WO2017061788A1 - Spiro compound and organic light-emitting device comprising same - Google Patents

Spiro compound and organic light-emitting device comprising same Download PDF

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WO2017061788A1
WO2017061788A1 PCT/KR2016/011184 KR2016011184W WO2017061788A1 WO 2017061788 A1 WO2017061788 A1 WO 2017061788A1 KR 2016011184 W KR2016011184 W KR 2016011184W WO 2017061788 A1 WO2017061788 A1 WO 2017061788A1
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group
substituted
unsubstituted
formula
same
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PCT/KR2016/011184
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French (fr)
Korean (ko)
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하재승
곽지원
김진주
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주식회사 엘지화학
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Priority claimed from KR1020160071248A external-priority patent/KR101991050B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/575,098 priority Critical patent/US10781366B2/en
Priority to CN201680031036.3A priority patent/CN107614494B/en
Publication of WO2017061788A1 publication Critical patent/WO2017061788A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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]
    • H10K50/17—Carrier injection layers

Definitions

  • the present specification relates to a spiro compound and an organic light emitting device including the same.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • the present specification provides a spiro compound and an organic light emitting device including the same.
  • spiro type compound represented by the following formula (1).
  • X 1 is O or S
  • R1 to R12 is the following Formula B, and the remaining and R13 to R16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted sily
  • L1 is the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
  • Ar1 and Ar2 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, or combine with each other to form a substituted or unsubstituted ring.
  • the spiro compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using this, it is possible to improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.
  • FIG. 1 illustrates an organic light emitting device 10 according to an exemplary embodiment of the present specification.
  • FIG. 2 illustrates an organic light emitting device 11 according to another exemplary embodiment of the present specification.
  • the present specification provides a spiro type compound represented by Chemical Formula 1.
  • substituted means that a hydrogen atom bonded to a 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 a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • substituted or unsubstituted is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Carbonyl group; Ester group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted or unsubstituted
  • a substituent to which two or more substituents are linked 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 linked.
  • the halogen group may be fluorine, chlorine, bromine or iodine.
  • carbon number of an imide group is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the amide group may be substituted with nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the ester group may be substituted with oxygen of the ester group having a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-o
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.
  • the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.
  • the amine group is -NH 2 ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-aryl heteroaryl amine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30.
  • Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group.
  • the N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted for N of the amine group.
  • the N-arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted for N in the amine group.
  • the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroarylamine group are substituted for N of the amine group.
  • the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkyl sulfoxy group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above.
  • the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group
  • the alkyl sulfoxy group includes mesyl, ethyl sulfoxy, propyl sulfoxy, and butyl sulfoxy groups. Etc., but is not limited thereto.
  • the alkenyl group may be linear or branched chain, 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, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
  • the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
  • the present invention is not limited thereto.
  • the boron group may be -BR 100 R 101 , wherein R 100 and R 101 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.
  • phosphine oxide groups include, but are not limited to, diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like.
  • the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
  • the aryl group is a monocyclic aryl group
  • carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
  • Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30.
  • the polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
  • the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
  • adjacent means a substituent substituted on an atom directly connected to an atom to which the substituent is substituted, a substituent positioned closest to the substituent, or another substituent substituted on an atom to which the substituent is substituted.
  • two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" groups.
  • the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, N-arylalkylamine group, N-arylheteroarylamine group, and arylphosphine group is the same as the examples of the aryl group described above.
  • the aryloxy group may be a phenoxy group, p-tolyloxy group, m-tolyloxy 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.
  • arylthioxy group examples include a phenylthioxy group and 2- The methylphenyl thioxy group, 4-tert- butylphenyl thioxy group, etc. are mentioned,
  • An aryl sulfoxy group includes a benzene sulfoxy group, p-toluene sulfoxy group, etc., but is not limited to this.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group.
  • the arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
  • the aryl group in the arylamine group may be selected from the examples of the aryl group described above.
  • the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic.
  • heterocyclic group examples include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene
  • examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group.
  • the heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group.
  • the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.
  • heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.
  • the arylene group refers to a divalent group having two bonding positions in the aryl group.
  • the description of the aforementioned aryl group can be applied except that they are each divalent.
  • the heteroarylene group means a divalent group having two bonding positions in the heteroaryl group.
  • the description of the aforementioned heteroaryl group can be applied except that they are each divalent.
  • a “ring” means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.
  • the ring is a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.
  • the hydrocarbon ring may be an aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group except for the above-mentioned monovalent one.
  • the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group except that it is not monovalent.
  • the heterocycle includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like.
  • the heterocycle may be monocyclic or polycyclic, may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group except that it is not monovalent.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-6.
  • R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boro
  • r101, r102 and r103 are each an integer of 1 to 3,
  • r101, r102 and r103 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-7 to 1-18.
  • R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boro
  • r101, r102 and r103 are each an integer of 1 to 3,
  • r101, r102 and r103 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.
  • R13 to R16 is hydrogen.
  • any one of R1 to R12 is the formula B, the rest is hydrogen.
  • R1 is the general formula (B).
  • R2 is the general formula (B).
  • R3 is the general formula (B).
  • R4 is the formula B.
  • R5 is the general formula (B).
  • R6 is the formula (B).
  • R7 is the formula (B).
  • R8 is the formula (B).
  • R9 is the formula (B).
  • R10 is the formula B.
  • R11 is the formula (B).
  • R12 is the formula (B).
  • L1 is a direct bond; Or a substituted or unsubstituted aryl group.
  • L1 is a direct bond; Or an aryl group.
  • L1 is a direct bond; Substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylylene group; Or a substituted or unsubstituted naphthylene group.
