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WO2020138964A1 - Compound and organic light-emitting element comprising same - Google Patents

Compound and organic light-emitting element comprising same Download PDF

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Publication number
WO2020138964A1
WO2020138964A1 PCT/KR2019/018487 KR2019018487W WO2020138964A1 WO 2020138964 A1 WO2020138964 A1 WO 2020138964A1 KR 2019018487 W KR2019018487 W KR 2019018487W WO 2020138964 A1 WO2020138964 A1 WO 2020138964A1
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substituted
group
unsubstituted
light emitting
compound
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PCT/KR2019/018487
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French (fr)
Korean (ko)
Inventor
김명곤
홍완표
서상덕
금수정
김경희
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주식회사 엘지화학
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Priority to CN201980076088.6A priority Critical patent/CN113166176B/en
Publication of WO2020138964A1 publication Critical patent/WO2020138964A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants

Definitions

  • the present specification relates to a compound and an organic light emitting device including the same.
  • the organic light emitting device is a light emitting device using an organic semiconductor material, and requires exchange of holes and/or electrons between the electrode and the organic semiconductor material.
  • the organic light emitting device can be roughly divided into two types according to the operation principle. First, excitons are formed in the organic layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and the electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is a light emitting device of the form.
  • the second is a light emitting device in which holes and/or electrons are injected into a layer of an organic semiconductor material that interfaces with an electrode by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.
  • the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween.
  • the organic material layer is often composed of a multi-layered structure composed of different materials, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron suppression layer, an electron transport layer, an electron injection layer, etc. Can lose.
  • Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron suppression materials, electron transport materials, and electron injection materials, depending on their function.
  • the light emitting materials include blue, green, and red light emitting materials, and yellow and orange light emitting materials necessary for realizing a better natural color depending on the light emitting color.
  • a host/dopant system may be used as a light emitting material to increase color purity and increase light emission efficiency through energy transfer.
  • the principle is that when a small amount of a dopant having a smaller energy band gap and higher luminous efficiency is mixed with a light emitting layer than a host mainly constituting the light emitting layer, exciton generated from the host is transported as a dopant to produce high efficiency light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of the dopant used.
  • materials constituting an organic material layer in the device such as a hole injection material, a hole transport material, a light emitting material, an electron suppressing material, an electron transport material, an electron injection material, are stable and efficient materials It is supported by, and the development of new materials continues to be required.
  • Described herein is a compound and an organic light emitting device comprising the same.
  • One embodiment of the present specification provides a compound represented by the following Chemical Formula 1.
  • X1 and X2 are each independently NR, O or S,
  • R1 and R2 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
  • R is a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • R' is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • a and b are each independently an integer from 0 to 4,
  • x is an integer from 1 to 3
  • y is an integer from 0 to 2
  • Another exemplary embodiment includes a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, and at least one layer of the organic material layer provides an organic light emitting device including the above-described compound.
  • the compound represented by Chemical Formula 1 of the present invention can be used as a material for the organic material layer of the organic light emitting device.
  • an organic light emitting device including the compound represented by Formula 1 of the present invention When an organic light emitting device including the compound represented by Formula 1 of the present invention is manufactured, an organic light emitting device having high efficiency, low voltage and long life characteristics can be obtained.
  • FIG. 1 shows a structure of an organic light emitting device according to an exemplary embodiment.
  • Figure 2 shows the structure of an organic light emitting device according to another embodiment.
  • substitution means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
  • substituted or unsubstituted in this specification is deuterium (-D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Boron group; Alkoxy groups; Alkyl groups; Cycloalkyl group; Aryl group; And 1 or 2 or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents among the above-described substituents, or having no substituents.
  • a substituent having two or more substituents may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).
  • the boron group may be represented by the formula -BY d Y e , wherein Y d and Y e are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group.
  • the boron group may include, but is not limited to, trimethyl boron group, triethyl boron group, tert-butyl dimethyl boron group, triphenyl boron group, phenyl boron group, and the like.
  • the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, and the like, but is not limited to these.
  • the alkenyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 2 to 30.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.
  • the alkynyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, and nonynyl. And the like, but is not limited thereto.
  • the alkoxy group may be a straight chain, branched chain or cyclic chain.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms.
  • Substituents comprising alkyl, alkoxy, and other alkyl group moieties described herein include both straight-chain or ground forms.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 39. According to one embodiment, the carbon number of the aryl group is 6 to 30.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, etc., as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto. no.
  • the fluorene group may be substituted, and two substituents may combine with each other to form a spiro structure.
  • Spirofluorene groups such as (9,9-dimethylfluorene group
  • It may be a substituted fluorene group such as (9,9-diphenylfluorene group).
  • substituted fluorene group such as (9,9-diphenylfluorene group
  • the heterocyclic group is a heteroatom as a ring group containing at least one of N, O, P, S, Si, and Se, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the number of carbon atoms in the heterocyclic group is 2 to 36.
  • heterocyclic group examples include pyridine group, pyrrole group, pyrimidine group, quinoline group, pyridazine group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group, Carbazole group, benzocarbazole group, benzonaphthofuran group, benzonaphthothiophene group, indenocarbazole group, indolocarbazole group, and the like, but are not limited thereto.
  • heterocyclic group may be applied, except that the heteroaryl group is aromatic.
  • heteroarylene group is a divalent aromatic group.
  • the amine group is -NH 2 ; Alkylamine groups; N-alkylarylamine group; Arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine groups and heteroarylamine groups, 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, anthracenylamine group, and 9-methyl-anthracenylamine group , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine Group, N-phenanthrenylfluorenylamine group,
  • the N-alkylarylamine group means an amine group in which N of an amine group is substituted with an alkyl group and an aryl group.
  • the N-aryl heteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.
  • the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.
  • the alkyl group, the aryl group, and the heteroaryl group in the N-alkylheteroarylamine group and the heteroarylamine group can be cited in the description of the alkyl group, aryl group, and heteroaryl group, respectively.
  • aryloxy groups include phenoxy group, p-toryloxy group, m-toryloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like.
  • the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted.
  • two substituents substituted in the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.
  • ring is a hydrocarbon ring; Or a hetero ring.
  • the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and a description of the cycloalkyl group or aryl group may be applied except that the divalent group.
  • heterocyclic group may be applied to the heterocycle except that it is divalent.
  • X1 and X2 are each independently NR, O, or S.
  • X1 and X2 are the same as or different from each other.
  • X1 and X2 is O.
  • X1 and X2 is S.
  • X1 and X2 are each independently, NR.
  • X1 and X2 are each independently, NR, and R is a substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • X1 and X2 are each independently, NR, and R is a substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group.
  • X1 and X2 are each independently NR, and R is a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
  • X1 and X2 are each independently NR, and R is a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • X1 and X2 are each independently NR, and R is a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
  • R1 and R2 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
  • R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
  • R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
  • R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
  • R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
  • R is a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
  • R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
  • R is a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.
  • Y1 is O.
  • Y1 is S.
  • R' is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R' is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
  • R' is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
  • R' is a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.
  • R' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
  • a and b are each independently an integer of 2 or more
  • the substituents in parentheses are the same or different from each other, and groups adjacent to each other may combine to form a substituted or unsubstituted ring. That is, a plurality of R1 or R2 may be combined with each other R1 or R2 to form a ring, or R1 and R2 may combine with each other to form a ring.
  • R1 and R2 each independently combine with an adjacent group to form a substituted or unsubstituted ring, a direct bond; Alternatively, any one of the following structures may be formed.
  • A1 to A24 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • a1 to a11 are each an integer from 0 to 4,
  • a12 is an integer from 0 to 6
  • the formula 1 is represented by the following formula 2 or 3.
  • R3 to R6 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
  • c and d are each independently an integer from 0 to 4,
  • e and f are each independently an integer from 0 to 3
  • R10 to R13 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
  • R14 to R16 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • X1, X2, Y1, R', x and y are as in the formula (1).
  • R3 to R6 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
  • R3 to R6 are each independently, hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
  • R3 to R6 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.
  • R3 to R6 are each independently, hydrogen; heavy hydrogen; It is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.
  • R10 to R13 are each independently, a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
  • R10 to R13 are each independently, a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
  • R10 to R13 are each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
  • R14 to R16 are each independently, a substituted or unsubstituted aryl group.
  • R14 to R16 are each independently, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • the substituents in parentheses are the same or different from each other, and groups adjacent to each other may combine to form a substituted or unsubstituted ring.
  • a plurality of R3, a plurality of R4, a plurality of R5 or a plurality of R6 may form a ring by combining R3, R4, R5 or R6 with each other.
  • R3 to R6 are each independently bonded to an adjacent group to form a substituted or unsubstituted ring, a direct bond; Alternatively, any one of the following structures may be formed.
  • A1 to A12 and A20 to A24 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • a1 to a11 are each an integer from 0 to 4,
  • a12 is an integer from 0 to 6
  • a compound not containing naphthalene among the compounds represented by the formula (1) has a delayed fluorescence property of less than ⁇ E st 0.25eV.
  • the number of excitons generated in the singlet and triplet in a general organic light emitting device is generated at a ratio of 25:75 (single term: triplet), and the fluorescent emission, phosphorescence emission, and thermal activation delayed fluorescence depending on the emission type according to exciton movement It can be divided into luminescence.
  • the thermally activated delayed fluorescence represents a phenomenon using a phenomenon of reverse intersystem crossing (RISC) from triplet exciton to singlet exciton, which is also referred to as Thermally Activated Delayed Fluorescence (TADF).
  • RISC reverse intersystem crossing
  • TADF Thermally Activated Delayed Fluorescence
  • naphthalene has a delayed fluorescence property of less than ⁇ E st 0.25 eV, so that excitons in a triplet excited state are typically singlet excited state. It is possible to implement an organic light emitting device having high efficiency by transferring the energy to the dopant by inverse transitioning.
  • the electron pull effect and the tetrahedral structure further reduce the half-width, increasing the distance between the material and the material to prevent stacking, thereby suppressing triplet-polaron quenching. It can increase the efficiency, tune the desired wavelength, form a rigid structure (Rigid form) and increase the safety of the material.
  • the formula 1 may be represented by any one of the following compounds.
  • compounds having various energy band gaps can be synthesized by introducing various substituents to the core structure as described above.
  • the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents to the core structure having the above structure.
  • the organic light emitting device includes a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, and at least one layer of the organic material layer comprises the above-described compound.
  • the organic light emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic material layers are formed using the compound represented by Chemical Formula 1 above.
  • an organic light emitting device having an organic material layer formed of the compound represented by the compound 1 it may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method.
  • the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
  • the organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention is a hole transport layer, a hole injection layer, an electron blocking layer, a layer simultaneously performing hole transport and hole injection, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection simultaneously as an organic material layer It may have a structure including one or more of the layers.
  • the structure of the organic light emitting device of the present specification is not limited to this, and may include fewer or more organic material layers.
  • the organic material layer includes an electron blocking layer, a hole injection layer, or a hole transport layer, and the electron blocking layer, a hole injection layer, or a hole transport layer includes a compound represented by Chemical Formula 1.
  • the organic material layer includes a hole blocking layer, an electron injection layer, or an electron transport layer, and the hole blocking layer, an electron injection layer, or an electron transport layer includes a compound represented by Chemical Formula 1.
  • the organic material layer includes a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1 described above.
  • the organic material layer includes a light emitting layer
  • the light emitting layer may include the compound represented by Chemical Formula 1 as a dopant in the light emitting layer.
  • the organic material layer includes a dopant comprising a compound represented by Formula 1 described above; And a host.
  • the weight ratio of the host and the dopant is 90: 10 or more, 91:9 or more, 92:8 or more, 93:7 or more, 94:6 or more, 95:5 or more, 96:4 or more, 97 :3 or more, or 98:2 or more, 99.9:0.1 or less, 99.8:0.2 or less, 99.7:0.3 or less, 99.6:0.4 or less, 99.5:0.5 or less, 99.4:0.6 or less, 99.3:0.7 or less, 99.2:0.8 or less , 99.1:0.9 or less, or 99:1 or less.
  • the organic material layer further includes one or two or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer. do.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the organic light emitting device may have, for example, a stacked structure as described below, but is not limited thereto.
  • the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
  • FIG. 1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1.
  • the compound may be included in the light emitting layer 3.
  • FIG. 2 the anode 2 on the substrate 1, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 3, the first electron transport layer 8-1, the second
  • the structure of the organic light emitting device in which the electron transport layer 8-2 and the cathode 4 are sequentially stacked is illustrated.
  • the organic light emitting device uses a metal vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to have a metal or conductive metal oxide on the substrate or alloys thereof
  • PVD metal vapor deposition
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer, and then depositing a material that can be used as a cathode thereon Can be.
  • an organic light emitting device may be made by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the organic material layer may be a multi-layer structure including a hole injection layer, a hole transport layer, an electron injection and electron transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, an electron injection layer, an electron injection and electron transport layer, and the like. However, it is not limited thereto, and may be a single-layer structure. In addition, the organic material layer may use a variety of polymer materials to reduce the number of solvent processes (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer) rather than deposition. Can be prepared in layers.
  • solvent processes e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer
  • the positive electrode is an electrode for injecting holes
  • a positive electrode material is preferably a material having a large work function to facilitate hole injection into an organic material layer.
  • Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
  • the cathode is an electrode for injecting electrons
  • the cathode material is preferably a material having a small work function to facilitate electron injection into an organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof;
  • There is a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
  • the hole injection layer is a layer that serves to smoothly inject holes from the anode to the light emitting layer.
  • a hole injection material can be well injected with holes from the anode at a low voltage, and HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances.
  • the hole injection layer may have a thickness of 1 to 150 nm.
  • the thickness of the hole injection layer is 1 nm or more, there is an advantage of preventing the hole injection characteristics from being deteriorated. If it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement. There is an advantage that can be prevented.
  • the hole transport layer may serve to facilitate the transport of holes.
  • a hole transport material a material capable of receiving holes from an anode or a hole injection layer and transferring them to the light emitting layer is suitable for a material having high mobility for holes.
  • Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • An electron blocking layer may be provided between the hole transport layer and the light emitting layer.
  • the electron blocking layer may be a material known in the art.
  • the light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material.
  • a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively is preferably a material having good quantum efficiency for fluorescence or phosphorescence.
  • the organic light emitting diode according to the exemplary embodiment of the present specification includes a light emitting layer, and the light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula H below.
  • L21 to L23 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
  • R21 to R27 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • a 0 or 1.
  • the position of -L23-Ar23 is connected to hydrogen or deuterium.
  • L21 to L23 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted C6-C30 arylene group; Or a substituted or unsubstituted C2-C30 heteroarylene group containing N, O, or S.
  • L21 to L23 are the same as or different from each other, and each independently a direct bond; C6-C30arylene group; Or a C2-C30 heteroarylene group containing N, O, or S, wherein the arylene group or heteroarylene group is substituted or unsubstituted with a C1-C10 alkyl group, a C6-C30 aryl group, or a C2-C30 heteroaryl group. Is bright.
  • L21 to L23 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted divalent dibenzofuran group; Or a substituted or unsubstituted divalent dibenzothiophene group.
  • Ar21 to Ar23 are the same or different from each other, and each independently a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted C2-C30 heteroaryl group.
  • Ar21 to Ar23 are the same or different from each other, and each independently a substituted or unsubstituted C6-C30 aryl group with deuterium; Or a C2-C30 heteroaryl group unsubstituted or substituted with deuterium.
  • Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic to 4 ring aryl group; Or a substituted or unsubstituted monocyclic to 4 ring heteroaryl group.
  • Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted deuterium monocyclic to 4 ring aryl group; Or a monocyclic to 4 ring heteroaryl group unsubstituted or substituted with deuterium.
  • Ar21 to Ar23 are the same as or different from each other, and each independently substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracene group; A substituted or unsubstituted phenanthryl group; A substituted or unsubstituted phenylene group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted benzofluorenyl group; A substituted or unsubstituted furan group; A substituted or unsubstituted thiophene group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted naphthobenzofuran group; A substituted or unsubstituted
  • Ar21 and Ar22 are different from each other.
  • Ar21 is a substituted or unsubstituted aryl group
  • Ar22 is a substituted or unsubstituted aryl group
  • Ar21 is a substituted or unsubstituted aryl group
  • Ar22 is a substituted or unsubstituted heteroaryl group.
  • Ar21 is an aryl group unsubstituted or substituted with deuterium
  • Ar22 is an aryl group unsubstituted or substituted with deuterium
  • Ar21 is an aryl group unsubstituted or substituted with deuterium
  • Ar22 is a heteroaryl group unsubstituted or substituted with deuterium.
