1 전극과 대향하여 구비된 제2 전극; 및a second electrode provided opposite to the first electrode; and
    상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층;을 포함하는 유기 발광 소자로서,An organic light-emitting device comprising: one or more organic material layers provided between the first electrode and the second electrode,
    상기 유기물층 중 1층 이상은 제1항 내지 제6항 중 어느 한 항에 따른 헤테로 고리 화합물을 포함하는 것인, 유기 발광 소자.An organic light-emitting device, wherein at least one layer of the organic material layer includes the heterocyclic compound according to any one of claims 1 to 6.
  8. 제7항에 있어서,In clause 7,
    상기 유기물층은 발광층을 포함하고, The organic layer includes a light-emitting layer,
    상기 발광층은 상기 헤테로 고리 화합물을 포함하는 것인, 유기 발광 소자.An organic light-emitting device wherein the light-emitting layer includes the heterocyclic compound.
  9. 제7항에 있어서,In clause 7,
    상기 유기물층은 발광층을 포함하고, The organic layer includes a light-emitting layer,
    상기 발광층은 호스트 물질을 포함하며, The light emitting layer includes a host material,
    상기 호스트 물질은 상기 헤테로 고리 화합물을 포함하는 것인, 유기 발광 소자.An organic light-emitting device wherein the host material includes the heterocyclic compound.
  10. 제7항에 있어서,In clause 7,
    상기 유기물층은 정공수송층 또는 정공수송 보조층을 포함하고, The organic material layer includes a hole transport layer or a hole transport auxiliary layer,
    상기 정공수송층 또는 정공수송 보조층은 상기 헤테로 고리 화합물을 포함하는 것인, 유기 발광 소자.An organic light-emitting device wherein the hole transport layer or the hole transport auxiliary layer includes the heterocyclic compound.
  11. 제7항에 있어서,In clause 7,
    상기 유기물층은 전자저지층을 포함하고, The organic material layer includes an electron blocking layer,
    상기 전자저지층은 상기 헤테로 고리 화합물을 포함하는 것인, 유기 발광 소자.An organic light-emitting device wherein the electron blocking layer includes the heterocyclic compound.
  12. 제7항에 있어서,In clause 7,
    상기 유기 발광 소자는 발광층, 정공주입층, 정공수송층, 정공수송 보조층, 전자주입층, 전자수송층, 전지저지층 및 정공저지층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함하는 것인, 유기 발광 소자.The organic light emitting device further includes one or two layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. Phosphorus, organic light emitting device.
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KR20190007257A (en) * 2017-07-12 2019-01-22 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
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KR20210013452A (en) * 2019-07-25 2021-02-04 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

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KR20170023388A (en) * 2015-08-21 2017-03-03 삼성디스플레이 주식회사 Organic light emitting device
KR20190007257A (en) * 2017-07-12 2019-01-22 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
KR20200089891A (en) * 2019-01-18 2020-07-28 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
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