  • L1 is a direct bond; Phenylene group; Biphenylylene group; Or a naphthylene group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently at least one selected from the group consisting of an aryl group unsubstituted or substituted with an alkyl group, and an alkyl group and an amine group. Substituted or unsubstituted aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; A substituted or unsubstituted quarterphenyl group; Substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted spirobifluorenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted phenanthrenylene group; Substituted or unsubstituted carbazolyl group; Substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenz
  • Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an alkyl group, or a phenyl group unsubstituted or substituted with an amine group; A biphenyl group unsubstituted or substituted with an aryl group; Terphenyl group unsubstituted or substituted with an aryl group; Quarter-phenyl group; Naphthyl group; A fluorenyl group unsubstituted or substituted with one or more from the group consisting of an alkyl group and an aryl group; Spirobifluorenyl group; Triphenylenyl group; Phenanthrenylene group; Carbazolyl group unsubstituted or substituted with an aryl group; Dibenzofuranyl group; Or a dibenzothiophene group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group substituted with a methyl group Or a phenyl group unsubstituted or substituted with a diphenylamine group; A biphenyl group unsubstituted or substituted with a phenyl group or a biphenyl group; Terphenyl group unsubstituted or substituted with a phenyl group; Quarter-phenyl group; Naphthyl group; A fluorenyl group unsubstituted or substituted with one or more from the group consisting of a methyl group, a phenyl group and a naphthyl group; Spirobifluorenyl group; Triphenyl group,
  • Ar1 and Ar2 are bonded to each other, to form a substituted or unsubstituted hetero ring.
  • Ar1 and Ar2 are bonded to each other, to form a ring represented by the structure of the formula (C).
  • X2 is CRR ', NR ", O or S,
  • R, R ', R ", R201 and R202 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group,
  • r201 and r202 are each an integer of 1 to 4,
  • R and R ' are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group.
  • R and R ' are the same as or different from each other, and each independently an alkyl group.
  • R and R ' is a methyl group.
  • R is a substituted or unsubstituted aryl group.
  • R is an aryl group.
  • R is a phenyl group.
  • R201 and R202 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted aryl group.
  • R201 and R202 are the same as or different from each other, and each independently hydrogen; Or an aryl group.
  • R201 and R202 are the same as or different from each other, and each independently hydrogen; Or a phenyl group.
  • Formula C is represented by any one of the following structures.
  • Formula 1 is selected from the following compounds.
  • the 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, wherein at least one of the organic material layers includes the aforementioned spiro-type compound.
  • the organic material layer of the organic light emitting device of the present specification may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.
  • 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.
  • 1 illustrates a structure of an organic light emitting device 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20.
  • 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.
  • FIG. 2 illustrates a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90, and a second electrode on a substrate 20.
  • a structure of an organic light emitting device in which 50) is sequentially stacked is illustrated.
  • 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.
  • the organic material layer includes a hole injection layer, and the hole injection layer includes a spiro type compound represented by Chemical Formula 1.
  • the organic material layer includes a hole transport layer
  • the hole transport layer comprises a spiro-type compound represented by the formula (1).
  • the organic material layer includes a hole control layer, and the hole control layer includes a spiro type compound represented by Chemical Formula 1.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a spiro type compound represented by Chemical Formula 1.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a spiro-type compound represented by Chemical Formula 1 as a dopant of the light emitting layer.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by the following Chemical Formula 1-A.
  • n1 is an integer of 1 or more
  • Ar3 is a substituted or unsubstituted monovalent or higher benzofluorene group; Substituted or unsubstituted monovalent or higher fluoranthene group; A substituted or unsubstituted monovalent or higher pyrene group; Or a substituted or unsubstituted monovalent or higher chrysene group,
  • L 1 is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
  • Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted arylalkyl group; Or a substituted or unsubstituted heteroaryl group, or may combine with each other to form a substituted or unsubstituted ring,
  • n1 is 2 or more
  • the structures in two or more parentheses are the same or different from each other.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1-A as a dopant of the light emitting layer.
  • L1 is a direct bond.
  • n1 is 2.
  • Ar3 is a divalent pyrene group unsubstituted or substituted with deuterium, methyl, ethyl, isopropyl, or tert-butyl groups; Or a divalent chrysene group unsubstituted or substituted with deuterium, methyl, ethyl or tert-butyl groups.
  • Ar4 and Ar5 are the same as or different from each other, each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted with a silyl group substituted with a methyl group, ethyl group, isopropyl group, tert-butyl group, nitrile group or alkyl group It is an aryl group.
  • Ar4 and Ar5 are the same or different from each other, and each independently an aryl group unsubstituted or substituted with a silyl group substituted with an alkyl group.
  • Ar4 and Ar5 are the same or different from each other, and each independently an aryl group unsubstituted or substituted with a trimethylsilyl group.
  • Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group.
  • Ar4 and Ar5 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a nitrile group, or a trimethylsilyl group.
  • Ar4 and Ar5 are the same as or different from each other, and each independently a biphenyl group unsubstituted or substituted with a methyl group, ethyl group, tert-butyl group, nitrile group or trimethylsilyl group.
  • Ar4 and Ar5 are the same as or different from each other, and each independently a terphenyl group unsubstituted or substituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group, or a trimethylsilyl group.
  • Ar4 and Ar5 are the same as or different from each other, and each independently represent a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms.
  • Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group, a silyl group substituted with an alkyl group or a phenyl group It is an aryl group.
  • Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted with a methyl group, ethyl group, tert-butyl group, nitrile group, trimethylsilyl group or phenyl group to be.
  • Formula 1-A is selected from the following compounds.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by the following Chemical Formula 2-A.
  • Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group,
  • G1 to G8 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group.
  • the organic material layer includes a light emitting layer
  • the light emitting layer includes a compound represented by Formula 2-A as a host of the light emitting layer.
  • Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted polycyclic aryl group.
  • Ar11 and Ar12 are the same as or different from each other, and each independently represent a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms.
  • Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted naphthyl group.
  • Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted 1-naphthyl group.
  • Ar11 and Ar12 are 1-naphthyl group.
  • the G1 to G8 is hydrogen.
  • Formula 2-A is selected from the following compounds.
  • the organic material layer includes a light emitting layer
  • the light emitting layer includes the compound represented by Formula 1-A as a dopant of the light emitting layer
  • the compound represented by Formula 2-A as a host of the light emitting layer Include as.
  • the organic material layer may further include one 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 and an electron injection layer.
  • the organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes a spiro-type compound of the present specification, that is, a spiro-type compound represented by Formula 1 above. Can be.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a physical vapor deposition PVD: physical vapor deposition
  • PVD physical vapor deposition
  • sputtering e-beam evaporation
  • a metal or conductive metal oxide or an alloy thereof on the substrate
  • It can be prepared by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon.