  • R21 to R27 are the same as or different from each other, and each independently hydrogen or deuterium.
  • R21 to R27 are hydrogen.
  • R21 to R27 are deuterium.
  • Chemical Formula H is represented by the following Chemical Formula H01 or H02.
  • L21 to L23 and Ar21 to Ar23 are as defined in Formula H, D means deuterium, k1 is 0 to 8, and k2 is an integer from 0 to 7.
  • the compound represented by Chemical Formula H is any one selected from the following compounds.
  • the organic light emitting device includes a light emitting layer, the light emitting layer includes a compound represented by Formula 1 as a dopant in the light emitting layer, and a compound represented by Formula H as a host of the light emitting layer.
  • the content of the compound represented by Formula 1 is 0.01 parts by weight to 30 parts by weight; 0.1 to 20 parts by weight; Or 0.5 to 10 parts by weight.
  • the compound represented by Chemical Formula H may be included as one type in the organic material layer (specifically, the light emitting layer), or may be included as two or more types. Specifically, the first host represented by Chemical Formula H and the second host represented by Chemical Formula H may be included in the organic material layer.
  • the weight ratio of the first host represented by Chemical Formula H and the second host represented by Chemical Formula H is 95:5 to 5:95, more preferably 30:70 to 70:30.
  • the first host and the second host are different from each other.
  • the light emitting layer includes one or two or more compounds represented by Formula H.
  • the light emitting layer including the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula H has a blue color.
  • the organic light emitting diode includes two or more light emitting layers, and at least one of the two or more light emitting layers includes a compound represented by Formula 1 and a compound represented by Formula H.
  • the light emitting layer including the compound represented by Formula 1 and the compound represented by Formula H has a blue color, and the light emitting layer not containing the compound represented by Formula 1 and the compound represented by Formula H is blue known in the art, Red or green light-emitting compounds.
  • the electron transport layer may serve to facilitate the transport of electrons.
  • the electron transporting material a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these.
  • the thickness of the electron transport layer may be 1 to 50 nm.
  • the thickness of the electron transport layer is 1 nm or more, there is an advantage of preventing the electron transport properties from deteriorating, and when it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from rising to improve the movement of electrons. There is an advantage.
  • the electron injection layer may serve to facilitate injection of electrons.
  • the electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect for the light emitting layer or the light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also , A compound having excellent thin film forming ability is preferred.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, and bis(8-hydroxyquinolinato) manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
  • the hole blocking layer is a layer that prevents the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.
  • the organic light emitting device may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
  • N,N'-((diphenylsilane)bis(5-(tert-butyl)-3,1-phenylene))bis(adamantan-1-amine) 50g, (3,4- Dibromo-5-iodophenyl) (difluoro(phenyl)methyl) sulfine 36g, sodium-tert-butoxide 19.7g and bis(tri-tert-butylphosphine)palladium(0) 0.4g toluene 600ml The mixture was stirred at reflux for 12 hours. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 18-1 (14.9g, yield 21%) was obtained through recrystallization. MS[M+H]+ 1054
  • a glass substrate coated with a thin film coated with ITO (indium tin oxide) at a thickness of 1,500 ⁇ was put in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • Fischer Co. was used as a detergent
  • distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water.
  • ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying, and then transported to a plasma cleaner.
  • the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.
  • the following chemical formula [HAT] was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer.
  • the following formula [NPB] was vacuum-deposited to a thickness of 1100 MPa on the hole injection layer to form a hole transport layer.
  • the following formula [HT-A] was vacuum deposited on the hole transport layer to a thickness of 200 ⁇ to form an electron blocking layer.
  • the second electron transport layer aluminum was deposited to a thickness of 1,000 mm 2 to form a cathode.
  • the deposition rate of the organic material was maintained at 0.4 to 0.9 ⁇ /sec
  • the lithium fluoride of the second electron transport layer was 0.3 0.3/sec
  • the aluminum of the negative electrode was maintained at a deposition rate of 2 ⁇ /sec.
  • Vacuum degree is 5 ⁇ 10 -8 ⁇ 1 ⁇ 10 -7
  • the torr was maintained to produce an organic light emitting device.
  • An organic light emitting diode was manufactured according to the same method as Example 1 except for using the dopant compound shown in Table 1 below as a light emitting layer dopant material instead of the compound 1 of Example 1.
  • Example 1 Compound 1 8.7 3.7 185 Example 2 Compound 2 8.7 3.7 188 Example 3 Compound 3 8.6 3.8 186 Example 4 Compound 4 8.6 3.8 189 Example 5 Compound 5 8.2 3.7 178 Example 6 Compound 6 8.2 3.7 179 Example 7 Compound 7 8.7 3.6 185 Example 8 Compound 8 8.6 3.7 186 Example 9 Compound 9 8.4 3.7 183 Example 10 Compound 10 8.9 3.8 189 Example 11 Compound 11 8.6 3.7 180 Example 12 Compound 12 8.7 3.7 181 Example 13 Compound 13 8.6 3.7 182 Example 14 Compound 14 8.8 3.8 183 Example 15 Compound 15 8.7 3.8 183 Example 16 Compound 16 8.7 3.7 182 Example 17 Compound 17 8.7 3.8 182 Example 18 Compound 18 8.6 3.8 183 Comparative Example 1 Compound BD 7.1 4.1 163
  • the devices of Examples 1 to 18 using the compound having the structure of Formula 1 have lower voltage, higher efficiency, and higher lifespan characteristics than the devices of Comparative Example 1. This is due to the substitution of the electron acceptor material at the para position of boron, which increases the polarity of the material, which results in improved charge transfer characteristics, and at the same time, a material having a structurally tetrahedral structure. By being substituted, it seems that the orientation characteristics of the material increase and the efficiency increases. In addition, the electron injection characteristic is strong and the driving voltage is reduced. The lifespan also showed a more stable effect in terms of balance of electrons and holes, showing an increasing pattern.

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Abstract

The present description provides a compound represented by chemical formula 1 and an organic light-emitting element comprising same.

Description

화합물 및 이를 포함하는 유기발광소자Compound and organic light emitting device comprising the same
본 명세서는 2018년 12월 26일 한국특허청에 제출된 한국 특허 출원 제10-2018-0169345호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This specification claims the benefit of the filing date of Korean Patent Application No. 10-2018-0169345 filed with the Korean Intellectual Property Office on December 26, 2018, all of which is included in this specification.
본 명세서는 화합물 및 이를 포함하는 유기발광소자에 관한 것이다.The present specification relates to a compound and an organic light emitting device including the same.
유기발광소자란 유기 반도체 물질을 이용한 발광소자로서, 전극과 유기 반도체 물질 사이에서의 정공 및/또는 전자의 교류를 필요로 한다. 유기발광소자는 동작 원리에 따라 하기와 같이 크게 두 가지로 나눌 수 있다. 첫째는 외부의 광원으로부터 소자로 유입된 광자에 의하여 유기물층에서 엑시톤(exiton)이 형성되고, 이 엑시톤이 전자와 정공으로 분리되고, 이 전자와 정공이 각각 다른 전극으로 전달되어 전류원(전압원)으로 사용되는 형태의 발광소자이다. 둘째는 2개 이상의 전극에 전압 또는 전류를 가하여 전극과 계면을 이루는 유기 반도체 물질층에 정공 및/또는 전자를 주입하고, 주입된 전자와 정공에 의하여 작동하는 형태의 발광소자이다.The organic light emitting device is a light emitting device using an organic semiconductor material, and requires exchange of holes and/or electrons between the electrode and the organic semiconductor material. The organic light emitting device can be roughly divided into two types according to the operation principle. First, excitons are formed in the organic layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and the electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is a light emitting device of the form. The second is a light emitting device in which holes and/or electrons are injected into a layer of an organic semiconductor material that interfaces with an electrode by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기발광소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자억제층, 전자수송층, 전자주입층 등으로 이루어 질 수 있다. 이러한 유기발광소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. 이러한 유기 발광 소자는 자발광, 고휘도, 고효율, 낮은 구동 전압, 넓은 시야각, 높은 콘트라스트 등의 특성을 갖는 것으로 알려져 있다.In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron suppression layer, an electron transport layer, an electron injection layer, etc. Can lose. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode and electrons are injected at the cathode, and excitons are formed when the injected holes meet the electrons. When it falls to the ground again, it will shine. It is known that such an organic light emitting device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, and high contrast.
유기발광소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공 주입 재료, 정공 수송 재료, 전자 억제 물질, 전자 수송 재료, 전자 주입 재료 등으로 분류될 수 있다. 발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료가 있다.Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron suppression materials, electron transport materials, and electron injection materials, depending on their function. The light emitting materials include blue, green, and red light emitting materials, and yellow and orange light emitting materials necessary for realizing a better natural color depending on the light emitting color.
또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도펀트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도펀트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도펀트로 수송되어 효율이 높은 빛을 내는 것이다. 이 때 호스트의 파장이 도펀트의 파장대로 이동하므로, 이용하는 도펀트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.In addition, a host/dopant system may be used as a light emitting material to increase color purity and increase light emission efficiency through energy transfer. The principle is that when a small amount of a dopant having a smaller energy band gap and higher luminous efficiency is mixed with a light emitting layer than a host mainly constituting the light emitting layer, exciton generated from the host is transported as a dopant to produce high efficiency light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of the dopant used.
전술한 유기발광소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공 주입 물질, 정공 수송 물질, 발광 물질, 전자 억제 물질, 전자 수송 물질, 전자 주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되므로 새로운 재료의 개발이 계속 요구되고 있다.In order to sufficiently exhibit the excellent characteristics of the aforementioned organic light emitting device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron suppressing material, an electron transport material, an electron injection material, are stable and efficient materials It is supported by, and the development of new materials continues to be required.
본 명세서에는 화합물 및 이를 포함하는 유기발광소자가 기재된다.Described herein is a compound and an organic light emitting device comprising the same.
본 명세서의 일 실시상태는 하기 화학식 1로 표시되는 화합물을 제공한다.One embodiment of the present specification provides a compound represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2019018487-appb-I000001
Figure PCTKR2019018487-appb-I000001
화학식 1에 있어서,In Formula 1,
X1 및 X2는 각각 독립적으로, NR, O 또는 S이고,X1 and X2 are each independently NR, O or S,
R1 및 R2는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 알키닐기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,R1 and R2 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
R은 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고, R is a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
Y1은 O, S 또는 S(=O)이며,Y1 is O, S or S(=O),
R’은 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R'is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a 및 b는 각각 독립적으로, 0 내지 4의 정수이며,a and b are each independently an integer from 0 to 4,
a 및 b가 각각 독립적으로 2 이상의 정수인 경우, 괄호 내의 치환기는 서로 같거나 상이하며, When a and b are each independently an integer of 2 or more, the substituents in parentheses are the same as or different from each other,
x는 1 내지 3의 정수이며,x is an integer from 1 to 3,
y는 0 내지 2의 정수이고,y is an integer from 0 to 2,
x+y = 3이다.x+y = 3.
또 하나의 일 실시상태는 제1 전극; 상기 제1 전극과 대향하여 구비되는 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상이 전술한 화합물을 포함하는 유기발광소자를 제공한다.Another exemplary embodiment includes a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, and at least one layer of the organic material layer provides an organic light emitting device including the above-described compound.
본 발명의 화학식 1로 표시되는 화합물은 유기발광소자의 유기물층의 재료로서 사용될 수 있다.The compound represented by Chemical Formula 1 of the present invention can be used as a material for the organic material layer of the organic light emitting device.
본 발명의 화학식 1로 표시되는 화합물을 포함하여 유기발광소자를 제조하는 경우, 고효율, 저전압 및 장수명 특성을 갖는 유기발광소자를 얻을 수 있다.When an organic light emitting device including the compound represented by Formula 1 of the present invention is manufactured, an organic light emitting device having high efficiency, low voltage and long life characteristics can be obtained.
도 1은 일 실시상태에 따른 유기발광소자의 구조를 도시한 것이다.1 shows a structure of an organic light emitting device according to an exemplary embodiment.
도 2는 또 다른 실시상태에 따른 유기발광소자의 구조를 도시한 것이다.Figure 2 shows the structure of an organic light emitting device according to another embodiment.
<부호의 설명><Description of code>
1: 기판1: Substrate
2: 양극2: anode
3: 발광층3: light emitting layer
4: 음극4: Cathode
5: 정공주입층5: hole injection layer
6: 정공수송층6: hole transport layer
7: 전자차단층7: Electronic blocking layer
8-1: 제1 전자수송층8-1: first electron transport layer
8-2: 제2 전자수송층8-2: second electron transport layer
이하 본 명세서에 대하여 더욱 상세히 설명한다. Hereinafter, this specification will be described in more detail.
본 명세서는 상기 화학식 1로 표시되는 화합물을 제공한다. The present specification provides a compound represented by Chemical Formula 1.
본 명세서에 있어서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.
본 명세서에 있어서, 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.In this specification, when a member is said to be "on" another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.
본 명세서에서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of the substituent in this specification are described below, but are not limited thereto.
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.The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소(-D); 할로겐기; 니트릴기; 니트로기; 히드록시기; 붕소기; 알콕시기; 알킬기; 시클로알킬기; 아릴기; 및 헤테로고리기로 이루어진 군에서 선택된 1 또는 2 이상의 치환기로 치환되었거나 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환기로 치환되거나, 또는 어떠한 치환기도 갖지 않는 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 바이페닐기일 수 있다. 즉, 바이페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수도 있다.The term "substituted or unsubstituted" in this specification is deuterium (-D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Boron group; Alkoxy groups; Alkyl groups; Cycloalkyl group; Aryl group; And 1 or 2 or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents among the above-described substituents, or having no substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
상기 치환기들의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다. Examples of the substituents are described below, but are not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소(-F), 염소(-Cl), 브롬(-Br) 또는 요오드(-I)가 있다.In the present specification, examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).
본 명세서에 있어서, 붕소기는 -BYdYe의 화학식으로 표시될 수 있고, 상기 Yd 및 Ye는 각각 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기일 수 있다. 상기 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, tert-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group may be represented by the formula -BY d Y e , wherein Y d and Y e are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The boron group may include, but is not limited to, trimethyl boron group, triethyl boron group, tert-butyl dimethyl boron group, triphenyl boron group, phenyl boron group, and the like.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 30이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 알킬기의 구체적인 예로는 메틸기, 에틸기, 프로필기, n-프로필기, 이소프로필기, 부틸기, n-부틸기, 이소부틸기, tert-부틸기, 펜틸기, n-펜틸기, 헥실기, n-헥실기, 헵틸기, n-헵틸기, 옥틸기, n-옥틸기 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to one embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, and the like, but is not limited to these.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 30인 것이 바람직하다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkenyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 상기 알키닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 30인 것이 바람직하다. 구체적인 예로는 에틴일(ethynyl), 프로핀일(propynyl), 부틴일(butynyl), 펜틴일(pentynyl), 헥신일(hexynyl), 헵틴일(heptynyl), 옥틴일(octynyl), 노닌일(nonynyl) 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkynyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, and nonynyl. And the like, but is not limited thereto.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 20인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, i-프로필옥시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, and the like, but is not limited thereto. .
본 명세서에 기재된 알킬기, 알콕시기 및 그 외 알킬기 부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함한다.Substituents comprising alkyl, alkoxy, and other alkyl group moieties described herein include both straight-chain or ground forms.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 시클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 시클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 시클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기, 시클로헵틸기, 시클로옥틸기 등이 있으나, 이에 한정되지 않는다. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 39이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기, 쿼터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트레닐기, 파이레닐기, 페릴레닐기, 트리페닐기, 크라이세닐기, 플루오레닐기, 트리페닐레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 39. According to one embodiment, the carbon number of the aryl group is 6 to 30. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto. no.
본 명세서에 있어서, 플루오렌기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다.In the present specification, the fluorene group may be substituted, and two substituents may combine with each other to form a spiro structure.