  • an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate.
  • the spiro compound represented by Chemical Formula 1 may be formed of an organic material layer by a solution coating method as well as a vacuum deposition method in manufacturing an organic light emitting device.
  • the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the anode material a material having a large work function is usually preferred to facilitate hole injection into the organic material layer.
  • the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, Mg / Ag, and the like, but are not limited thereto.
  • the hole injection layer is a layer for injecting holes from an electrode with a hole injection material, and has a capability of transporting holes with a hole injection material, and thus has a hole injection effect at an anode, and an excellent hole injection effect with respect to a light emitting layer or a light emitting material.
  • generated in the light emitting layer to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable.
  • the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer.
  • the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer.
  • the material is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • the hole control layer effectively receives holes from the hole transport layer and serves to control hole mobility to adjust the amount of holes transferred to the light emitting layer.
  • it may simultaneously serve as an electron barrier to prevent electrons supplied from the light emitting layer from falling into the hole transport layer. This can maximize the balance of holes and electrons in the light emitting layer to increase the luminous efficiency, improve the life of the device through the electron stability of the hole control layer, it is possible to use materials known in the art.
  • the light emitting material of the light emitting layer is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.
  • Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
  • the light emitting layer may include a host material and a dopant material.
  • the host material is a condensed aromatic ring derivative or a hetero ring-containing compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the dopant material examples include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted.
  • At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted.
  • substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted.
  • the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.
  • the electron transporting material of the electron transporting layer is a layer for receiving electrons from the electron injection layer and transporting electrons to the light emitting layer.
  • the electron transporting material is a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer. This large material is suitable. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material as used in accordance with the prior art.
  • suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.
  • the electron injection layer is a layer that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer.
  • the compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-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, 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) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double side emission type according to a material used.
  • the spiro compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • Benzofuran-2-boronic acid (30 g, 185 mmol) and 1-bromo-2-iodobenzene (53.2 g, 189 mmol) were added to dioxane (300 ml) followed by 2M aqueous potassium carbonate solution (100 ml). Tetrakistriphenyl-phosphinopalladium (4.28 g, 2 mol%) was added thereto, followed by heating and stirring for 4 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate solution was removed to separate the layers. After the solvent was removed, the compound A-1, a colorless oil (42.7 g, 85%) was prepared by column with hexane.
  • Compound A-2 was prepared in the same manner as in Preparation Example A-1, except that benzofuran-3-boronic acid was used instead of benzofuran-2-boronic acid.
  • Compound A-3 was prepared by the same method as Example 1-2 except for using 1-bromo-3-chloro-2-iodobenzene instead of 1-bromo-2-iodobenzene. .
  • Compound A-4 was prepared in the same manner as in Preparation Example A-1, except that benzothiophene-2-boronic acid was used instead of benzofuran-2-boronic acid.
  • Compound A-5 was prepared in the same manner as in Preparation Example A-1, except that benzothiophene-3-boronic acid was used instead of benzofuran-2-boronic acid.
  • Compound B-2 was synthesized in the same manner as in Production Example B-1, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
  • Compound B-3 was prepared in the same manner as in Preparation Example B-1, except that Compound A-2 was used instead of Compound A-1.
  • Compound B-5 was prepared in the same manner as in Preparation Example B-1, except that Compound A-3 was used instead of Compound A-1.
  • Compound B-6 was prepared in the same manner as in Preparation Example B-1, except that Compound A-4 was used instead of Compound A-1.
  • Compound B-7 was synthesized in the same manner as in Production Example B-6, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
  • Compound B-9 was synthesized in the same manner as in Preparation Example B-8, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
  • Compound B-10 was synthesized in the same manner as in Example B-8, except that 1-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
  • Compound C-2 was prepared in the same manner as in Preparation Example C-1, except that Compound B-2 was used instead of Compound B-1.
  • Compound C-3 was prepared in the same manner as in Preparation Example C-1, except that Compound B-3 was used instead of Compound B-1.
  • Compound C-4 was prepared in the same manner as in Preparation Example C-1, except that Compound B-4 was used instead of Compound B-1.
  • Compound C-5 was prepared in the same manner as in Preparation Example C-1, except that Compound B-5 was used instead of Compound B-1.
  • Compound C-6 was prepared by the same method as the preparation method C-1 except that compound B-6 was used instead of compound B-1.
  • Compound C-7 was prepared in the same manner as in Preparation Example C-1, except that Compound B-7 was used instead of Compound B-1.
  • Compound C-9 was prepared by the same method as the preparation method C-1 except that compound B-9 was used instead of compound B-1.
  • Compound C-10 was prepared in the same manner as in Preparation Example C-1, except that Compound B-10 was used instead of Compound B-1.
  • Compound D-2 was prepared in the same manner as in Preparation Example D-1, except that Compound C-9 was used instead of Compound C-3.
  • a glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) with a thickness of 1,000 ⁇ was placed in distilled water in which a dispersant was dissolved, and ultrasonically washed. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.
  • ITO Indium Tin Oxide
  • Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.
  • the host H1 and the dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 kPa.
  • E1 compound (300 kPa) was thermally vacuum deposited sequentially into the electron injection and transport layer.
  • An organic light emitting device was manufactured by sequentially depositing 12 ⁇ thick lithium fluoride (LiF) and 2,000 ⁇ thick aluminum on the electron transport layer to form a cathode.
  • the deposition rate of the organic material was maintained at 1 ⁇ / sec
  • the lithium fluoride was 0.2 ⁇ / sec
  • the aluminum was maintained at a deposition rate of 3 to 7 ⁇ / sec.
  • the organic light emitting diodes of Examples 1-1 to 1-6 manufactured by using a spiro type compound according to an exemplary embodiment of the present specification have a lower voltage and higher efficiency than those of Comparative Example 1-1, which are benzidine-type materials. It can be seen that it exhibits characteristics.
  • a glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) with a thickness of 1,000 ⁇ was placed in distilled water in which a dispersant was dissolved, and ultrasonically washed. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.
  • ITO Indium Tin Oxide
  • Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.
  • HT1 900 kPa
  • Compound 2 was vacuum deposited at a film thickness of 100 kPa on the hole transport layer to form a hole control layer.
  • the host H1 and the dopant D1 25: 1 were vacuum deposited to a thickness of 300 kPa.
  • E1 300 kPa was then thermally vacuum deposited sequentially into the electron injection and transport layer.
  • An organic light emitting device was manufactured by sequentially depositing 12 ⁇ thick lithium fluoride (LiF) and 2,000 ⁇ thick aluminum on the electron transport layer to form a cathode.
  • the deposition rate of the organic material was maintained at 1 ⁇ / sec
  • the lithium fluoride was 0.2 ⁇ / sec
  • the aluminum was maintained at a deposition rate of 3 to 7 ⁇ / sec.
  • the organic light emitting diodes of Examples 2-1 to 2-4 prepared using the spiro type compound represented by Formula 1 according to the exemplary embodiment of the present specification are compared with HT2, which is a carbazole type material. It can be seen that the characteristics of lower voltage and higher efficiency are shown than the organic light emitting element of Example 2-1.
  • the spiro compound represented by Formula 1 may play a role of hole transport and hole control in an organic electronic device including an organic light emitting device, and the organic light emitting device according to the present specification may include efficiency, driving voltage, Excellent properties in terms of stability.

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Abstract

The present specification relates to a spiro compound and an organic light-emitting device comprising same.

Description

스피로형 화합물 및 이를 포함하는 유기 발광 소자Spiro compound and organic light emitting device comprising the same
본 출원은 2015년 10월 6일에 한국특허청에 제출된 한국 특허 출원 제10-2015-0140423호 및 2016년 6월 8일에 한국특허청에 제출된 한국 특허 출원 제10-2016-0071248호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application is subject to the Korean Patent Application No. 10-2015-0140423 filed with the Korean Patent Office on October 6, 2015 and the Korean Patent Application No. 10-2016-0071248 filed with the Korean Patent Office on June 8, 2016. Claiming benefit, the entire contents of which are incorporated herein by reference.
본 명세서는 스피로형 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present specification relates to a spiro compound and an organic light emitting device including the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어 질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.
상기와 같은 유기 발광 소자를 위한 새로운 재료의 개발이 계속 요구되고 있다.There is a continuing need for the development of new materials for such organic light emitting devices.
[특허문헌][Patent Documents]
국제 특허 출원 공개 제2003-012890호International Patent Application Publication No. 2003-012890
본 명세서는 스피로형 화합물 및 이를 포함하는 유기 발광 소자를 제공한다.The present specification provides a spiro compound and an organic light emitting device including the same.
본 명세서의 일 실시상태에 따르면 하기 화학식 1로 표시되는 스피로형 화합물을 제공한다.According to an exemplary embodiment of the present specification provides a spiro type compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2016011184-appb-I000001
Figure PCTKR2016011184-appb-I000001
상기 화학식 1에 있어서,In Chemical Formula 1,
X1은 O 또는 S이고,X 1 is O or S,
R1 내지 R12 중 어느 하나는 하기 화학식 B이고, 나머지 및 R13 내지 R16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 니트릴기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이며,Any one of R1 to R12 is the following Formula B, and the remaining and R13 to R16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
[화학식 B][Formula B]
Figure PCTKR2016011184-appb-I000002
Figure PCTKR2016011184-appb-I000002
상기 화학식 B에 있어서,In Chemical Formula B,
L1은 서로 같거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이고,L1 is the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 서로 결합하여, 치환 또는 비치환된 고리를 형성한다.Ar1 and Ar2 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, or combine with each other to form a substituted or unsubstituted ring.
또한, 본 명세서의 일 실시상태에 따르면, 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 상기 화학식 1로 표시되는 스피로형 화합물을 포함하는 것인 유기 발광 소자를 제공한다.Further, according to one embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a spiro-type compound represented by Chemical Formula 1. to provide.
본 명세서의 일 실시상태에 따른 스피로형 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있고, 이를 사용함으로써 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성의 향상이 가능하다.The spiro compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using this, it is possible to improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.
도 1은 본 명세서의 일 실시상태에 따르는 유기 발광 소자(10)를 도시한 것이다.1 illustrates an organic light emitting device 10 according to an exemplary embodiment of the present specification.
도 2는 본 명세서의 또 하나의 실시상태에 따르는 유기 발광 소자(11)를 도시한 것이다.2 illustrates an organic light emitting device 11 according to another exemplary embodiment of the present specification.
이하, 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, this specification is demonstrated in detail.
본 명세서는 상기 화학식 1로 표시되는 스피로형 화합물을 제공한다.The present specification provides a spiro type 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, this means that it may further include other components, without excluding other components unless specifically stated otherwise.
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 located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.
본 명세서에 있어서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of substituents in the present 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 "substituted" means that a hydrogen atom bonded to a 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 a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 니트릴기; 니트로기; 이미드기; 아미드기; 카르보닐기; 에스테르기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 및 치환 또는 비치환된 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 수 있다. As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Carbonyl group; Ester group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent to which two or more substituents are linked" 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 linked.
본 명세서에 있어서,
Figure PCTKR2016011184-appb-I000003
는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the present specification,
Figure PCTKR2016011184-appb-I000003
Means a site which is bonded to another substituent or binding moiety.
본 명세서에 있어서, 할로겐기는 불소, 염소, 브롬 또는 요오드가 될 수 있다.In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
Figure PCTKR2016011184-appb-I000004
Figure PCTKR2016011184-appb-I000004
본 명세서에 있어서, 아미드기는 아미드기의 질소가 수소, 탄소수 1 내지 30의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 30의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the amide group may be substituted with nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2016011184-appb-I000005
Figure PCTKR2016011184-appb-I000005
본 명세서에서 카르보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
Figure PCTKR2016011184-appb-I000006
Figure PCTKR2016011184-appb-I000006
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 30의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the ester group may be substituted with oxygen of the ester group having a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2016011184-appb-I000007
Figure PCTKR2016011184-appb-I000007
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 30인 것이 바람직하다. 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 시클로펜틸메틸, 시클로헥실메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 30인 것이 바람직하며, 구체적으로 시클로프로필, 시클로부틸, 시클로펜틸, 3-메틸시클로펜틸, 2,3-디메틸시클로펜틸, 시클로헥실, 3-메틸시클로헥실, 4-메틸시클로헥실, 2,3-디메틸시클로헥실, 3,4,5-트리메틸시클로헥실, 4-tert-부틸시클로헥실, 시클로헵틸, 시클로옥틸 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, i-프로필옥시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시, 벤질옥시, p-메틸벤질옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.