상기 플루오렌기가 치환되는 경우,
Figure PCTKR2019018487-appb-I000002
등의 스피로플루오렌기,
Figure PCTKR2019018487-appb-I000003
(9,9-디메틸플루오렌기), 및
Figure PCTKR2019018487-appb-I000004
(9,9-디페닐플루오렌기) 등의 치환된 플루오렌기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorene group is substituted,
Figure PCTKR2019018487-appb-I000002
Spirofluorene groups, such as
Figure PCTKR2019018487-appb-I000003
(9,9-dimethylfluorene group), and
Figure PCTKR2019018487-appb-I000004
It may be a substituted fluorene group such as (9,9-diphenylfluorene group). However, it is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 이종원자로 N, O, P, S, Si 및 Se 중 1개 이상을 포함하는 고리기로서, 탄소수는 특별히 한정되지 않으나 탄소수 2 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 헤테로고리기의 탄소수는 2 내지 36이다. 헤테로 고리기의 예로는 예로는 피리딘기, 피롤기, 피리미딘기, 퀴놀린기, 피리다진기, 퓨란기, 티오펜기, 이미다졸기, 피라졸기, 디벤조퓨란기, 디벤조티오펜기, 카바졸기, 벤조카바졸기, 벤조나프토퓨란기, 벤조나프토티오펜기, 인데노카바졸기, 인돌로카바졸기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heteroatom as a ring group containing at least one of N, O, P, S, Si, and Se, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the number of carbon atoms in the heterocyclic group is 2 to 36. Examples of the heterocyclic group include pyridine group, pyrrole group, pyrimidine group, quinoline group, pyridazine group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group, Carbazole group, benzocarbazole group, benzonaphthofuran group, benzonaphthothiophene group, indenocarbazole group, indolocarbazole group, and the like, but are not limited thereto.
본 명세서에 있어서, 헤테로아릴기는 방향족인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, a description of the aforementioned heterocyclic group may be applied, except that the heteroaryl group is aromatic.
본 명세서에 있어서, 헤테로아릴렌기는 2가의 방향족인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, the description of the aforementioned heterocyclic group may be applied, except that the heteroarylene group is a divalent aromatic group.
본 명세서에 있어서, 아민기는 -NH2; 알킬아민기; N-알킬아릴아민기; 아릴아민기; N-아릴헤테로아릴아민기; N-알킬헤테로아릴아민기 및 헤테로아릴아민기로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 1 내지 30인 것이 바람직하다. 아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 바이페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, N-페닐나프틸아민기, 디톨릴아민기, N-페닐톨릴아민기, 트리페닐아민기, N-페닐바이페닐아민기, N-페닐나프틸아민기, N-바이페닐나프틸아민기, N-나프틸플루오레닐아민기, N-페닐페난트레닐아민기, N-바이페닐페난트레닐아민기, N-페닐플루오레닐아민기, N-페닐터페닐아민기, N-페난트레닐플루오레닐아민기, N-바이페닐플루오레닐아민기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the amine group is -NH 2 ; Alkylamine groups; N-alkylarylamine group; Arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine groups and heteroarylamine groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine Group, N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, and the like, but is not limited thereto.
본 명세서에 있어서, N-알킬아릴아민기는 아민기의 N에 알킬기 및 아릴기가 치환된 아민기를 의미한다.In the present specification, the N-alkylarylamine group means an amine group in which N of an amine group is substituted with an alkyl group and an aryl group.
본 명세서에 있어서, N-아릴헤테로아릴아민기는 아민기의 N에 아릴기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-aryl heteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.
본 명세서에 있어서, N-알킬헤테로아릴아민기는 아민기의 N에 알킬기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.
본 명세서에 있어서, 아릴옥시기; 알킬아민기; N-알킬아릴아민기; 아릴아민기; N-아릴헤테로아릴아민기; N-알킬헤테로아릴아민기 및 헤테로아릴아민기 중의 알킬기, 아릴기 및 헤테로아릴기는 각각 전술한 알킬기, 아릴기 및 헤테로아릴기의 설명이 인용될 수 있다. 구체적으로 아릴옥시기로는 페녹시기, p-토릴옥시기, m-토릴옥시기, 3,5-디메틸-페녹시기, 2,4,6-트리메틸페녹시기, p-tert-부틸페녹시기, 3-바이페닐옥시기, 4-바이페닐옥시기, 1-나프틸옥시기, 2-나프틸옥시기, 4-메틸-1-나프틸옥시기, 5-메틸-2-나프틸옥시기, 1-안트릴옥시기, 2-안트릴옥시기, 9-안트릴옥시기, 1-페난트릴옥시기, 3-페난트릴옥시기, 9-페난트릴옥시기 등이 있다.In the present specification, an aryloxy group; Alkylamine groups; N-alkylarylamine group; Arylamine group; N-aryl heteroarylamine group; The alkyl group, the aryl group, and the heteroaryl group in the N-alkylheteroarylamine group and the heteroarylamine group can be cited in the description of the alkyl group, aryl group, and heteroaryl group, respectively. Specifically, aryloxy groups include phenoxy group, p-toryloxy group, m-toryloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like.
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 오르토(ortho)위치로 치환된 2개의 치환기 및 지방족 고리에서 동일 탄소에 치환된 2개의 치환기는 서로 "인접한" 기로 해석될 수 있다.In the present specification, the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. Can. For example, two substituents substituted in the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.
본 명세서에 있어서, 인접한 기와 서로 결합하여 형성되는 치환 또는 비치환된 고리에서, "고리"는 탄화수소 고리; 또는 헤테로 고리를 의미한다.In the present specification, in the substituted or unsubstituted ring formed by bonding with adjacent groups to each other, "ring" is a hydrocarbon ring; Or a hetero ring.
상기 탄화수소 고리는 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 2가기인 것을 제외하고 상기 시클로알킬기 또는 아릴기에 관한 설명이 적용될 수 있다.The hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and a description of the cycloalkyl group or aryl group may be applied except that the divalent group.
상기 헤테로고리는 2가인 것을 제외하고는 상기 헤테로고리기에 대한 설명이 적용될 수 있다.The description of the heterocyclic group may be applied to the heterocycle except that it is divalent.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR, O 또는 S이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently NR, O, or S.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 서로 동일하거나, 상이하다. According to an exemplary embodiment of the present specification, X1 and X2 are the same as or different from each other.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 O이다.According to an exemplary embodiment of the present specification, X1 and X2 is O.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 S이다.According to an exemplary embodiment of the present specification, X1 and X2 is S.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently, NR.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR이고, R은 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently, NR, and R is a substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR이고, R은 치환 또는 비치환된 시클로알킬기; 또는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently, NR, and R is a substituted or unsubstituted cycloalkyl group; Or a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR이고, R은 치환 또는 비치환된 탄소수 3 내지 60의 시클로알킬기; 또는 치환 또는 비치환된 탄소수 6 내지 60의 아릴기이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently NR, and R is a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR이고, R은 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently NR, and R is a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, X1 및 X2는 각각 독립적으로, NR이고, R은 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기; 또는 치환 또는 비치환된 탄소수 6 내지 20의 아릴기이다.According to an exemplary embodiment of the present specification, X1 and X2 are each independently NR, and R is a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
본 명세서의 일 실시상태에 따르면, R1 및 R2는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 알키닐기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R1 및 R2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 아민기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R1 및 R2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 아민기; 치환 또는 비치환된 탄소수 1 내지 60의 알킬기; 치환 또는 비치환된 탄소수 3 내지 60의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 60의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R1 및 R2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 아민기; 치환 또는 비치환된 탄소수 1 내지 30의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R1 및 R2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 아민기; 치환 또는 비치환된 탄소수 1 내지 15의 알킬기; 치환 또는 비치환된 탄소수 3 내지 15의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 15의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 15의 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R은 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 따르면, R은 치환 또는 비치환된 탄소수 1 내지 60의 알킬기; 치환 또는 비치환된 탄소수 3 내지 60의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 60의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
본 명세서의 일 실시상태에 따르면, R은 치환 또는 비치환된 탄소수 1 내지 30의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, R은 치환 또는 비치환된 탄소수 1 내지 15의 알킬기; 치환 또는 비치환된 탄소수 3 내지 15의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 15의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 15의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.
본 명세서의 일 실시상태에 따르면, Y1은 O, S 또는 S(=O)이다.According to an exemplary embodiment of the present specification, Y1 is O, S or S (= O).
본 명세서의 일 실시상태에 따르면, Y1은 O이다.According to an exemplary embodiment of the present specification, Y1 is O.
본 명세서의 일 실시상태에 따르면, Y1은 S이다.According to an exemplary embodiment of the present specification, Y1 is S.
본 명세서의 일 실시상태에 따르면, Y1은 S(=O)이다.According to the exemplary embodiment of the present specification, Y1 is S(=O).
본 명세서의 일 실시상태에 따르면, R'은 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. According to an exemplary embodiment of the present specification, R'is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 따르면, R'은 치환 또는 비치환된 탄소수 1 내지 60의 알킬기; 치환 또는 비치환된 탄소수 6 내지 60의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R'is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
본 명세서의 일 실시상태에 따르면, R'은 치환 또는 비치환된 탄소수 1 내지 30의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R'is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, R'은 치환 또는 비치환된 탄소수 1 내지 15의 알킬기; 치환 또는 비치환된 탄소수 6 내지 15의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 15의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R'is a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.
본 명세서의 일 실시상태에 따르면, R'은 치환 또는 비치환된 탄소수 6 내지 60의 아릴기이다.According to an exemplary embodiment of the present specification, R'is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
본 명세서의 일 실시상태에 따르면, a 및 b가 각각 독립적으로 2 이상의 정수인 경우, 괄호 내의 치환기는 서로 같거나 상이하며, 서로 인접한 기는 결합하여 치환 또는 비치환된 고리를 형성할 수 있다. 즉, 복수의 R1 또는 R2는 R1끼리 또는 R2끼리 서로 결합하여 고리를 형성할 수도 있으며, R1 및 R2가 서로 결합하여 고리를 형성할 수도 있다.According to an exemplary embodiment of the present specification, when a and b are each independently an integer of 2 or more, the substituents in parentheses are the same or different from each other, and groups adjacent to each other may combine to form a substituted or unsubstituted ring. That is, a plurality of R1 or R2 may be combined with each other R1 or R2 to form a ring, or R1 and R2 may combine with each other to form a ring.
본 명세서의 일 실시상태에 따르면, R1 및 R2가 각각 독립적으로 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하는 경우, 직접결합; 또는 하기 구조 중 어느 하나의 고리를 형성할 수 있다.According to one embodiment of the present specification, when R1 and R2 each independently combine with an adjacent group to form a substituted or unsubstituted ring, a direct bond; Alternatively, any one of the following structures may be formed.
Figure PCTKR2019018487-appb-I000005
Figure PCTKR2019018487-appb-I000005
상기 구조에서,In the above structure,
A1 내지 A24은 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,A1 to A24 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a1 내지 a11은 각각 0 내지 4의 정수이고, a1 to a11 are each an integer from 0 to 4,
a12는 0 내지 6의 정수이며,a12 is an integer from 0 to 6,
*는 치환되는 위치를 표시한 것이다.* Indicates the position to be substituted.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 2 또는 3으로 표시된다.According to an exemplary embodiment of the present specification, the formula 1 is represented by the following formula 2 or 3.
[화학식 2][Formula 2]
Figure PCTKR2019018487-appb-I000006
Figure PCTKR2019018487-appb-I000006
[화학식 3][Formula 3]
Figure PCTKR2019018487-appb-I000007
Figure PCTKR2019018487-appb-I000007
R3 내지 R6는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 알키닐기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,R3 to R6 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
c 및 d는 각각 독립적으로, 0 내지 4의 정수이고,c and d are each independently an integer from 0 to 4,
e 및 f는 각각 독립적으로, 0 내지 3의 정수이고,e and f are each independently an integer from 0 to 3,
c 내지 f가 2 이상인 경우, 괄호 내의 치환기는 서로 같거나 상이하며,When c to f are 2 or more, the substituents in parentheses are the same as or different from each other,
Y2는 CR10R11, SiR12R13, NR14, O, S, P(=O)R15, PR16, S(=O) 또는 S(=O)2이고,Y2 is CR10R11, SiR12R13, NR14, O, S, P(=O)R15, PR16, S(=O) or S(=O) 2 ,
R10 내지 R13은 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,R10 to R13 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
R14 내지 R16는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R14 to R16 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
X1, X2, Y1, R', x 및 y는 화학식 1과 같다.X1, X2, Y1, R', x and y are as in the formula (1).
본 명세서의 일 실시상태에 따르면, R3 내지 R6은 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 알키닐기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다. According to an exemplary embodiment of the present specification, R3 to R6 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R3 내지 R6는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 아민기; 치환 또는 비치환된 탄소수 1 내지 30의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R3 to R6 are each independently, hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면 R3 내지 R6은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 아민기; 치환 또는 비치환된 탄소수 1 내지 15의 알킬기; 치환 또는 비치환된 탄소수 6 내지 15의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 15의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R3 to R6 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkyl group having 1 to 15 carbon atoms; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.
본 명세서의 일 실시상태에 따르면, R3 내지 R6은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 탄소수 6 내지 15의 아릴기이다.According to an exemplary embodiment of the present specification, R3 to R6 are each independently, hydrogen; heavy hydrogen; It is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.
본 명세서의 일 실시상태에 따르면, R10 내지 R13은 각각 독립적으로, 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R10 to R13 are each independently, a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R10 내지 R13은 각각 독립적으로, 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R10 to R13 are each independently, a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group, or may combine with an adjacent group to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R10 내지 R13은 각각 독립적으로, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, R10 to R13 are each independently, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or may be combined with adjacent groups to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 따르면, R14 내지 R16는 각각 독립적으로, 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, R14 to R16 are each independently, a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, R14 내지 R16는 각각 독립적으로, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.According to an exemplary embodiment of the present specification, R14 to R16 are each independently, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, c 내지 f가 각각 독립적으로 2 이상의 정수인 경우, 괄호 내의 치환기는 서로 같거나 상이하며, 서로 인접한 기는 결합하여 치환 또는 비치환된 고리를 형성할 수 있다. 구체적으로, 복수의 R3, 복수의 R4, 복수의 R5 또는 복수의 R6은 R3끼리, R4끼리, R5끼리 또는 R6끼리 서로 결합하여 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, when c to f are each independently an integer of 2 or more, the substituents in parentheses are the same or different from each other, and groups adjacent to each other may combine to form a substituted or unsubstituted ring. Specifically, a plurality of R3, a plurality of R4, a plurality of R5 or a plurality of R6 may form a ring by combining R3, R4, R5 or R6 with each other.
본 명세서의 일 실시상태에 따르면, R3 내지 R6이 각각 독립적으로 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하는 경우, 직접결합; 또는 하기 구조 중 어느 하나의 고리를 형성할 수 있다.According to an exemplary embodiment of the present specification, when R3 to R6 are each independently bonded to an adjacent group to form a substituted or unsubstituted ring, a direct bond; Alternatively, any one of the following structures may be formed.
Figure PCTKR2019018487-appb-I000008
Figure PCTKR2019018487-appb-I000008
A1 내지 A12 및 A20 내지 A24은 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,A1 to A12 and A20 to A24 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a1 내지 a11은 각각 0 내지 4의 정수이고, a1 to a11 are each an integer from 0 to 4,
a12는 0 내지 6의 정수이며,a12 is an integer from 0 to 6,
*는 치환되는 위치를 표시한 것이다.* Indicates the position to be substituted.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1로 표시되는 화합물 중 나프탈렌이 포함되지 않은 화합물은 ΔEst 0.25eV 미만의 지연형광 특성을 갖는다.According to an exemplary embodiment of the present specification, a compound not containing naphthalene among the compounds represented by the formula (1) has a delayed fluorescence property of less than ΔE st 0.25eV.
일반적인 유기발광소자에서 일중항과 삼중항에서 생성되는 엑시톤의 수가 25:75(일중항:삼중항)의 비율로 생성되며, 엑시톤 이동에 따른 발광 형태에 따라 형광 발광, 인광 발광 및 열활성화 지연형광 발광으로 나눌 수 있다. 상기 열활성화 지연형광은 삼중항 여기자로부터 일중항 여기자로의 역항간 교차(Reverse Intersystem Crossing(RISC))가 일어나는 현상을 이용한 현상을 나타내며, 이는 Thermally Activated Delayed Fluorescence(TADF)라고 지칭하기도 한다. 이러한 열활성화 지연형광을 이용하면, 전계 여기에 의한 형광 발광에 있어서도, 이론적으로는 인광 발광과 동등한 100%의 내부 양자 효율이 가능하게 된다The number of excitons generated in the singlet and triplet in a general organic light emitting device is generated at a ratio of 25:75 (single term: triplet), and the fluorescent emission, phosphorescence emission, and thermal activation delayed fluorescence depending on the emission type according to exciton movement It can be divided into luminescence. The thermally activated delayed fluorescence represents a phenomenon using a phenomenon of reverse intersystem crossing (RISC) from triplet exciton to singlet exciton, which is also referred to as Thermally Activated Delayed Fluorescence (TADF). When such a heat activated delayed fluorescence is used, even in fluorescence emission by electric field excitation, theoretically, an internal quantum efficiency of 100% equivalent to phosphorescence emission is possible.