본 명세서에 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 group; N-alkylarylamine group; Arylamine group; N-aryl heteroaryl amine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group. A diphenylamine group, an N-phenylnaphthylamine group, a tolylamine group, an N-phenyltolylamine group, a triphenylamine group, and an N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenyl fluorenyl amine group; N-phenylterphenylamine group; N-phenanthrenyl fluorenyl amine group; N-biphenyl fluorenyl amine 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 an alkyl group and an aryl group are substituted for N of the amine group.
본 명세서에 있어서, N-아릴헤테로아릴아민기는 아민기의 N에 아릴기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted for N in the amine group.
본 명세서에 있어서, N-알킬헤테로아릴아민기는 아민기의 N에 알킬기 및 헤테로아릴아민기가 치환된 아민기를 의미한다.In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroarylamine group are substituted for N of the amine group.
본 명세서에 있어서, 알킬아민기, N-아릴알킬아민기, 알킬티옥시기, 알킬술폭시기, N-알킬헤테로아릴아민기 중의 알킬기는 전술한 알킬기의 예시와 같다. 구체적으로 알킬티옥시기로는 메틸티옥시기, 에틸티옥시기, tert－부틸티옥시기, 헥실티옥시기, 옥틸티옥시기 등이 있고, 알킬술폭시기로는 메실, 에틸술폭시기, 프로필술폭시기, 부틸술폭시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkyl sulfoxy group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group, and the alkyl sulfoxy group includes mesyl, ethyl sulfoxy, propyl sulfoxy, and butyl sulfoxy groups. Etc., but is not limited thereto.
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 linear or branched chain, 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, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.
본 명세서에 있어서, 붕소기는 -BR100R101일 수 있으며, 상기 R100 및 R101은 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 니트릴기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 및 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로아릴기로 이루어진 군으로부터 선택될 수 있다.In the present specification, the boron group may be -BR 100 R 101 , wherein R 100 and R 101 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.
본 명세서에 있어서, 포스핀옥사이드기는 구체적으로 디페닐포스핀옥사이드기, 디나프틸포스핀옥사이드 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, phosphine oxide groups include, but are not limited to, diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하며, 상기 아릴기는 단환식 또는 다환식일 수 있다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
상기 아릴기가 단환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하다. 구체적으로 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
상기 아릴기가 다환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나. 탄소수 10 내지 30인 것이 바람직하다. 구체적으로 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 트리페닐기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
본 명세서에 있어서, 상기 플루오레닐기는 치환될 수 있으며, 인접한 기들이 서로 결합하여 고리를 형성할 수 있다. In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2016011184-appb-I000008
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,
Figure PCTKR2016011184-appb-I000008
And so on. However, the present invention is not limited thereto.
부재가 존재하는 경우도 포함한다.It also includes the case where the member is present.
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.As used herein, the term "adjacent" means a substituent substituted on an atom directly connected to an atom to which the substituent is substituted, a substituent positioned closest to the substituent, or another substituent substituted on an atom to which the substituent is substituted. Can be. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" groups.
본 명세서에 있어서, 아릴옥시기, 아릴티옥시기, 아릴술폭시기, N-아릴알킬아민기, N-아릴헤테로아릴아민기 및 아릴포스핀기 중의 아릴기는 전술한 아릴기의 예시와 같다. 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 있고, 아릴티옥시기로는 페닐티옥시기, 2－메틸페닐티옥시기, 4－tert－부틸페닐티옥시기 등이 있으며, 아릴술폭시기로는 벤젠술폭시기, p－톨루엔술폭시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, N-arylalkylamine group, N-arylheteroarylamine group, and arylphosphine group is the same as the examples of the aryl group described above. Specifically, the aryloxy group may be a phenoxy group, p-tolyloxy group, m-tolyloxy 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. Examples of the arylthioxy group include a phenylthioxy group and 2- The methylphenyl thioxy group, 4-tert- butylphenyl thioxy group, etc. are mentioned, An aryl sulfoxy group includes a benzene sulfoxy group, p-toluene sulfoxy group, etc., but is not limited to this.
본 명세서에 있어서, 아릴아민기의 예로는 치환 또는 비치환된 모노아릴아민기, 치환 또는 비치환된 디아릴아민기, 또는 치환 또는 비치환된 트리아릴아민기가 있다. 상기 아릴아민기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기일 수 있다. 상기 아릴기가 2 이상을 포함하는 아릴아민기는 단환식 아릴기, 다환식 아릴기, 또는 단환식 아릴기와 다환식 아릴기를 동시에 포함할 수 있다. 예컨대, 상기 아릴아민기 중의 아릴기는 전술한 아릴기의 예시 중에서 선택될 수 있다.In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.
본 명세서에 있어서, 헤테로아릴기는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 30인 것이 바람직하며, 상기 헤테로아릴기는 단환식 또는 다환식일 수 있다. 헤테로고리기의 예로는 티오펜기, 퓨라닐기, 피롤기, 이미다졸릴기, 티아졸릴기, 옥사졸릴기, 옥사디아졸릴기, 피리딜기, 바이피리딜기, 피리미딜기, 트리아지닐기, 트리아졸릴기, 아크리딜기, 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미딜기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀리닐기, 인돌릴기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤리닐기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but is not limited thereto.
본 명세서에 있어서, 헤테로아릴아민기의 예로는 치환 또는 비치환된 모노헤테로아릴아민기, 치환 또는 비치환된 디헤테로아릴아민기, 또는 치환 또는 비치환된 트리헤테로아릴아민기가 있다. 상기 헤테로아릴기가 2 이상을 포함하는 헤테로아릴아민기는 단환식 헤테로아릴기, 다환식 헤테로아릴기, 또는 단환식 헤테로아릴기와 다환식 헤테로아릴기를 동시에 포함할 수 있다. 예컨대, 상기 헤테로아릴아민기 중의 헤테로아릴기는 전술한 헤테로아릴기의 예시 중에서 선택될 수 있다.In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.
본 명세서에 있어서, N-아릴헤테로아릴아민기 및 N-알킬헤테로아릴아민기 중의 헤테로아릴기의 예시는 전술한 헤테로아릴기의 예시와 같다.In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.
본 명세서에 있어서, 아릴렌기는 아릴기에 결합 위치가 두 개 있는 것 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 아릴기의 설명이 적용될 수 있다.In the present specification, the arylene group refers to a divalent group having two bonding positions in the aryl group. The description of the aforementioned aryl group can be applied except that they are each divalent.
본 명세서에 있어서, 헤테로아릴렌기는 헤테로아릴기에 결합 위치가 두 개 있는 것 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 헤테로아릴기의 설명이 적용될 수 있다.In the present specification, the heteroarylene group means a divalent group having two bonding positions in the heteroaryl group. The description of the aforementioned heteroaryl group can be applied except that they are each divalent.
본 명세서에 있어서, 인접한 기가 서로 결합하여 형성되는 치환 또는 비치환된 고리에서, "고리"는 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 의미한다.In the present specification, in a substituted or unsubstituted ring in which adjacent groups are formed by bonding to each other, a “ring” means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.
본 명세서에 있어서, 고리는 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 의미한다.In the present specification, the ring is a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.
본 명세서에 있어서, 탄화수소고리는 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 1가가 아닌 것을 제외하고 상기 시클로알킬기 또는 아릴기의 예시 중에서 선택될 수 있다.In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group except for the above-mentioned monovalent one.
본 명세서에 있어서, 방향족고리는 단환 또는 다환일 수 있으며, 1가가 아닌 것을 제외하고 상기 아릴기의 예시 중에서 선택될 수 있다.In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group except that it is not monovalent.
본 명세서에 있어서, 헤테로고리는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 상기 헤테로고리는 단환 또는 다환일 수 있으며, 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 1가가 아닌 것을 제외하고 상기 헤테로아릴기의 예시 중에서 선택될 수 있다.In the present specification, the heterocycle includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocycle may be monocyclic or polycyclic, may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group except that it is not monovalent.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-1 내지 1-6 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-6.
[화학식 1-1][Formula 1-1]
Figure PCTKR2016011184-appb-I000009
Figure PCTKR2016011184-appb-I000009
[화학식 1-2][Formula 1-2]
Figure PCTKR2016011184-appb-I000010
Figure PCTKR2016011184-appb-I000010
[화학식 1-3][Formula 1-3]
Figure PCTKR2016011184-appb-I000011
Figure PCTKR2016011184-appb-I000011
[화학식 1-4][Formula 1-4]
Figure PCTKR2016011184-appb-I000012
Figure PCTKR2016011184-appb-I000012
[화학식 1-5][Formula 1-5]
Figure PCTKR2016011184-appb-I000013
Figure PCTKR2016011184-appb-I000013
[화학식 1-6][Formula 1-6]
Figure PCTKR2016011184-appb-I000014
Figure PCTKR2016011184-appb-I000014
상기 화학식 1-1 내지 1-6에 있어서,In Chemical Formulas 1-1 to 1-6,
X1 및 R1 내지 R16의 정의는 상기 화학식 1과 동일하고, Definitions of X1 and R1 to R16 are the same as in the above formula (1),
L1, Ar1 및 Ar2의 정의는 상기 화학식 B와 동일하며,Definition of L1, Ar1 and Ar2 is the same as in the above formula B,
R101 내지 R103은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 니트릴기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고,R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r101, r102 및 r103은 각각 1 내지 3의 정수이며,r101, r102 and r103 are each an integer of 1 to 3,
r101, r102 및 r103이 각각 2 이상인 경우, 2 이상의 괄호 내의 구조는 서로 같거나 상이하다.When r101, r102 and r103 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-7 내지 1-18 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-7 to 1-18.
[화학식 1-7][Formula 1-7]
Figure PCTKR2016011184-appb-I000015
Figure PCTKR2016011184-appb-I000015
[화학식 1-8][Formula 1-8]
Figure PCTKR2016011184-appb-I000016
Figure PCTKR2016011184-appb-I000016
[화학식 1-9][Formula 1-9]
Figure PCTKR2016011184-appb-I000017
Figure PCTKR2016011184-appb-I000017
[화학식 1-10][Formula 1-10]
Figure PCTKR2016011184-appb-I000018
Figure PCTKR2016011184-appb-I000018
[화학식 1-11][Formula 1-11]
Figure PCTKR2016011184-appb-I000019
Figure PCTKR2016011184-appb-I000019
[화학식 1-12][Formula 1-12]
Figure PCTKR2016011184-appb-I000020
Figure PCTKR2016011184-appb-I000020
[화학식 1-13][Formula 1-13]
Figure PCTKR2016011184-appb-I000021
Figure PCTKR2016011184-appb-I000021
[화학식 1-14][Formula 1-14]
Figure PCTKR2016011184-appb-I000022
Figure PCTKR2016011184-appb-I000022
[화학식 1-15][Formula 1-15]
Figure PCTKR2016011184-appb-I000023
Figure PCTKR2016011184-appb-I000023
[화학식 1-16][Formula 1-16]
Figure PCTKR2016011184-appb-I000024
Figure PCTKR2016011184-appb-I000024
[화학식 1-17][Formula 1-17]
Figure PCTKR2016011184-appb-I000025
Figure PCTKR2016011184-appb-I000025
[화학식 1-18][Formula 1-18]
Figure PCTKR2016011184-appb-I000026
Figure PCTKR2016011184-appb-I000026
상기 화학식 1-7 내지 1-18에 있어서,In Chemical Formulas 1-7 to 1-18,
R1 내지 R16의 정의는 상기 화학식 1과 동일하고, Definitions of R1 to R16 are the same as in the above formula (1),
L1, Ar1 및 Ar2의 정의는 상기 화학식 B와 동일하며,Definition of L1, Ar1 and Ar2 is the same as in the above formula B,
R101 내지 R103은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 니트릴기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고,R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r101, r102 및 r103은 각각 1 내지 3의 정수이며,r101, r102 and r103 are each an integer of 1 to 3,
r101, r102 및 r103이 각각 2 이상인 경우, 2 이상의 괄호 내의 구조는 서로 같거나 상이하다.When r101, r102 and r103 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R13 내지 R16은 수소이다.According to an exemplary embodiment of the present specification, in the general formula 1, R13 to R16 is hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R1 내지 R12 중 어느 하나는 상기 화학식 B이고, 나머지는 수소이다.According to an exemplary embodiment of the present specification, in the general formula 1, any one of R1 to R12 is the formula B, the rest is hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R1은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R1 is the general formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R2는 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R2 is the general formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R3은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R3 is the general formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R4는 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R4 is the formula B.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R5는 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R5 is the general formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R6은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R6 is the formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R7은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R7 is the formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R8은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R8 is the formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R9는 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R9 is the formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R10은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R10 is the formula B.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R11은 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R11 is the formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, R12는 상기 화학식 B이다.According to an exemplary embodiment of the present specification, in the general formula 1, R12 is the formula (B).