열활성화 지연형광을 발현시키기 위해서는, 실온 또는 발광 소자 중의 발광층 온도에서 전계 여기에 의해 발생한 75%의 삼중항 여기자로부터 일중항 여기자로의 역항간 교차가 일어날 필요가 있다. 또한, 역항간 교차에 의해 발생한 일중항 여기자가, 직접 여기에 의해 발생한 25%의 일중항 여기자와 마찬가지로 형광 발광함으로써, 전술한 100%의 내부 양자 효율이 이론상 가능하게 된다. 이 역항간 교차가 일어나기 위해서는, 최저 여기 일중항 에너지 준위(S1)와 최저 삼중항 여기 에너지 준위(T1)와의 차의 절댓값(ΔEst)이 작을 것이 요구된다.In order to express the thermally activated delayed fluorescence, it is necessary that an inverse crossover from 75% of triplet excitons generated by electric field excitation to singlet excitation occurs at room temperature or at the temperature of the light emitting layer in the light emitting element. In addition, by fluorescing the singlet excitons generated by inverse crossing between the singlet excitons of 25% generated by direct excitation, the above-described internal quantum efficiency of 100% is theoretically possible. In order for this inverse intersection to occur, it is required that the absolute value ΔE st of the difference between the lowest excitation singlet energy level S1 and the lowest triplet excitation energy level T1 is small.
상기 화학식 1로 표시되는 화합물 중 나프탈렌이 포함되지 않은 물질은 β Est 0.25eV 미만의 지연 형광 특성을 가짐으로써, 일반적으로 삼중항 여기 상태(excited state)의 엑시톤들이 일중항 여기 상태(excited state)로 역계간전이하여 그 에너지를 도펀트로 전달하여 고효율을 갖는 유기발광소자를 구현할 수 있다. 또한 메톡시기(전자주개)와는 다르게 전자 당김 효과와 정사면체 구조(Tetrahedral structure)로 인하여 반치폭을 더 줄이면서, 물질과 물질간의 거리를 증가시켜 스태킹(stacking)이 되지 않게 하여 Triplet-polaron quenching을 억제하여 효율을 증가 시킬 수 있고, 원하는 파장을 조율(tuning)하며, 단단한 구조(Rigid form)를 형성하고 물질의 안전성을 높일 수 있다.Among the compounds represented by Chemical Formula 1, a substance that does not contain naphthalene has a delayed fluorescence property of less than β E st 0.25 eV, so that excitons in a triplet excited state are typically singlet excited state. It is possible to implement an organic light emitting device having high efficiency by transferring the energy to the dopant by inverse transitioning. In addition, unlike the methoxy group (electron donor), the electron pull effect and the tetrahedral structure further reduce the half-width, increasing the distance between the material and the material to prevent stacking, thereby suppressing triplet-polaron quenching. It can increase the efficiency, tune the desired wavelength, form a rigid structure (Rigid form) and increase the safety of the material.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화합물들 중 어느 하나로 표시될 수 있다.According to an exemplary embodiment of the present specification, the formula 1 may be represented by any one of the following compounds.
Figure PCTKR2019018487-appb-I000009
Figure PCTKR2019018487-appb-I000009
Figure PCTKR2019018487-appb-I000010
Figure PCTKR2019018487-appb-I000010
Figure PCTKR2019018487-appb-I000011
Figure PCTKR2019018487-appb-I000011
Figure PCTKR2019018487-appb-I000012
Figure PCTKR2019018487-appb-I000012
Figure PCTKR2019018487-appb-I000013
Figure PCTKR2019018487-appb-I000013
Figure PCTKR2019018487-appb-I000014
Figure PCTKR2019018487-appb-I000014
Figure PCTKR2019018487-appb-I000015
Figure PCTKR2019018487-appb-I000015
Figure PCTKR2019018487-appb-I000016
Figure PCTKR2019018487-appb-I000016
Figure PCTKR2019018487-appb-I000017
Figure PCTKR2019018487-appb-I000017
Figure PCTKR2019018487-appb-I000018
Figure PCTKR2019018487-appb-I000018
Figure PCTKR2019018487-appb-I000019
Figure PCTKR2019018487-appb-I000019
Figure PCTKR2019018487-appb-I000020
Figure PCTKR2019018487-appb-I000020
Figure PCTKR2019018487-appb-I000021
Figure PCTKR2019018487-appb-I000021
Figure PCTKR2019018487-appb-I000022
Figure PCTKR2019018487-appb-I000022
Figure PCTKR2019018487-appb-I000023
Figure PCTKR2019018487-appb-I000023
Figure PCTKR2019018487-appb-I000024
Figure PCTKR2019018487-appb-I000024
Figure PCTKR2019018487-appb-I000025
Figure PCTKR2019018487-appb-I000025
Figure PCTKR2019018487-appb-I000026
Figure PCTKR2019018487-appb-I000026
Figure PCTKR2019018487-appb-I000027
Figure PCTKR2019018487-appb-I000027
Figure PCTKR2019018487-appb-I000028
Figure PCTKR2019018487-appb-I000028
Figure PCTKR2019018487-appb-I000029
Figure PCTKR2019018487-appb-I000029
Figure PCTKR2019018487-appb-I000030
Figure PCTKR2019018487-appb-I000030
Figure PCTKR2019018487-appb-I000031
Figure PCTKR2019018487-appb-I000031
Figure PCTKR2019018487-appb-I000032
Figure PCTKR2019018487-appb-I000032
Figure PCTKR2019018487-appb-I000033
Figure PCTKR2019018487-appb-I000033
Figure PCTKR2019018487-appb-I000034
Figure PCTKR2019018487-appb-I000034
Figure PCTKR2019018487-appb-I000035
Figure PCTKR2019018487-appb-I000035
Figure PCTKR2019018487-appb-I000036
Figure PCTKR2019018487-appb-I000036
Figure PCTKR2019018487-appb-I000037
Figure PCTKR2019018487-appb-I000037
Figure PCTKR2019018487-appb-I000038
Figure PCTKR2019018487-appb-I000038
Figure PCTKR2019018487-appb-I000039
Figure PCTKR2019018487-appb-I000039
Figure PCTKR2019018487-appb-I000040
Figure PCTKR2019018487-appb-I000040
Figure PCTKR2019018487-appb-I000041
Figure PCTKR2019018487-appb-I000041
Figure PCTKR2019018487-appb-I000042
Figure PCTKR2019018487-appb-I000042
Figure PCTKR2019018487-appb-I000043
Figure PCTKR2019018487-appb-I000043
Figure PCTKR2019018487-appb-I000044
Figure PCTKR2019018487-appb-I000044
Figure PCTKR2019018487-appb-I000045
Figure PCTKR2019018487-appb-I000045
Figure PCTKR2019018487-appb-I000046
Figure PCTKR2019018487-appb-I000046
Figure PCTKR2019018487-appb-I000047
Figure PCTKR2019018487-appb-I000047
Figure PCTKR2019018487-appb-I000048
Figure PCTKR2019018487-appb-I000048
본 명세서에서는 상기와 같이 코어 구조에 다양한 치환기를 도입함으로써 다양한 에너지 밴드갭을 갖는 화합물을 합성할 수 있다. 또한, 본 명세서에서는 상기와 같은 구조의 코어 구조에 다양한 치환기를 도입함으로써 화합물의 HOMO 및 LUMO 에너지 준위도 조절할 수 있다.In the present specification, compounds having various energy band gaps can be synthesized by introducing various substituents to the core structure as described above. In addition, in this specification, the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents to the core structure having the above structure.
또한, 본 명세서에 따른 유기발광소자는 제1 전극; 상기 제1 전극과 대향하여 구비되는 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상은 상기 전술한 화합물을 포함하는 것을 특징으로 한다.In addition, the organic light emitting device according to the present specification includes a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, and at least one layer of the organic material layer comprises the above-described compound.
본 명세서의 유기발광소자는 전술한 화학식 1로 표시되는 화합물을 이용하여 1층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기발광소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic light emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic material layers are formed using the compound represented by Chemical Formula 1 above.
상기 화합물 1로 표시되는 화합물을 포함하는 유기물층이 형성된 유기발광소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥 코팅, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.When manufacturing an organic light emitting device having an organic material layer formed of the compound represented by the compound 1, it may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method. Here, the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
본 명세서의 유기발광소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기발광소자는 유기물층으로서 정공수송층, 정공주입층, 전자차단층, 정공수송 및 정공주입을 동시에 하는 층, 전자수송층, 전자주입층, 정공차단층, 및 전자수송 및 주입을 동시에 하는 층 중 1층 이상을 포함하는 구조를 가질 수 있다. 그러나, 본 명세서의 유기발광소자의 구조는 이에 한정되지 않고 더 적은 수 또는 더 많은 수의 유기물층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention is a hole transport layer, a hole injection layer, an electron blocking layer, a layer simultaneously performing hole transport and hole injection, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection simultaneously as an organic material layer It may have a structure including one or more of the layers. However, the structure of the organic light emitting device of the present specification is not limited to this, and may include fewer or more organic material layers.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 전자 차단층, 정공 주입층 또는 정공 수송층을 포함하고, 상기 전자 차단층, 정공 주입층 또는 정공 수송층은 상기 화학식 1로 표시되는 화합물을 포함한다. In one embodiment of the present specification, the organic material layer includes an electron blocking layer, a hole injection layer, or a hole transport layer, and the electron blocking layer, a hole injection layer, or a hole transport layer includes a compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 정공 차단층, 전자 주입층 또는 전자 수송층을 포함하고, 상기 정공 차단층, 전자 주입층 또는 전자 수송층은 상기 화학식 1로 표시되는 화합물을 포함한다. In one embodiment of the present specification, the organic material layer includes a hole blocking layer, an electron injection layer, or an electron transport layer, and the hole blocking layer, an electron injection layer, or an electron transport layer includes a compound represented by Chemical Formula 1.
또 하나의 본 명세서의 유기발광소자에서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 전술한 화학식 1로 표시되는 화합물을 포함할 수 있다.In another organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1 described above.
또 하나의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 전술한 화학식 1로 표시되는 화합물을 발광층의 도펀트로 포함할 수 있다.According to another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer may include the compound represented by Chemical Formula 1 as a dopant in the light emitting layer.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 전술한 화학식 1로 표시되는 화합물을 포함하는 도펀트; 및 호스트를 포함할 수 있다. 이때, 상기 발광층 내에서, 호스트와 도펀트의 중량비율은 90: 10 이상, 91:9 이상, 92:8 이상, 93:7 이상, 94:6 이상, 95:5 이상, 96:4 이상, 97:3 이상, 또는 98:2 이상이며, 99.9:0.1 이하, 99.8:0.2 이하, 99.7:0.3 이하, 99.6:0.4 이하, 99.5:0.5 이하, 99.4:0.6 이하, 99.3:0.7 이하, 99.2:0.8 이하, 99.1:0.9 이하 또는 99:1 이하일 수 있다.In one embodiment of the present specification, the organic material layer includes a dopant comprising a compound represented by Formula 1 described above; And a host. At this time, in the light emitting layer, the weight ratio of the host and the dopant is 90: 10 or more, 91:9 or more, 92:8 or more, 93:7 or more, 94:6 or more, 95:5 or more, 96:4 or more, 97 :3 or more, or 98:2 or more, 99.9:0.1 or less, 99.8:0.2 or less, 99.7:0.3 or less, 99.6:0.4 or less, 99.5:0.5 or less, 99.4:0.6 or less, 99.3:0.7 or less, 99.2:0.8 or less , 99.1:0.9 or less, or 99:1 or less.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층, 정공 차단층 및 전자 차단층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함한다.In one embodiment of the present specification, the organic material layer further includes one or two or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer. do.
본 명세서의 일 실시상태에 있어서, 상기 제1 전극은 양극이고, 제2 전극은 음극이다.In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.
또 하나의 일 실시상태에 따르면, 상기 제1 전극은 음극이고, 제2 전극은 양극이다.According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.
상기 유기발광소자는 예컨대 하기와 같은 적층 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.The organic light emitting device may have, for example, a stacked structure as described below, but is not limited thereto.
(1) 양극/정공수송층/발광층/음극(1) anode/hole transport layer/light emitting layer/cathode
(2) 양극/정공주입층/정공수송층/발광층/음극(2) anode/hole injection layer/hole transport layer/light emitting layer/cathode
(3) 양극/정공수송층/발광층/전자수송층/음극(3) anode/hole transport layer/light emitting layer/electron transport layer/cathode
(4) 양극/정공수송층/발광층/전자수송층/전자주입층/음극(4) anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(5) 양극/정공주입층/정공수송층/발광층/전자수송층/음극(5) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode
(6) 양극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/음극(6) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(7) 양극/정공수송층/전자차단층/발광층/전자수송층/음극(7) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
(8) 양극/ 정공수송층/전자차단층/발광층/전자수송층/전자주입층/음극(8) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode
(9) 양극/정공주입층/정공수송층/전자차단층/발광층/전자수송층/음극(9) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
(10) 양극/정공주입층/정공수송층/전자차단층/발광층/전자수송층/전자주입 층/음극(10) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode
(11) 양극/정공수송층/발광층/정공차단층/전자수송층/음극(11) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode
(12) 양극/정공수송층/발광층/정공차단층/전자수송층/전자주입층/음극(12) Anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
(13) 양극/정공주입층/정공수송층/발광층/정공차단층/전자수송층/음극(13) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode
(14) 양극/정공주입층/정공수송층/발광층/정공차단층/전자수송층/전자주입 층/음극(14) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
(15) 양극/정공주입층/정공수송층/전자차단층/발광층/제1 전자수송층/제2 전자수송층/음극(15) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/first electron transport layer/second electron transport layer/cathode
(16) 양극/정공주입층/정공수송층/전자차단층/발광층/전자주입 및 전자수송을 동시에 하는 층/음극(16) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/layer/cathode simultaneously performing electron injection and electron transport
본 명세서의 유기발광소자의 구조는 도 1 및 도 2에 나타낸 것과 같은 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.The structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
도 1에는 기판(1) 위에 양극(2), 발광층(3) 및 음극(4)이 순차적으로 적층된 유기발광소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서, 상기 화합물은 상기 발광층(3)에 포함될 수 있다.1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In such a structure, the compound may be included in the light emitting layer 3.
도 2에는 기판(1) 위에 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(7), 발광층(3), 제1 전자수송층(8-1), 제2 전자수송층(8-2) 및 음극(4)이 순차적으로 적층된 유기발광소자의 구조가 예시되어 있다. In FIG. 2, the anode 2 on the substrate 1, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 3, the first electron transport layer 8-1, the second The structure of the organic light emitting device in which the electron transport layer 8-2 and the cathode 4 are sequentially stacked is illustrated.
예컨대, 본 명세서에 따른 유기발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자차단층, 전자수송층 및 전자주입층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수도 있다.For example, the organic light emitting device according to the present specification uses a metal vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to have a metal or conductive metal oxide on the substrate or alloys thereof To form an anode, to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer, and then depositing a material that can be used as a cathode thereon Can be. In addition to this method, an organic light emitting device may be made by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
상기 유기물층은 정공주입층, 정공수송층, 전자주입 및 전자수송을 동시에 하는 층, 전자차단층, 발광층 및 전자수송층, 전자주입층, 전자주입 및 전자수송을 동시에 하는 층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. 또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용매 공정(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.The organic material layer may be a multi-layer structure including a hole injection layer, a hole transport layer, an electron injection and electron transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, an electron injection layer, an electron injection and electron transport layer, and the like. However, it is not limited thereto, and may be a single-layer structure. In addition, the organic material layer may use a variety of polymer materials to reduce the number of solvent processes (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer) rather than deposition. Can be prepared in layers.