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, L1은 직접결합; 또는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, in the general formula B, L1 is a direct bond; Or a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, L1은 직접결합; 또는 아릴기이다.According to an exemplary embodiment of the present specification, in the general formula B, L1 is a direct bond; Or an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, L1은 직접결합; 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 바이페닐릴렌기; 또는 치환 또는 비치환된 나프틸렌기이다.According to an exemplary embodiment of the present specification, in the general formula B, L1 is a direct bond; Substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylylene group; Or a substituted or unsubstituted naphthylene group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, L1은 직접결합; 페닐렌기; 바이페닐릴렌기; 또는 나프틸렌기이다.According to an exemplary embodiment of the present specification, in the general formula B, L1 is a direct bond; Phenylene group; Biphenylylene group; Or a naphthylene group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 알킬기로 치환 또는 비치환된 아릴기, 및 알킬기 및 아민기로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된 아릴기; 또는 아릴기로 치환 또는 비치환된 헤테로아릴기이다.According to an exemplary embodiment of the present specification, in the general formula B, Ar1 and Ar2 are the same as or different from each other, and each independently at least one selected from the group consisting of an aryl group unsubstituted or substituted with an alkyl group, and an alkyl group and an amine group. Substituted or unsubstituted aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 바이페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 쿼터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 플루오레닐기; 치환 또는 비치환된 스피로비플루오레닐기; 치환 또는 비치환된 트리페닐레닐기; 치환 또는 비치환된 페난트레닐렌기; 치환 또는 비치환된 카바졸릴기; 치환 또는 비치환된 디벤조퓨라닐기; 또는 치환 또는 비치환된 디벤조티오펜기이다.According to an exemplary embodiment of the present specification, in the general formula B, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; A substituted or unsubstituted quarterphenyl group; Substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted spirobifluorenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted phenanthrenylene group; Substituted or unsubstituted carbazolyl group; Substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophene group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 알킬기로 치환 또는 비치환된 아릴기, 또는 아민기로 치환 또는 비치환된 페닐기; 아릴기로 치환 또는 비치환된 바이페닐기; 아릴기로 치환 또는 비치환된 터페닐기; 쿼터페닐기; 나프틸기; 알킬기 및 아릴기로 이루어진 군으로부터 1 이상으로 치환 또는 비치환된 플루오레닐기; 스피로비플루오레닐기; 트리페닐레닐기; 페난트레닐렌기; 아릴기로 치환 또는 비치환된 카바졸릴기; 디벤조퓨라닐기; 또는 디벤조티오펜기이다.According to an exemplary embodiment of the present specification, in the general formula B, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an alkyl group, or a phenyl group unsubstituted or substituted with an amine group; A biphenyl group unsubstituted or substituted with an aryl group; Terphenyl group unsubstituted or substituted with an aryl group; Quarter-phenyl group; Naphthyl group; A fluorenyl group unsubstituted or substituted with one or more from the group consisting of an alkyl group and an aryl group; Spirobifluorenyl group; Triphenylenyl group; Phenanthrenylene group; Carbazolyl group unsubstituted or substituted with an aryl group; Dibenzofuranyl group; Or a dibenzothiophene group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 페닐기, 바이페닐기, 터페닐기,나프틸기, 페난트레닐기, 메틸기로 치환된 플루오레닐기 또는 디페닐아민기로 치환 또는 비치환된 페닐기; 페닐기 또는 바이페닐기로 치환 또는 비치환된 바이페닐기; 페닐기로 치환 또는 비치환된 터페닐기; 쿼터페닐기; 나프틸기; 메틸기, 페닐기 및 나프틸기로 이루어진 군으로부터 1 이상으로 치환 또는 비치환된 플루오레닐기; 스피로비플루오레닐기; 트리페닐레닐기; 페난트레닐렌기; 페닐기로 치환 또는 비치환된 카바졸릴기; 디벤조퓨라닐기; 또는 디벤조티오펜기이다.According to an exemplary embodiment of the present specification, in the general formula B, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group substituted with a methyl group Or a phenyl group unsubstituted or substituted with a diphenylamine group; A biphenyl group unsubstituted or substituted with a phenyl group or a biphenyl group; Terphenyl group unsubstituted or substituted with a phenyl group; Quarter-phenyl group; Naphthyl group; A fluorenyl group unsubstituted or substituted with one or more from the group consisting of a methyl group, a phenyl group and a naphthyl group; Spirobifluorenyl group; Triphenylenyl group; Phenanthrenylene group; Carbazolyl group unsubstituted or substituted with a phenyl group; Dibenzofuranyl group; Or a dibenzothiophene group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, Ar1 및 Ar2는 서로 결합하여, 치환 또는 비치환된 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, in the general formula B, Ar1 and Ar2 are bonded to each other, to form a substituted or unsubstituted hetero ring.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B에 있어서, Ar1 및 Ar2는 서로 결합하여, 하기 화학식 C의 구조로 표시되는 고리를 형성한다.According to an exemplary embodiment of the present specification, in the general formula B, Ar1 and Ar2 are bonded to each other, to form a ring represented by the structure of the formula (C).