상기 양극은 정공을 주입하는 전극으로, 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO, Indium Tin Oxide), 인듐아연 산화물(IZO, Indium Zinc Oxide)과 같은 금속 산화물; ZnO : Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The positive electrode is an electrode for injecting holes, and a positive electrode material is preferably a material having a large work function to facilitate hole injection into an organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 음극은 전자를 주입하는 전극으로, 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.The cathode is an electrode for injecting electrons, and the cathode material is preferably a material having a small work function to facilitate electron injection into an organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; There is a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
상기 정공주입층은 양극으로부터 발광층으로 정공의 주입을 원활하게 하는 역할을 하는 층이며, 정공 주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입 받을 수 있는 물질로서, 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. 정공주입층의 두께는 1 내지 150nm일 수 있다. 상기 정공주입층의 두께가 1nm 이상이면, 정공 주입 특성이 저하되는 것을 방지할 수 있는 이점이 있고, 150nm 이하이면, 정공주입층의 두께가 너무 두꺼워 정공의 이동을 향상시키기 위해 구동전압이 상승되는 것을 방지할 수 있는 이점이 있다.The hole injection layer is a layer that serves to smoothly inject holes from the anode to the light emitting layer. As the hole injection material, a hole injection material can be well injected with holes from the anode at a low voltage, and HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto. The hole injection layer may have a thickness of 1 to 150 nm. When the thickness of the hole injection layer is 1 nm or more, there is an advantage of preventing the hole injection characteristics from being deteriorated. If it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement. There is an advantage that can be prevented.
상기 정공수송층은 정공의 수송을 원활하게 하는 역할을 할 수 있다. 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer may serve to facilitate the transport of holes. As a hole transport material, a material capable of receiving holes from an anode or a hole injection layer and transferring them to the light emitting layer is suitable for a material having high mobility for holes. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
상기 정공수송층과 발광층 사이에 전자차단층이 구비될 수 있다. 상기 전자차단층은 당 기술분야에 알려져 있는 재료가 사용될 수 있다.An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron blocking layer may be a material known in the art.
상기 발광층은 적색, 녹색 또는 청색을 발광할 수 있으며, 인광 물질 또는 형광 물질로 이루어질 수 있다. 상기 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다.The light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence.
본 명세서의 일 실시상태에 따른 유기 발광 소자는 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물 및 하기 화학식 H로 표시되는 화합물을 포함한다. The organic light emitting diode according to the exemplary embodiment of the present specification includes a light emitting layer, and the light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula H below.
[화학식 H][Formula H]
Figure PCTKR2019018487-appb-I000049
Figure PCTKR2019018487-appb-I000049
상기 화학식 H에 있어서,In the formula H,
L21 내지 L23은 서로 동일하거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이고,L21 to L23 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R21 내지 R27은 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고,R21 to R27 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar21 내지 Ar23은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고, Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
a은 0 또는 1이다.a is 0 or 1.
본 명세서의 일 실시상태에 있어서, a이 0인 경우, -L23-Ar23의 위치는 수소 또는 중수소가 연결된다.In one embodiment of the present specification, when a is 0, the position of -L23-Ar23 is connected to hydrogen or deuterium.
본 명세서의 일 실시상태에 있어서, L21 내지 L23은 서로 동일하거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 C6-C30의 아릴렌기; 또는 치환 또는 비치환되고 N, O, 또는 S를 포함하는 C2-C30의 헤테로아릴렌기이다.In one embodiment of the present specification, L21 to L23 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted C6-C30 arylene group; Or a substituted or unsubstituted C2-C30 heteroarylene group containing N, O, or S.
본 명세서의 일 실시상태에 있어서, L21 내지 L23은 서로 동일하거나 상이하고, 각각 독립적으로 직접결합; C6-C30의 아릴렌기; 또는 N, O, 또는 S를 포함하는 C2-C30의 헤테로아릴렌기이고, 상기 아릴렌기 또는 헤테로아릴렌기는 C1-C10의 알킬기, C6-C30의 아릴기 또는 C2-C30의 헤테로아릴기로 치환되거나 비치환된다. In one embodiment of the present specification, L21 to L23 are the same as or different from each other, and each independently a direct bond; C6-C30arylene group; Or a C2-C30 heteroarylene group containing N, O, or S, wherein the arylene group or heteroarylene group is substituted or unsubstituted with a C1-C10 alkyl group, a C6-C30 aryl group, or a C2-C30 heteroaryl group. Is bright.
본 명세서의 일 실시상태에 있어서, L21 내지 L23은 서로 동일하거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 비페닐렌기; 치환 또는 비치환된 나프틸렌기; 치환 또는 비치환된 2가의 디벤조퓨란기; 또는 치환 또는 비치환된 2가의 디벤조티오펜기이다. In one embodiment of the present specification, L21 to L23 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted divalent dibenzofuran group; Or a substituted or unsubstituted divalent dibenzothiophene group.
본 명세서의 일 실시상태에 있어서, Ar21 내지 Ar23은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 C6-C30의 아릴기; 또는 치환 또는 비치환된 C2-C30의 헤테로아릴기이다.In one embodiment of the present specification, Ar21 to Ar23 are the same or different from each other, and each independently a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted C2-C30 heteroaryl group.
본 명세서의 일 실시상태에 있어서, Ar21 내지 Ar23은 서로 동일하거나 상이하고, 각각 독립적으로 중수소로 치환 또는 비치환된 C6-C30의 아릴기; 또는 중수소로 치환 또는 비치환된 C2-C30의 헤테로아릴기이다.In one embodiment of the present specification, Ar21 to Ar23 are the same or different from each other, and each independently a substituted or unsubstituted C6-C30 aryl group with deuterium; Or a C2-C30 heteroaryl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 있어서, Ar21 내지 Ar23은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 단환 내지 4환의 아릴기; 또는 치환 또는 비치환된 단환 내지 4환의 헤테로아릴기이다.In one embodiment of the present specification, Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic to 4 ring aryl group; Or a substituted or unsubstituted monocyclic to 4 ring heteroaryl group.
본 명세서의 일 실시상태에 있어서, Ar21 내지 Ar23은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 중수소로 단환 내지 4환의 아릴기; 또는 중수소로 치환 또는 비치환된 단환 내지 4환의 헤테로아릴기이다.In one embodiment of the present specification, Ar21 to Ar23 are the same as or different from each other, and each independently a substituted or unsubstituted deuterium monocyclic to 4 ring aryl group; Or a monocyclic to 4 ring heteroaryl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 있어서, Ar21 내지 Ar23은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 안트라센기; 치환 또는 비치환된 페난트릴기; 치환 또는 비치환된 페날렌기; 치환 또는 비치환된 플루오레닐기; 치환 또는 비치환된 벤조플루오레닐기; 치환 또는 비치환된 퓨란기; 치환 또는 비치환된 티오펜기; 치환 또는 비치환된 디벤조퓨란기; 치환 또는 비치환된 나프토벤조퓨란기; 치환 또는 비치환된 디벤조티오펜기; 또는 치환 또는 비치환된 나프토벤조티오펜기이다.In one embodiment of the present specification, Ar21 to Ar23 are the same as or different from each other, and each independently substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracene group; A substituted or unsubstituted phenanthryl group; A substituted or unsubstituted phenylene group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted benzofluorenyl group; A substituted or unsubstituted furan group; A substituted or unsubstituted thiophene group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted naphthobenzofuran group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted naphthobenzothiophene group.
본 명세서의 일 실시상태에 있어서, Ar21 및 Ar22는 서로 상이하다.In one embodiment of the present specification, Ar21 and Ar22 are different from each other.
본 명세서의 일 실시상태에 있어서, Ar21은 치환 또는 비치환된 아릴기이고, Ar22는 치환 또는 비치환된 아릴기이다.In one embodiment of the present specification, Ar21 is a substituted or unsubstituted aryl group, and Ar22 is a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 있어서, Ar21은 치환 또는 비치환된 아릴기이고, Ar22는 치환 또는 비치환된 헤테로아릴기이다.In one embodiment of the present specification, Ar21 is a substituted or unsubstituted aryl group, and Ar22 is a substituted or unsubstituted heteroaryl group.
본 명세서의 일 실시상태에 있어서, Ar21은 중수소로 치환 또는 비치환된 아릴기이고, Ar22는 중수소로 치환 또는 비치환된 아릴기이다.In one embodiment of the present specification, Ar21 is an aryl group unsubstituted or substituted with deuterium, and Ar22 is an aryl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 있어서, Ar21은 중수소로 치환 또는 비치환된 아릴기이고, Ar22는 중수소로 치환 또는 비치환된 헤테로아릴기이다.In one embodiment of the present specification, Ar21 is an aryl group unsubstituted or substituted with deuterium, and Ar22 is a heteroaryl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 있어서, R21 내지 R27은 서로 동일하거나 상이하고, 각각 독립적으로 수소 또는 중수소이다.In one embodiment of the present specification, R21 to R27 are the same as or different from each other, and each independently hydrogen or deuterium.
본 명세서의 일 실시상태에 있어서, R21 내지 R27은 수소이다.In one embodiment of the present specification, R21 to R27 are hydrogen.
본 명세서의 일 실시상태에 있어서, R21 내지 R27은 중수소이다.In one embodiment of the present specification, R21 to R27 are deuterium.
본 명세서의 일 실시상태에 있어서, 상기 화학식 H는 하기 화학식 H01 또는 H02로 표시된다.In one embodiment of the present specification, Chemical Formula H is represented by the following Chemical Formula H01 or H02.
[화학식 H01][Formula H01]
Figure PCTKR2019018487-appb-I000050
Figure PCTKR2019018487-appb-I000050
[화학식 H02][Formula H02]
Figure PCTKR2019018487-appb-I000051
Figure PCTKR2019018487-appb-I000051
상기 화학식 H01 및 H02에 있어서,In the above formula H01 and H02,
L21 내지 L23 및 Ar21 내지 Ar23의 정의는 화학식 H에서 정의한 바와 같고, D는 중수소를 의미하고, k1은 0 내지 8이고, k2는 0 내지 7의 정수이다.The definitions of L21 to L23 and Ar21 to Ar23 are as defined in Formula H, D means deuterium, k1 is 0 to 8, and k2 is an integer from 0 to 7.
본 명세서의 일 실시상태에 있어서, 상기 화학식 H로 표시되는 화합물은 하기 화합물 중 선택된 어느 하나이다. In one embodiment of the present specification, the compound represented by Chemical Formula H is any one selected from the following compounds.
Figure PCTKR2019018487-appb-I000052
Figure PCTKR2019018487-appb-I000052
Figure PCTKR2019018487-appb-I000053
Figure PCTKR2019018487-appb-I000053
Figure PCTKR2019018487-appb-I000054
Figure PCTKR2019018487-appb-I000054
Figure PCTKR2019018487-appb-I000055
Figure PCTKR2019018487-appb-I000055
Figure PCTKR2019018487-appb-I000056
Figure PCTKR2019018487-appb-I000056
본 명세서의 일 실시상태에 따른 유기 발광 소자는 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 발광층의 도펀트로서 포함하고, 상기 화학식 H로 표시되는 화합물을 발광층의 호스트로서 포함한다.The organic light emitting device according to an exemplary embodiment of the present specification includes a light emitting layer, the light emitting layer includes a compound represented by Formula 1 as a dopant in the light emitting layer, and a compound represented by Formula H as a host of the light emitting layer.
본 명세서의 일 실시상태에 있어서, 상기 화학식 H로 표시되는 화합물의 중량 100 중량부 기준으로, 상기 화학식 1로 표시되는 화합물의 함량은 0.01 중량부 내지 30 중량부; 0.1 중량부 내지 20 중량부; 또는 0.5 중량부 내지 10 중량부이다.In one embodiment of the present specification, based on 100 parts by weight of the compound represented by Formula H, the content of the compound represented by Formula 1 is 0.01 parts by weight to 30 parts by weight; 0.1 to 20 parts by weight; Or 0.5 to 10 parts by weight.
상기 화학식 H로 표시되는 화합물은 유기물층(구체적으로는 발광층)에 1종으로 포함될 수 있으며, 2종 이상으로 포함될 수도 있다. 구체적으로 상기 화학식 H로 표시되는 제1 호스트 및 상기 화학식 H로 표시되는 제2 호스트가 유기물층에 포함될 수 있다.The compound represented by Chemical Formula H may be included as one type in the organic material layer (specifically, the light emitting layer), or may be included as two or more types. Specifically, the first host represented by Chemical Formula H and the second host represented by Chemical Formula H may be included in the organic material layer.
상기 화학식 H로 표시되는 제1 호스트 및 상기 화학식 H로 표시되는 제2 호스트의 중량비는 95:5 내지 5:95, 더욱 바람직하게는 30:70 내지 70:30 이다.The weight ratio of the first host represented by Chemical Formula H and the second host represented by Chemical Formula H is 95:5 to 5:95, more preferably 30:70 to 70:30.
본 명세서의 일 실시상태에 있어서, 상기 제1 호스트 및 제2 호스트는 서로 상이하다.In one embodiment of the present specification, the first host and the second host are different from each other.
본 명세서의 일 실시상태에 있어서, 상기 발광층은 상기 화학식 H로 표시되는 화합물을 1종 또는 2종 이상 포함한다.In one embodiment of the present specification, the light emitting layer includes one or two or more compounds represented by Formula H.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물 및 상기 화학식 H로 표시되는 화합물을 포함한 발광층은 청색을 띤다.In one embodiment of the present specification, the light emitting layer including the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula H has a blue color.
본 명세서의 일 실시상태에 따른 유기 발광 소자는 2층 이상의 발광층을 포함하고, 상기 2층 이상의 발광층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물 및 상기 화학식 H로 표시되는 화합물을 포함한다. 상기 화학식 1로 표시되는 화합물 및 상기 화학식 H로 표시되는 화합물을 포함한 발광층은 청색을 띠며, 상기 화학식 1로 표시되는 화합물 및 상기 화학식 H로 표시되는 화합물을 포함하지 않은 발광층은 당업계에 알려진 청색, 적색 또는 녹색 발광 화합물을 포함할 수 있다.The organic light emitting diode according to the exemplary embodiment of the present specification includes two or more light emitting layers, and at least one of the two or more light emitting layers includes a compound represented by Formula 1 and a compound represented by Formula H. The light emitting layer including the compound represented by Formula 1 and the compound represented by Formula H has a blue color, and the light emitting layer not containing the compound represented by Formula 1 and the compound represented by Formula H is blue known in the art, Red or green light-emitting compounds.
상기 전자수송층은 전자의 수송을 원활하게 하는 역할을 할 수 있다. 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자수송층의 두께는 1 내지 50nm일 수 있다. 전자수송층의 두께가 1nm 이상이면, 전자 수송 특성이 저하되는 것을 방지할 수 있는 이점이 있고, 50nm 이하이면, 전자수송층의 두께가 너무 두꺼워 전자의 이동을 향상시키기 위해 구동전압이 상승되는 것을 방지할 수 있는 이점이 있다.The electron transport layer may serve to facilitate the transport of electrons. As the electron transporting material, a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The thickness of the electron transport layer may be 1 to 50 nm. When the thickness of the electron transport layer is 1 nm or more, there is an advantage of preventing the electron transport properties from deteriorating, and when it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from rising to improve the movement of electrons. There is an advantage.
상기 전자주입층은 전자의 주입을 원활하게 하는 역할을 할 수 있다. 전자 주입 물질로는 전자를 수송하는 능력을 갖고, 음극으로부터의 전자주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공 주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 플루오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체 등이 있으나, 이에 한정되지 않는다. The electron injection layer may serve to facilitate injection of electrons. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect for the light emitting layer or the light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also , A compound having excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, and bis(8-hydroxyquinolinato) manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
상기 정공차단층은 정공의 음극 도달을 저지하는 층으로, 일반적으로 정공주입층과 동일한 조건으로 형성될 수 있다. 구체적으로 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP, 알루미늄 착물 (aluminum complex) 등이 있으나, 이에 한정되지 않는다.The hole blocking layer is a layer that prevents the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.
본 발명에 따른 유기발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
이하에서, 실시예를 통하여 본 명세서를 더욱 상세하게 설명한다. 그러나, 이하의 실시예는 본 명세서를 예시하기 위한 것일 뿐, 본 명세서를 한정하기 위한 것은 아니다.Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only intended to illustrate the present specification and are not intended to limit the present specification.
[합성예 1] 화합물 1의 합성[Synthesis Example 1] Synthesis of Compound 1
1) 중간체 1-1의 합성1) Synthesis of Intermediate 1-1
Figure PCTKR2019018487-appb-I000057
Figure PCTKR2019018487-appb-I000057
질소 분위기하에서 디([1,1'-바이페닐]-4-일)아민 26.7g, 2-브로모-1,3-다이아오드-5-(트리플로로메톡시)벤젠 20g, 소듐-tert-부톡사이드 16.0g 및 비스(트리-tert-부틸포스핀)팔라듐(0) 0.2g을 톨루엔 300ml에 넣은 후 4시간 동안 환류 교반하였다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 1-1(25g, 수율 70%)을 수득하였다. MS[M+H]+ = 87926.7 g of di([1,1'-biphenyl]-4-yl)amine under a nitrogen atmosphere, 20 g of 2-bromo-1,3-diode-5-(trifluoromethoxy)benzene, sodium-tert- 16.0 g of butoxide and 0.2 g of bis(tri-tert-butylphosphine)palladium (0) were added to 300 ml of toluene, followed by stirring under reflux for 4 hours. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 1-1 (25 g, yield 70%) was obtained through recrystallization. MS[M+H]+ = 879
2) 화합물1의 합성2) Synthesis of Compound 1
Figure PCTKR2019018487-appb-I000058
Figure PCTKR2019018487-appb-I000058
질소 분위기하에서 중간체 1-1 25g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 17.0ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.0ml를 적가하고, 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 22ml를 투입하고, 반응을 종료한 후 추출한 뒤 재결정을 통하여 화합물 1(8.0g, 수율 35%)을 수득하였다. MS[M+H]+ = 808In a nitrogen atmosphere, 25 g of intermediate 1-1 was added to 400 ml of toluene, lowered to 0° C., and 17.0 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.0 ml of boron tribromide was added dropwise, and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 22 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 1 (8.0 g, yield 35%). MS[M+H]+ = 808
[합성예 2] 화합물 2의 합성[Synthesis Example 2] Synthesis of Compound 2
1) 중간체 2-1의 합성1) Synthesis of Intermediate 2-1
Figure PCTKR2019018487-appb-I000059
Figure PCTKR2019018487-appb-I000059
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g 대신 비스([1,1'-바이페닐]-4-일-2',3',4',5',6'-d5)아민 27.6g을 사용하여 같은 방법으로 반응시켰다. 이 후, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 2-1(24.7g, 수율 68%)을 수득하였다. MS[M+H]+ = 899Under a nitrogen atmosphere, in the synthesis of intermediate 1-1, bis([1,1'-biphenyl]-4-yl-2', instead of 26.7 g of di([1,1'-biphenyl]-4-yl)amine, The reaction was conducted in the same manner using 27.6 g of 3',4',5',6'-d5)amine. Thereafter, after purification with an ethyl acetate:hexane column, intermediate 2-1 (24.7 g, yield 68%) was obtained through recrystallization. MS[M+H]+ = 899
2) 화합물 2의 합성2) Synthesis of Compound 2
Figure PCTKR2019018487-appb-I000060
Figure PCTKR2019018487-appb-I000060
질소 분위기하에서 중간체 2-1 24g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 16.0ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 3.8ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 21ml를 투입하고 반응을 종료한 후 추출한 뒤 재결정을 통하여 화합물 2(7.6g, 수율 34%)를 수득하였다. MS[M+H]+ = 828Under nitrogen atmosphere, 24 g of intermediate 2-1 was added to 400 ml of toluene, lowered to 0° C., and 16.0 ml of n-butyl lithium (1.6M) was slowly added dropwise. After 1 hour, 3.8 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 21 ml of diisopropylethylamine was added, the reaction was terminated, and then extracted and compound 2 (7.6 g, yield 34%) was obtained through recrystallization. MS[M+H]+ = 828
[합성예 3] 화합물 3의 합성[Synthesis Example 3] Synthesis of Compound 3
1) 중간체 3-1의 합성1) Synthesis of Intermediate 3-1
Figure PCTKR2019018487-appb-I000061
Figure PCTKR2019018487-appb-I000061
질소 분위기하에서, 중간체 1-1의 합성법 중 2-브로모-1,3-다이아오드-5-(트리플로로메톡시)벤젠 20g 대신, (4-브로모-3,5-다이아이오드페닐)(트리플로로메틸)설페인 20g을 사용하여 같은 방법으로 반응시켰다. 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 3-1(26.0g, 수율 74%)을 수득하였다. MS[M+H]+ = 895Under a nitrogen atmosphere, instead of 20 g of 2-bromo-1,3-diode-5-(trifluoromethoxy)benzene in the synthesis of intermediate 1-1, (4-bromo-3,5-diiodephenyl) ( The reaction was conducted in the same manner using 20 g of trifluoromethyl) sulfane. After purification with an ethyl acetate:hexane column, intermediate 3-1 (26.0 g, yield 74%) was obtained through recrystallization. MS[M+H]+ = 895
2) 화합물 3의 합성2) Synthesis of Compound 3
Figure PCTKR2019018487-appb-I000062
Figure PCTKR2019018487-appb-I000062
질소 분위기하에서, 중간체 3-1 25g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 16.7ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.0ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 21.8ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 3(7.2g, 수율 31%)을 수득하였다. MS[M+H]+ = 824In a nitrogen atmosphere, 25 g of intermediate 3-1 was added to 400 ml of toluene, lowered to 0° C., and 16.7 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.0 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 21.8 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 3 (7.2 g, yield 31%). MS[M+H]+ = 824
[합성예 4] 화합물 4의 합성[Synthesis Example 4] Synthesis of Compound 4
1) 중간체 4-1의 합성1) Synthesis of Intermediate 4-1
Figure PCTKR2019018487-appb-I000063
Figure PCTKR2019018487-appb-I000063
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g과 2-브로모-1,3-다이아오드-5-(트리플로로메톡시)벤젠 20g 대신, bis([1,1'-바이페닐]-4-yl-2',3',4',5',6'-d5)아민 26.7g과 (4-브로모-3,5-다이아이오드페닐)(트리플로로메틸)설페인 20g을 사용하여 같은 방법으로 반응시켰다. 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 4-1(25.3g, 수율 70%)를 수득하였다. MS[M+H]+ = 916Under a nitrogen atmosphere, 26.7 g of di([1,1'-biphenyl]-4-yl)amine and 2-bromo-1,3-diode-5-(trifluoromethoxy) in the synthesis of intermediate 1-1 ) Instead of 20g of benzene, 26.7g of bis([1,1'-biphenyl]-4-yl-2',3',4',5',6'-d5)amine and (4-bromo-3, The reaction was carried out in the same manner using 20 g of 5-diiodophenyl) (trifluoromethyl) sulfane. After purification with an ethyl acetate:hexane column, intermediate 4-1 (25.3 g, yield 70%) was obtained through recrystallization. MS[M+H]+ = 916
2) 화합물 4의 합성2) Synthesis of Compound 4
Figure PCTKR2019018487-appb-I000064
Figure PCTKR2019018487-appb-I000064
질소 분위기하에서, 중간체 4-1 25g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 16.4ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 3.9ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 22ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 4(7.4g, 수율 32%)를 수득하였다. MS[M+H]+ = 844Under nitrogen atmosphere, 25 g of intermediate 4-1 was added to 400 ml of toluene, lowered to 0° C., and 16.4 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 3.9 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 22 ml of diisopropylethylamine was added, and after completion of the reaction, extraction was carried out, followed by recrystallization to obtain compound 4 (7.4 g, yield 32%). MS[M+H]+ = 844
[합성예 5] 화합물 5의 합성[Synthesis Example 5] Synthesis of Compound 5
1) 중간체 5-1의 합성1) Synthesis of Intermediate 5-1
Figure PCTKR2019018487-appb-I000065
Figure PCTKR2019018487-appb-I000065
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g 대신, N-(4-(tert-부틸)페닐)-[1,1'-바이페닐]-2-아민 24.3g을 사용하여 같은 방법으로 반응시켰다. 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 5-1(24.2g, 수율 73%)를 수득하였다. MS[M+H]+ = 839Under nitrogen atmosphere, instead of 26.7 g of di([1,1'-biphenyl]-4-yl)amine in the synthesis of intermediate 1-1, N-(4-(tert-butyl)phenyl)-[1,1' -Byphenyl]-2-amine was reacted in the same manner using 24.3 g. After purification with an ethyl acetate:hexane column, intermediate 5-1 (24.2 g, yield 73%) was obtained through recrystallization. MS[M+H]+ = 839
2) 화합물 5의 합성2) Synthesis of Compound 5
Figure PCTKR2019018487-appb-I000066
Figure PCTKR2019018487-appb-I000066
질소 분위기하에서, 중간체 5-1 24g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 17.2ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.1ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 22.4ml를 투입하고 반응을 종료한 후 추출한 뒤 재결정을 통하여 화합물 5(7.1g, 수율 32%)를 수득하였다. MS[M+H]+ = 768Under nitrogen atmosphere, 24 g of intermediate 5-1 was added to 400 ml of toluene, lowered to 0° C., and 17.2 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.1 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 22.4 ml of diisopropylethylamine was added, the reaction was terminated, and then extracted and compound 5 (7.1 g, yield 32%) was obtained through recrystallization. MS[M+H]+ = 768
[합성예 6] 화합물 6의 합성[Synthesis Example 6] Synthesis of Compound 6
1) 중간체 6-1의 합성1) Synthesis of Intermediate 6-1
Figure PCTKR2019018487-appb-I000067
Figure PCTKR2019018487-appb-I000067
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g과 2-브로모-1,3-다이아오드-5-(트리플로로메톡시)벤젠 20g 대신, N-(4-(tert-부틸)페닐)-[1,1'-바이페닐]-2-아민 24.3g과 (4-브로모-3,5-다이아이오드페닐)(트리플로로메틸)설페인 20g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 6-1(23.9g, 수율 71%)을 수득하였다. MS[M+H]+ = 855Under a nitrogen atmosphere, 26.7 g of di([1,1'-biphenyl]-4-yl)amine and 2-bromo-1,3-diode-5-(trifluoromethoxy) in the synthesis of intermediate 1-1 ) Instead of 20 g of benzene, 24.3 g of N-(4-(tert-butyl)phenyl)-[1,1'-biphenyl]-2-amine and (4-bromo-3,5-diiodophenyl) (triple The reaction was performed in the same manner using 20 g of roromethyl) sulfane. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 6-1 (23.9 g, yield 71%) was obtained through recrystallization. MS[M+H]+ = 855
2) 화합물 6의 합성2) Synthesis of Compound 6
Figure PCTKR2019018487-appb-I000068
Figure PCTKR2019018487-appb-I000068
질소 분위기하에서, 중간체 6-1 23g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 16.1ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 3.8ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 21.1ml를 투입하고 반응을 종료한 후 추출한 뒤 재결정을 통하여 화합물 6(7.0g, 수율 33%)을 수득하였다. MS[M+H]+ = 784Under nitrogen atmosphere, 23 g of intermediate 6-1 was added to 400 ml of toluene, lowered to 0° C., and 16.1 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 3.8 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 21.1 ml of diisopropylethylamine was added, the reaction was terminated and extracted, and then compound 6 (7.0 g, yield 33%) was obtained through recrystallization. MS[M+H]+ = 784
[합성예 7] 화합물 7의 합성[Synthesis Example 7] Synthesis of Compound 7
1) 중간체 7-1의 합성1) Synthesis of Intermediate 7-1
Figure PCTKR2019018487-appb-I000069
Figure PCTKR2019018487-appb-I000069
질소 분위기하에서, 중간체 1-1의 합성법 중 2-브로모-1,3-다이아오드-5-(트리플로로메톡시)벤젠 20g 대신, 2-브로모-5-(다이플로로(페닐)메톡시)-1,3-다이아이오드벤젠 20g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 7-1(24g, 수율 70%)을 수득하였다. MS[M+H]+ = 937Under a nitrogen atmosphere, instead of 20 g of 2-bromo-1,3-diode-5-(trifluoromethoxy)benzene in the synthesis of intermediate 1-1, 2-bromo-5-(difluoro(phenyl)meth The reaction was carried out in the same manner using 20 g of ethoxy)-1,3-diiodinebenzene. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 7-1 (24 g, yield 70%) was obtained through recrystallization. MS[M+H]+ = 937
2) 화합물 7의 합성2) Synthesis of Compound 7
Figure PCTKR2019018487-appb-I000070
Figure PCTKR2019018487-appb-I000070
질소 분위기하에서, 중간체 7-1 24g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 15.3ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 3.6ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 20.1ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 7(6.4g, 수율 29%)을 수득하였다. MS[M+H]+ = 866Under nitrogen atmosphere, 24 g of intermediate 7-1 was added to 400 ml of toluene, lowered to 0° C., and 15.3 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 3.6 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 20.1 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 7 (6.4 g, yield 29%). MS[M+H]+ = 866
[합성예 8] 화합물 8의 합성[Synthesis Example 8] Synthesis of Compound 8
1) 중간체 8-1의 합성1) Synthesis of Intermediate 8-1
Figure PCTKR2019018487-appb-I000071
Figure PCTKR2019018487-appb-I000071
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g과 2-브로모-1,3-다이아오드-5-(트리플로로메톡시)벤젠 20g 대신, 비스(4'-메틸-[1,1'-바이페닐]-4-일)아민과 25.3(4-브로모-3,5-다이아이오드페닐)(다이플로로(페닐)메틸)설페인 20g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 8-1(22g, 수율 62%)을 수득하였다. MS[M+H]+ = 1010Under a nitrogen atmosphere, 26.7 g of di([1,1'-biphenyl]-4-yl)amine and 2-bromo-1,3-diode-5-(trifluoromethoxy) in the synthesis of intermediate 1-1 ) Instead of 20 g of benzene, bis(4'-methyl-[1,1'-biphenyl]-4-yl)amine and 25.3 (4-bromo-3,5-diiodphenyl) (difluoro (phenyl) The reaction was performed in the same manner using 20 g of methyl) sulfane. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 8-1 (22 g, yield 62%) was obtained through recrystallization. MS[M+H]+ = 1010
2) 화합물 8의 합성2) Synthesis of Compound 8
Figure PCTKR2019018487-appb-I000072
Figure PCTKR2019018487-appb-I000072
질소 분위기하에서, 중간체 8-1 22g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 14.3ml를 천천히 적가하였다. 1시간후 보론트리브로마이드 3.4ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 18.6ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 8(6.4g, 수율 29%)을 수득하였다. MS[M+H]+ = 938Under nitrogen atmosphere, 22 g of intermediate 8-1 was added to 400 ml of toluene, lowered to 0° C., and 14.3 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 3.4 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 18.6 ml of diisopropylethylamine was added, and after completion of the reaction, extraction was performed, and then compound 8 (6.4 g, yield 29%) was obtained through recrystallization. MS[M+H]+ = 938
[합성예 9] 화합물 9의 합성[Synthesis Example 9] Synthesis of Compound 9
1) 중간체 9-1의 합성1) Synthesis of Intermediate 9-1
Figure PCTKR2019018487-appb-I000073
Figure PCTKR2019018487-appb-I000073
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g 대신, N-(나프탈렌-1-일)아다만테인-1-아민 23.1g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 9-1(23.8g, 수율 74%)를 수득하였다. MS[M+H]+ = 79123.1 g of N-(naphthalen-1-yl) adamantane-1-amine instead of 26.7 g of di([1,1'-biphenyl]-4-yl)amine in the synthesis of intermediate 1-1 under a nitrogen atmosphere. Was reacted in the same way. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 9-1 (23.8 g, yield 74%) was obtained through recrystallization. MS[M+H]+ = 791
2) 화합물 9의 합성2) Synthesis of Compound 9
Figure PCTKR2019018487-appb-I000074
Figure PCTKR2019018487-appb-I000074
질소 분위기하에서, 중간체 9-1 23g을 톨루엔 400ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 17.4ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.1ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 22.8ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 9(6.8g, 수율 32%)를 수득하였다. MS[M+H]+ = 720Under nitrogen atmosphere, 23 g of intermediate 9-1 was added to 400 ml of toluene, lowered to 0°C, and 17.4 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.1 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 22.8 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 9 (6.8 g, yield 32%). MS[M+H]+ = 720
[합성예 10] 화합물 10의 합성[Synthesis Example 10] Synthesis of Compound 10
1) 중간체 10-1의 합성1) Synthesis of Intermediate 10-1
Figure PCTKR2019018487-appb-I000075
Figure PCTKR2019018487-appb-I000075
질소 분위기하에서, 중간체 1-1의 합성법 중 디([1,1'-바이페닐]-4-일)아민 26.7g 대신, 비스(9,9-다이메틸-9H-플로렌-2-일)아민 33.4g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 10-1(25.5g, 수율 60%)을 수득하였다. MS[M+H]+ = 1040Under a nitrogen atmosphere, in the synthesis of intermediate 1-1, instead of 26.7 g of di([1,1'-biphenyl]-4-yl)amine, bis(9,9-dimethyl-9H-floren-2-yl) The reaction was carried out in the same manner using 33.4 g of amine. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 10-1 (25.5 g, yield 60%) was obtained through recrystallization. MS[M+H]+ = 1040
2) 화합물 10의 합성2) Synthesis of Compound 10
Figure PCTKR2019018487-appb-I000076
Figure PCTKR2019018487-appb-I000076
질소 분위기하에서, 중간체 10-1 25g을 톨루엔 500ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 14.4ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 3.4ml를 적가하고 100℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 18.8ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 10(7.2g, 수율 31%)을 수득하였다. MS[M+H]+ = 968Under nitrogen atmosphere, 25 g of intermediate 10-1 was added to 500 ml of toluene, lowered to 0°C, and 14.4 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 3.4 ml of boron tribromide was added dropwise and heated to 100° C. and stirred for 6 hours. After lowering the temperature to 0° C., 18.8 ml of diisopropylethylamine was added, and after completion of the reaction, extraction was performed, and then compound 10 (7.2 g, yield 31%) was obtained through recrystallization. MS[M+H]+ = 968
[합성예 11] 화합물 11의 합성[Synthesis Example 11] Synthesis of Compound 11
1) 중간체 11-1의 합성1) Synthesis of Intermediate 11-1
Figure PCTKR2019018487-appb-I000077
Figure PCTKR2019018487-appb-I000077
질소 분위기하에서, 5,5'-(프로판-2,2-디일)비스(3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g, 1,2-다이브로모-3-아이요드-5-(트리플로로메톡시)벤젠 20g, 소듐-tert-부톡사이드 36.9g 및 비스(트리-tert-부틸포스핀)팔라듐(0) 0.4g을 톨루엔 600ml에 넣은 후 12시간 동안 환류 교반하였다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 11-1(14g, 수율 20%)을 수득하였다. MS[M+H]+ = 839Under nitrogen atmosphere, 5,5'-(propane-2,2-diyl)bis(3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) 50g, 1,2-dibromo 12 hours after adding 20 g of -3-iodine-5-(trifluoromethoxy)benzene, 36.9 g of sodium-tert-butoxide and 0.4 g of bis(tri-tert-butylphosphine) palladium (0) to 600 ml of toluene While stirring at reflux. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 11-1 (14 g, yield 20%) was obtained through recrystallization. MS[M+H]+ = 839
2) 화합물 11의 합성2) Synthesis of Compound 11
Figure PCTKR2019018487-appb-I000078
Figure PCTKR2019018487-appb-I000078
질소 분위기하에서 중간체 11-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 23.8ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 5.1ml를 적가하고 70℃로 올린 후 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 24ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 11(2.0g, 수율 9%)을 수득하였다. MS[M+H]+ = 76814g of intermediate 11-1 was added to 200ml of toluene under a nitrogen atmosphere, and then lowered to 0°C, and 23.8ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 5.1 ml of boron tribromide was added dropwise, raised to 70° C., and stirred for 6 hours. After lowering the temperature to 0° C., 24 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 11 (2.0 g, yield 9%). MS[M+H]+ = 768
[합성예 12] 화합물 12의 합성[Synthesis Example 12] Synthesis of Compound 12
1) 중간체 12-1의 합성1) Synthesis of Intermediate 12-1
Figure PCTKR2019018487-appb-I000079
Figure PCTKR2019018487-appb-I000079
질소 분위기하에서, 5,5'-옥시비스 (3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g, 1,2-다이브로모-3-아이요드-5-(트리플로로메톡시)벤젠 20g, 소듐-tert-부톡사이드 38.6g 및 비스(트리-tert-부틸포스핀)팔라듐(0) 0.4g을 톨루엔 600ml에 넣은 후 12시간 동안 환류 교반하였다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 12-1(14.5g, 수율 21%)를 수득하였다. MS[M+H]+ = 813Under nitrogen atmosphere, 5,5'-oxybis (3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) 50g, 1,2-dibromo-3-iodine-5- 20 g of (trifluoromethoxy) benzene, 38.6 g of sodium-tert-butoxide and 0.4 g of bis(tri-tert-butylphosphine)palladium (0) were added to 600 ml of toluene and stirred at reflux for 12 hours. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 12-1 (14.5 g, yield 21%) was obtained through recrystallization. MS[M+H]+ = 813
2) 화합물 12의 합성2) Synthesis of Compound 12
Figure PCTKR2019018487-appb-I000080
Figure PCTKR2019018487-appb-I000080
질소 분위기하에서, 중간체 12-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 24.6ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 5.3ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 24ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 12(2.3g, 수율 10%)을 수득하였다. MS[M+H]+ = 742In a nitrogen atmosphere, 14 g of intermediate 12-1 was added to 200 ml of toluene, lowered to 0° C., and 24.6 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 5.3 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. After lowering the temperature to 0° C., 24 ml of diisopropylethylamine was added, and after the reaction was completed, extraction was carried out, followed by recrystallization to obtain compound 12 (2.3 g, yield 10%). MS[M+H]+ = 742
[합성예 13] 화합물 13의 합성[Synthesis Example 13] Synthesis of Compound 13
1) 중간체 13-1의 합성1) Synthesis of Intermediate 13-1
Figure PCTKR2019018487-appb-I000081
Figure PCTKR2019018487-appb-I000081
질소 분위기하에서, 중간체 11-1의 합성법 중 5,5'-(프로판-2,2-디일)비스(3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g 대신, 5,5'-싸이오비스 (3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 13-1(14.3g, 수율 20%)을 수득하였다. MS[M+H]+ = 82950 g of 5,5'-(propane-2,2-diyl)bis(3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) in the synthesis of intermediate 11-1 under a nitrogen atmosphere Instead, 5,5'-thiobis (3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) was used to react 50 g. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 13-1 (14.3 g, yield 20%) was obtained through recrystallization. MS[M+H]+ = 829
2) 화합물 13의 합성2) Synthesis of Compound 13
Figure PCTKR2019018487-appb-I000082
Figure PCTKR2019018487-appb-I000082
질소 분위기하에서, 중간체 13-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 24.1ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 5.2ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 24ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 13(2.1g, 수율 9%)을 수득하였다. MS[M+H]+ = 756Under nitrogen atmosphere, 14 g of intermediate 13-1 was added to 200 ml of toluene, lowered to 0° C., and 24.1 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 5.2 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. After lowering the temperature to 0° C., 24 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 13 (2.1 g, yield 9%). MS[M+H]+ = 756
[합성예 14] 화합물 14의 합성[Synthesis Example 14] Synthesis of Compound 14
1) 중간체 14-1의 합성1) Synthesis of Intermediate 14-1
Figure PCTKR2019018487-appb-I000083
Figure PCTKR2019018487-appb-I000083
질소 분위기하에서, 중간체 11-1의 합성법 중 5,5'-(프로판-2,2-디일)비스(3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g 대신, 5,5'-(다이페닐실란디일)비스(3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 14-1(14.0g, 수율 21%)를 수득하였다. MS[M+H]+ = 98050 g of 5,5'-(propane-2,2-diyl)bis(3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) in the synthesis of intermediate 11-1 under a nitrogen atmosphere Instead, 5,5'-(diphenylsilanediyl)bis(3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) was reacted in the same manner using 50 g. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 14-1 (14.0 g, yield 21%) was obtained through recrystallization. MS[M+H]+ = 980
2) 화합물 14의 합성2) Synthesis of Compound 14
Figure PCTKR2019018487-appb-I000084
Figure PCTKR2019018487-appb-I000084
질소 분위기하에서 중간체 14-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 20.4ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.4ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 20ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 14(1.8g, 수율 8%)을 수득하였다. MS[M+H]+ = 909In a nitrogen atmosphere, 14 g of intermediate 14-1 was added to 200 ml of toluene, lowered to 0° C., and 20.4 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.4 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. After lowering the temperature to 0°C, 20 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 14 (1.8 g, yield 8%). MS[M+H]+ = 909
[합성예 15] 화합물 15의 합성[Synthesis Example 15] Synthesis of Compound 15
1) 중간체 15-1의 합성1) Synthesis of Intermediate 15-1
Figure PCTKR2019018487-appb-I000085
Figure PCTKR2019018487-appb-I000085
질소 분위기하에서, 중간체 11-1의 합성법 중 5,5'-(프로판-2,2-디일)비스(3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g 대신, N,N'-((다이페닐메틸렌)비스(5-(tert-부틸)-3,1-페닐렌))비스(아다만탄-1-아민) 50g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 15-1(14.6g, 수율 22%)를 수득하였다. MS[M+H]+ = 96850 g of 5,5'-(propane-2,2-diyl)bis(3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) in the synthesis of intermediate 11-1 under a nitrogen atmosphere Instead, 50 g of N,N'-((diphenylmethylene)bis(5-(tert-butyl)-3,1-phenylene))bis(adamantan-1-amine) was used to react in the same manner. . After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 15-1 (14.6 g, yield 22%) was obtained through recrystallization. MS[M+H]+ = 968
2) 화합물 15의 합성2) Synthesis of Compound 15
Figure PCTKR2019018487-appb-I000086
Figure PCTKR2019018487-appb-I000086
질소 분위기하에서, 중간체 15-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 20.7ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.4ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 그 후 0℃로 온도를 내린 후 다이아이소프로필에틸아민 20ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 15(2.3g, 수율 10%)를 수득하였다. MS[M+H]+ = 896In a nitrogen atmosphere, 14 g of intermediate 15-1 was added to 200 ml of toluene, lowered to 0° C., and 20.7 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.4 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. Thereafter, after lowering the temperature to 0° C., 20 ml of diisopropylethylamine was added, and after the reaction was completed, extraction was performed, and then compound 15 (2.3 g, yield 10%) was obtained through recrystallization. MS[M+H]+ = 896
[합성예 16] 화합물 16의 합성[Synthesis Example 16] Synthesis of Compound 16
1) 중간체 16-1의 합성1) Synthesis of Intermediate 16-1
Figure PCTKR2019018487-appb-I000087
Figure PCTKR2019018487-appb-I000087
질소 분위기하에서, 중간체 11-1의 합성법 중 5,5'-(프로판-2,2-디일)비스(3-(tert-부틸)-N-(4-(tert-부틸)페닐)아닐린) 50g 대신, N,N'-((다이페닐실란디일)비스(5-(tert-부틸)-3,1-페닐렌))비스(아다만탄-1-아민) 50g을 사용하여 같은 방법으로 반응시켰다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 16-1(14.8g, 수율 22%)을 수득하였다. MS[M+H]+ = 98450 g of 5,5'-(propane-2,2-diyl)bis(3-(tert-butyl)-N-(4-(tert-butyl)phenyl)aniline) in the synthesis of intermediate 11-1 under a nitrogen atmosphere Instead, 50 g of N,N'-((diphenylsilanediyl)bis(5-(tert-butyl)-3,1-phenylene))bis(adamantan-1-amine) was used in the same manner. To react. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 16-1 (14.8 g, yield 22%) was obtained through recrystallization. MS[M+H]+ = 984
2) 화합물 16의 합성2) Synthesis of Compound 16
Figure PCTKR2019018487-appb-I000088
Figure PCTKR2019018487-appb-I000088
질소 분위기하에서, 중간체 16-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 20.3ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.4ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 20ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 16(1.9g, 수율 8%)을 수득하였다. MS[M+H]+ = 913Under nitrogen atmosphere, 14 g of intermediate 16-1 was added to 200 ml of toluene, lowered to 0° C., and 20.3 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.4 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. After lowering the temperature to 0°C, 20 ml of diisopropylethylamine was added, and after the reaction was completed, the mixture was extracted and recrystallized to obtain compound 16 (1.9 g, yield 8%). MS[M+H]+ = 913
[합성예 17] 화합물 17의 합성[Synthesis Example 17] Synthesis of Compound 17
1) 중간체 17-1의 합성1) Synthesis of Intermediate 17-1
Figure PCTKR2019018487-appb-I000089
Figure PCTKR2019018487-appb-I000089
질소 분위기하에서, N,N'-((다이페닐실란)비스(5-(tert-부틸)-3,1-페닐렌))비스(아다만탄-1-아민) 50g, 1,2-다이브로모-5-(다이플로로(페닐)메톡시)-3-아이오도벤젠 35g, 소듐-tert-부톡사이드 19.7g 및 비스(트리-tert-부틸포스핀)팔라듐(0) 0.4g을 톨루엔 600ml에 넣은 후 12시간 동안 환류 교반하였다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 17-1(14.1g, 수율 20%)을 수득하였다. MS[M+H]+ = 1042Under nitrogen atmosphere, N,N'-((diphenylsilane)bis(5-(tert-butyl)-3,1-phenylene))bis(adamantan-1-amine) 50g, 1,2-dive Lomo-5-(difluoro(phenyl)methoxy)-3-iodobenzene 35g, sodium-tert-butoxide 19.7g and bis(tri-tert-butylphosphine)palladium(0) 0.4g toluene 600ml The mixture was stirred at reflux for 12 hours. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 17-1 (14.1 g, yield 20%) was obtained through recrystallization. MS[M+H]+ = 1042
2) 화합물 17의 합성2) Synthesis of Compound 17
Figure PCTKR2019018487-appb-I000090
Figure PCTKR2019018487-appb-I000090
질소 분위기하에서, 중간체 17-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 19.2ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.1ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 19ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 17(2.5g, 수율 11%)을 수득하였다. MS[M+H]+ = 971Under a nitrogen atmosphere, 14 g of intermediate 17-1 was added to 200 ml of toluene, lowered to 0° C., and 19.2 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.1 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. After lowering the temperature to 0° C., 19 ml of diisopropylethylamine was added, and after the reaction was completed, extraction was carried out, followed by recrystallization to obtain compound 17 (2.5 g, yield 11%). MS[M+H]+ = 971
[합성예 18] 화합물 18의 합성[Synthesis Example 18] Synthesis of Compound 18
1) 중간체 18-1의 합성1) Synthesis of Intermediate 18-1
Figure PCTKR2019018487-appb-I000091
Figure PCTKR2019018487-appb-I000091
질소 분위기하에서, N,N'-((다이페닐실란)비스(5-(tert-부틸)-3,1-페닐렌))비스(아다만탄-1-아민) 50g, (3,4-다이브로모-5-아이오도페닐)(다이플로로(페닐)메틸)설파인 36g, 소듐-tert-부톡사이드 19.7g 및 비스(트리-tert-부틸포스핀)팔라듐(0) 0.4g을 톨루엔 600ml에 넣은 후 12시간 동안 환류 교반하였다. 반응 종료 후 추출한 뒤, 에틸아세테이트:헥산 컬럼으로 정제 후 재결정을 통하여 중간체 18-1(14.9g, 수율 21%)을 수득하였다. MS[M+H]+ = 1054Under nitrogen atmosphere, N,N'-((diphenylsilane)bis(5-(tert-butyl)-3,1-phenylene))bis(adamantan-1-amine) 50g, (3,4- Dibromo-5-iodophenyl) (difluoro(phenyl)methyl) sulfine 36g, sodium-tert-butoxide 19.7g and bis(tri-tert-butylphosphine)palladium(0) 0.4g toluene 600ml The mixture was stirred at reflux for 12 hours. After extraction after completion of the reaction, after purification with an ethyl acetate:hexane column, intermediate 18-1 (14.9g, yield 21%) was obtained through recrystallization. MS[M+H]+ = 1054
2) 화합물 18의 합성2) Synthesis of Compound 18
Figure PCTKR2019018487-appb-I000092
Figure PCTKR2019018487-appb-I000092
질소 분위기하에서, 중간체 18-1 14g을 톨루엔 200ml에 넣고 0℃까지 낮춘 후 n-부틸리튬(1.6M) 19.0ml를 천천히 적가하였다. 1시간 후 보론트리브로마이드 4.1ml를 적가하고 70℃로 가열하여 6시간 동안 교반하였다. 0℃로 온도를 내린 후 다이아이소프로필에틸아민 19ml를 투입하고 반응 종료 후 추출한 뒤 재결정을 통하여 화합물 18(2.8g, 수율 12%)을 수득하였다. MS[M+H]+ = 983In a nitrogen atmosphere, 14 g of intermediate 18-1 was added to 200 ml of toluene, lowered to 0°C, and 19.0 ml of n-butyllithium (1.6M) was slowly added dropwise. After 1 hour, 4.1 ml of boron tribromide was added dropwise and heated to 70° C. and stirred for 6 hours. After lowering the temperature to 0° C., 19 ml of diisopropylethylamine was added, and after the reaction was completed, extraction was carried out, followed by recrystallization to obtain compound 18 (2.8 g, yield 12%). MS[M+H]+ = 983
Figure PCTKR2019018487-appb-I000093
Figure PCTKR2019018487-appb-I000093
Figure PCTKR2019018487-appb-I000094
Figure PCTKR2019018487-appb-I000094
<실험예 1> 유기 발광 소자 제작<Experimental Example 1> Preparation of organic light emitting device
실시예 1Example 1
ITO(indium tin oxide)가 1,500Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척 하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀리포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후, 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후, 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다. A glass substrate coated with a thin film coated with ITO (indium tin oxide) at a thickness of 1,500Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer Co. was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying, and then transported to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에 하기 화학식 [HAT]을 50Å의 두께로 열 진공증착하여 정공주입층을 형성하였다. 상기 정공 주입층 위에 하기 화학식 [NPB]를 1100Å의 두께로 진공 증착하여 정공수송층을 형성하였다. 상기 정공수송층 위에 하기 화학식 [HT-A]를 200 Å의 두께로 진공 증착하여 전자차단층을 형성하였다. 이어서, 상기 전자차단층 위에 청색 발광 도펀트로 화합물 1을 발광층 총 중량 대비 2wt%, 호스트로 2-(10-페닐안트라센-9-yl)다이벤조[b,d]퓨란[BH]을 발광층 총 중량 대비 98wt%로 하여, 300Å의 두께로 진공 증착하여 발광층을 형성하였다. 상기 발광층 위에 [TPBI] 및 하기 화학식 [LiQ] 를 1:1 중량비로 진공증착하여 200Å의 두께로 제1 전자수송층을 형성하였다. 상기 제1 전자수송층 위에 [LiF]을 진공 증착하여 100Å의 두께로 제2 전자수송층을 형성하였다. 상기 제2 전자수송층 위에 1,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. 상기의 과정에서 유기물의 증착속도는 0.4 ~ 0.9 Å/sec를 유지하였고, 제2 전자수송층의 리튬플루오라이드는 0.3 Å/sec, 음극의 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 5 × 10-8 ~ 1 × 10-7 torr를 유지하여, 유기 발광 소자를 제작하였다.On the ITO transparent electrode prepared as above, the following chemical formula [HAT] was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. The following formula [NPB] was vacuum-deposited to a thickness of 1100 MPa on the hole injection layer to form a hole transport layer. The following formula [HT-A] was vacuum deposited on the hole transport layer to a thickness of 200 Å to form an electron blocking layer. Subsequently, 2 wt% of the total weight of the light emitting layer as a blue light emitting dopant on the electron blocking layer, and 2-(10-phenylanthracene-9-yl)dibenzo[b,d]furan [BH] as the total weight of the light emitting layer Contrast 98 wt%, vacuum-deposited to a thickness of 300 Å to form a light emitting layer. [TPBI] and the following formula [LiQ] were vacuum-deposited on the light emitting layer in a 1:1 weight ratio to form a first electron transport layer with a thickness of 200 Pa. [LiF] was vacuum deposited on the first electron transport layer to form a second electron transport layer with a thickness of 100 mm 2. On the second electron transport layer, aluminum was deposited to a thickness of 1,000 mm 2 to form a cathode. In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 Å/sec, the lithium fluoride of the second electron transport layer was 0.3 0.3/sec, and the aluminum of the negative electrode was maintained at a deposition rate of 2 Å/sec. Vacuum degree is 5 × 10 -8 ~ 1 × 10 -7 The torr was maintained to produce an organic light emitting device.
Figure PCTKR2019018487-appb-I000095
Figure PCTKR2019018487-appb-I000095
[실시예 2 내지 18 및 비교예 1][Examples 2 to 18 and Comparative Example 1]
상기 실시예 1의 화합물 1 대신, 발광층 도펀트 물질로 하기 표 1에 기재된 도펀트 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다.An organic light emitting diode was manufactured according to the same method as Example 1 except for using the dopant compound shown in Table 1 below as a light emitting layer dopant material instead of the compound 1 of Example 1.
Figure PCTKR2019018487-appb-I000096
Figure PCTKR2019018487-appb-I000096
상기에서 실시예 1 내지 18 및 비교예 1에서 제조된 유기 발광 소자의 10 mA/㎠의 전류밀도에서의 효율, 수명 및 전압을 측정하여, 그 결과를 하기 표 1에 나타내었다.The efficiency, life, and voltage at a current density of 10 mA/cm 2 of the organic light-emitting devices prepared in Examples 1 to 18 and Comparative Example 1 were measured above, and the results are shown in Table 1 below.
화합물compound 효율(%)efficiency(%) 전압(V)Voltage (V) 수명life span
T95(hr)T95(hr)
실시예 1Example 1 화합물 1 Compound 1 8.78.7 3.73.7 185185
실시예 2Example 2 화합물 2 Compound 2 8.78.7 3.73.7 188188
실시예 3Example 3 화합물 3 Compound 3 8.68.6 3.83.8 186186
실시예 4Example 4 화합물 4 Compound 4 8.68.6 3.83.8 189189
실시예 5Example 5 화합물 5 Compound 5 8.28.2 3.73.7 178178
실시예 6Example 6 화합물 6 Compound 6 8.28.2 3.73.7 179179
실시예 7Example 7 화합물 7 Compound 7 8.78.7 3.63.6 185185
실시예 8Example 8 화합물 8Compound 8 8.68.6 3.73.7 186186
실시예 9Example 9 화합물 9Compound 9 8.48.4 3.73.7 183183
실시예 10Example 10 화합물 10Compound 10 8.98.9 3.83.8 189189
실시예 11Example 11 화합물 11Compound 11 8.68.6 3.73.7 180180
실시예 12Example 12 화합물 12Compound 12 8.78.7 3.73.7 181181
실시예 13Example 13 화합물 13Compound 13 8.68.6 3.73.7 182182
실시예 14Example 14 화합물 14Compound 14 8.88.8 3.83.8 183183
실시예 15Example 15 화합물 15Compound 15 8.78.7 3.83.8 183183
실시예 16Example 16 화합물 16Compound 16 8.78.7 3.73.7 182182
실시예 17Example 17 화합물 17Compound 17 8.78.7 3.83.8 182182
실시예 18Example 18 화합물 18Compound 18 8.68.6 3.83.8 183183
비교예 1Comparative Example 1 화합물 BDCompound BD 7.17.1 4.14.1 163163
상기 표 1에서 보는 바와 같이, 화학식 1의 구조를 갖는 화합물을 사용한 실시예 1 내지 18의 소자는 비교예 1의 소자보다 저전압, 고효율 및 높은 수명 특성을 가진다. 이는 붕소(Boron)의 파라(Para) 위치에 전자 받개 물질이 치환 됨으로써, 물질의 극성이 강해져 전하 전이 특성이 나타나 효율이 향상되는 특징과 함께, 동시에 구조적으로 정사면체 구조(tetrahedral structure)를 갖는 물질이 치환 됨으로써, 물질의 배향(orientation) 특성이 증가하여 효율이 증가하는 것으로 보인다. 또한 전자 주입 특성이 강해져 구동 전압이 줄어드는 특성을 보인다. 수명 또한 전자, 정공의 균형(balance) 측면에서 좀더 안정적인 효과를 보여 증가하는 양상을 나타내었다.As shown in Table 1, the devices of Examples 1 to 18 using the compound having the structure of Formula 1 have lower voltage, higher efficiency, and higher lifespan characteristics than the devices of Comparative Example 1. This is due to the substitution of the electron acceptor material at the para position of boron, which increases the polarity of the material, which results in improved charge transfer characteristics, and at the same time, a material having a structurally tetrahedral structure. By being substituted, it seems that the orientation characteristics of the material increase and the efficiency increases. In addition, the electron injection characteristic is strong and the driving voltage is reduced. The lifespan also showed a more stable effect in terms of balance of electrons and holes, showing an increasing pattern.

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019018487-appb-I000097
    Figure PCTKR2019018487-appb-I000097
    화학식 1에 있어서,In Formula 1,
    X1 및 X2는 각각 독립적으로, NR, O 또는 S이고,X1 and X2 are each independently NR, O or S,
    R1 및 R2는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 알키닐기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,R1 and R2 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
    R은 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고, R is a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
    Y1은 O, S 또는 S(=O)이며,Y1 is O, S or S(=O),
    R’은 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R'is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
    a 및 b는 각각 독립적으로, 0 내지 4의 정수이며,a and b are each independently an integer from 0 to 4,
    a 및 b가 각각 독립적으로 2 이상의 정수인 경우, 괄호 내의 치환기는 서로 같거나 상이하며, When a and b are each independently an integer of 2 or more, the substituents in parentheses are the same as or different from each other,
    x는 1 내지 3의 정수이며,x is an integer from 1 to 3,
    y는 0 내지 2의 정수이고,y is an integer from 0 to 2,
    x+y = 3이다.x+y = 3.
  2. 청구항 1에 있어서,The method according to claim 1,
    X1 및 X2는 각각 독립적으로, NR이고, X1 and X2 are each independently, NR,
    R은 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기인 것인 화합물.R is a substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1은 하기 화학식 2 또는 3으로 표시되는 화합물:Formula 1 is a compound represented by the following formula 2 or 3:
    [화학식 2][Formula 2]
    Figure PCTKR2019018487-appb-I000098
    Figure PCTKR2019018487-appb-I000098
    [화학식 3][Formula 3]
    Figure PCTKR2019018487-appb-I000099
    Figure PCTKR2019018487-appb-I000099
    화학식 2 및 3에 있어서,In Formulas 2 and 3,
    R3 내지 R6는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 알키닐기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R3 to R6 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted amine group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with adjacent groups to form a substituted or unsubstituted ring,
    c 및 d는 각각 독립적으로, 0 내지 4의 정수이고,c and d are each independently an integer from 0 to 4,
    e 및 f는 각각 독립적으로, 0 내지 3의 정수이고,e and f are each independently an integer from 0 to 3,
    c 내지 f가 2 이상인 경우, 괄호 내의 치환기는 서로 같거나 상이하며,When c to f are 2 or more, the substituents in parentheses are the same as or different from each other,
    Y2는 CR10R11, SiR12R13, NR14, O, S, P(=O)R15, PR16, S(=O) 또는 S(=O)2이고,Y2 is CR10R11, SiR12R13, NR14, O, S, P(=O)R15, PR16, S(=O) or S(=O) 2 ,
    R10 내지 R13은 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 또는 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,R10 to R13 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with an adjacent group to form a substituted or unsubstituted ring,
    R14 내지 R16는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R14 to R16 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
    X1, X2, Y1, R', x 및 y는 화학식 1과 같다.X1, X2, Y1, R', x and y are as in the formula (1).
  4. 청구항 1에 있어서,The method according to claim 1,
    R1 및 R2가 각각 독립적으로 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하는 경우, 직접결합; 또는 하기 구조 중 어느 하나의 고리를 형성하는 것인 화합물:When R1 and R2 each independently combine with an adjacent group to form a substituted or unsubstituted ring, a direct bond; Or a compound that forms a ring of any one of the following structures:
    Figure PCTKR2019018487-appb-I000100
    Figure PCTKR2019018487-appb-I000100
    상기 구조에서,In the above structure,
    A1 내지 A24는 각각 독립적으로, 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,A1 to A24 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
    a1 내지 a11은 각각 0 내지 4의 정수이고, a1 to a11 are each an integer from 0 to 4,
    a12는 0 내지 6의 정수이며,a12 is an integer from 0 to 6,
    *는 치환되는 위치를 표시한 것이다.* Indicates the position to be substituted.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1은 하기 화합물들 중 어느 하나로 표시되는 화합물:Formula 1 is a compound represented by any one of the following compounds:
    Figure PCTKR2019018487-appb-I000101
    Figure PCTKR2019018487-appb-I000101
    Figure PCTKR2019018487-appb-I000102
    Figure PCTKR2019018487-appb-I000102
    Figure PCTKR2019018487-appb-I000103
    Figure PCTKR2019018487-appb-I000103
    Figure PCTKR2019018487-appb-I000104
    Figure PCTKR2019018487-appb-I000104
    Figure PCTKR2019018487-appb-I000105
    Figure PCTKR2019018487-appb-I000105
    Figure PCTKR2019018487-appb-I000106
    Figure PCTKR2019018487-appb-I000106
    Figure PCTKR2019018487-appb-I000107
    Figure PCTKR2019018487-appb-I000107
    Figure PCTKR2019018487-appb-I000108
    Figure PCTKR2019018487-appb-I000108
    Figure PCTKR2019018487-appb-I000109
    Figure PCTKR2019018487-appb-I000109
    Figure PCTKR2019018487-appb-I000110
    Figure PCTKR2019018487-appb-I000110
    Figure PCTKR2019018487-appb-I000111
    Figure PCTKR2019018487-appb-I000111
    Figure PCTKR2019018487-appb-I000112
    Figure PCTKR2019018487-appb-I000112
    Figure PCTKR2019018487-appb-I000113
    Figure PCTKR2019018487-appb-I000113
    Figure PCTKR2019018487-appb-I000114
    Figure PCTKR2019018487-appb-I000114
    Figure PCTKR2019018487-appb-I000115
    Figure PCTKR2019018487-appb-I000115
    Figure PCTKR2019018487-appb-I000116
    Figure PCTKR2019018487-appb-I000116
    Figure PCTKR2019018487-appb-I000117
    Figure PCTKR2019018487-appb-I000117
    Figure PCTKR2019018487-appb-I000118
    Figure PCTKR2019018487-appb-I000118
    Figure PCTKR2019018487-appb-I000119
    Figure PCTKR2019018487-appb-I000119
    Figure PCTKR2019018487-appb-I000120
    Figure PCTKR2019018487-appb-I000120
    Figure PCTKR2019018487-appb-I000121
    Figure PCTKR2019018487-appb-I000121
    Figure PCTKR2019018487-appb-I000122
    Figure PCTKR2019018487-appb-I000122
    Figure PCTKR2019018487-appb-I000123
    Figure PCTKR2019018487-appb-I000123
    Figure PCTKR2019018487-appb-I000124
    Figure PCTKR2019018487-appb-I000124
    Figure PCTKR2019018487-appb-I000125
    Figure PCTKR2019018487-appb-I000125
    Figure PCTKR2019018487-appb-I000126
    Figure PCTKR2019018487-appb-I000126
    Figure PCTKR2019018487-appb-I000127
    Figure PCTKR2019018487-appb-I000127
    Figure PCTKR2019018487-appb-I000128
    Figure PCTKR2019018487-appb-I000128
    Figure PCTKR2019018487-appb-I000129
    Figure PCTKR2019018487-appb-I000129
    Figure PCTKR2019018487-appb-I000130
    Figure PCTKR2019018487-appb-I000130
    Figure PCTKR2019018487-appb-I000131
    Figure PCTKR2019018487-appb-I000131
    Figure PCTKR2019018487-appb-I000132
    Figure PCTKR2019018487-appb-I000132
    Figure PCTKR2019018487-appb-I000133
    Figure PCTKR2019018487-appb-I000133
    Figure PCTKR2019018487-appb-I000134
    Figure PCTKR2019018487-appb-I000134
    Figure PCTKR2019018487-appb-I000135
    Figure PCTKR2019018487-appb-I000135
    Figure PCTKR2019018487-appb-I000136
    Figure PCTKR2019018487-appb-I000136
    Figure PCTKR2019018487-appb-I000137
    Figure PCTKR2019018487-appb-I000137
    Figure PCTKR2019018487-appb-I000138
    Figure PCTKR2019018487-appb-I000138
    Figure PCTKR2019018487-appb-I000139
    Figure PCTKR2019018487-appb-I000139
    Figure PCTKR2019018487-appb-I000140
    .
    Figure PCTKR2019018487-appb-I000140
    .
  6. 제1 전극; 상기 제1 전극과 대향하여 구비되는 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상이 청구항 1 내지 5 중 어느 한 항에 따른 화합물을 포함하는 유기발광소자.A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound according to any one of claims 1 to 5.
  7. 청구항 6에 있어서,The method according to claim 6,
    상기 유기물층은 정공수송층 또는 정공주입층을 포함하고, 상기 정공수송층 또는 정공주입층은 상기 화합물을 포함하는 유기발광소자.The organic material layer includes a hole transport layer or a hole injection layer, and the hole transport layer or a hole injection layer comprises the compound.
  8. 청구항 6에 있어서,The method according to claim 6,
    상기 유기물층은 전자수송층 또는 전자주입층을 포함하고, 상기 전자수송층 또는 전자주입층은 상기 화합물을 포함하는 유기발광소자.The organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound.
  9. 청구항 6에 있어서,The method according to claim 6,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 포함하는 유기발광소자.The organic material layer includes a light emitting layer, the light emitting layer is an organic light emitting device comprising the compound.
  10. 청구항 6에 있어서,The method according to claim 6,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 발광층의 도펀트로 포함하는 유기발광소자.The organic material layer includes a light emitting layer, the light emitting layer is an organic light emitting device comprising the compound as a dopant of the light emitting layer.
PCT/KR2019/018487 2018-12-26 2019-12-26 Compound and organic light-emitting element comprising same WO2020138964A1 (en)

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