[화학식 C][Formula C]
Figure PCTKR2016011184-appb-I000027
Figure PCTKR2016011184-appb-I000027
상기 화학식 C에 있어서, In Chemical Formula C,
X2는 CRR', NR", O 또는 S이고,X2 is CRR ', NR ", O or S,
R, R', R", R201 및 R202는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이고,R, R ', R ", R201 and R202 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group,
r201 및 r202는 각각 1 내지 4의 정수이고,r201 and r202 are each an integer of 1 to 4,
상기 r201 및 r202가 각각 2 이상인 경우, 2 이상의 괄호 내의 구조는 서로 같거나 상이하며,When r201 and r202 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,
Figure PCTKR2016011184-appb-I000028
는 상기 화학식 B의 L1에 결합되는 부위이다.
Figure PCTKR2016011184-appb-I000028
Is a moiety bound to L1 of the formula (B).
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R 및 R'는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기이다.According to yet an embodiment of the present disclosure, in the general formula C, R and R 'are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R 및 R'는 서로 같거나 상이하고, 각각 독립적으로 알킬기이다.According to yet an embodiment of the present disclosure, in the general formula C, R and R 'are the same as or different from each other, and each independently an alkyl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R 및 R'는 메틸기이다.According to yet an embodiment of the present disclosure, in the general formula C, R and R 'is a methyl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R"는 치환 또는 비치환된 아릴기이다.According to yet an embodiment of the present disclosure, in the general formula C, R "is a substituted or unsubstituted aryl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R"는 아릴기이다.According to yet an embodiment of the present disclosure, in the general formula C, R "is an aryl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R"는 페닐기이다.According to yet an embodiment of the present disclosure, in the general formula C, R "is a phenyl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R201 및 R202는 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 아릴기이다.According to yet an embodiment of the present disclosure, in the general formula C, R201 and R202 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted aryl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R201 및 R202는 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 아릴기이다.According to yet an embodiment of the present disclosure, in the general formula C, R201 and R202 are the same as or different from each other, and each independently hydrogen; Or an aryl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C에 있어서, R201 및 R202는 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 페닐기이다.According to yet an embodiment of the present disclosure, in the general formula C, R201 and R202 are the same as or different from each other, and each independently hydrogen; Or a phenyl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 C는 하기 구조 중 어느 하나로 표시된다.According to yet an embodiment of the present disclosure, Formula C is represented by any one of the following structures.
Figure PCTKR2016011184-appb-I000029
Figure PCTKR2016011184-appb-I000029
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화합물 중에서 선택된다.According to an exemplary embodiment of the present specification, Formula 1 is selected from the following compounds.
Figure PCTKR2016011184-appb-I000030
Figure PCTKR2016011184-appb-I000030
Figure PCTKR2016011184-appb-I000031
Figure PCTKR2016011184-appb-I000031
Figure PCTKR2016011184-appb-I000032
Figure PCTKR2016011184-appb-I000032
Figure PCTKR2016011184-appb-I000033
Figure PCTKR2016011184-appb-I000033
Figure PCTKR2016011184-appb-I000034
Figure PCTKR2016011184-appb-I000034
Figure PCTKR2016011184-appb-I000035
Figure PCTKR2016011184-appb-I000035
Figure PCTKR2016011184-appb-I000036
Figure PCTKR2016011184-appb-I000036
Figure PCTKR2016011184-appb-I000037
Figure PCTKR2016011184-appb-I000037
Figure PCTKR2016011184-appb-I000038
Figure PCTKR2016011184-appb-I000038
Figure PCTKR2016011184-appb-I000039
Figure PCTKR2016011184-appb-I000039
Figure PCTKR2016011184-appb-I000040
Figure PCTKR2016011184-appb-I000040
Figure PCTKR2016011184-appb-I000041
Figure PCTKR2016011184-appb-I000041
Figure PCTKR2016011184-appb-I000042
Figure PCTKR2016011184-appb-I000042
Figure PCTKR2016011184-appb-I000043
Figure PCTKR2016011184-appb-I000043
Figure PCTKR2016011184-appb-I000044
Figure PCTKR2016011184-appb-I000044
Figure PCTKR2016011184-appb-I000045
Figure PCTKR2016011184-appb-I000045
Figure PCTKR2016011184-appb-I000046
Figure PCTKR2016011184-appb-I000046
Figure PCTKR2016011184-appb-I000047
Figure PCTKR2016011184-appb-I000047
Figure PCTKR2016011184-appb-I000048
Figure PCTKR2016011184-appb-I000048
Figure PCTKR2016011184-appb-I000049
Figure PCTKR2016011184-appb-I000049
Figure PCTKR2016011184-appb-I000050
Figure PCTKR2016011184-appb-I000050
Figure PCTKR2016011184-appb-I000051
Figure PCTKR2016011184-appb-I000051
Figure PCTKR2016011184-appb-I000052
Figure PCTKR2016011184-appb-I000052
Figure PCTKR2016011184-appb-I000053
Figure PCTKR2016011184-appb-I000053
Figure PCTKR2016011184-appb-I000054
Figure PCTKR2016011184-appb-I000054
본 명세서의 일 실시상태에 따르면, 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 전술한 스피로형 화합물을 포함하는 것인 유기 발광 소자를 제공한다.According to an exemplary embodiment of the present specification, the 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, wherein at least one of the organic material layers includes the aforementioned spiro-type compound.
본 명세서의 일 실시상태에 따르면, 본 명세서의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물층으로서 정공주입층, 정공수송층, 전자차단층, 발광층, 정공 차단층, 전자수송층, 전자전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적거나 많은 수의 유기층을 포함할 수 있다.According to an exemplary embodiment of the present specification, the organic material layer of the organic light emitting device of the present specification may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.
예컨대, 본 명세서의 유기 발광 소자의 구조는 도 1 및 도 2에 나타난 것과 같은 구조를 가질 수 있으나 이에만 한정되는 것은 아니다.For example, 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(20) 위에 제1 전극(30), 발광층(40) 및 제2 전극(50)이 순차적으로 적층된 유기 발광 소자(10)의 구조가 예시 되어 있다. 상기 도 1은 본 명세서의 일 실시상태에 따른 유기 발광 소자의 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.1 illustrates a structure of an organic light emitting device 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.
도 2에는 기판(20) 위에 제1 전극(30), 정공주입층(60), 정공수송층(70), 발광층(40), 전자수송층(80), 전자주입층(90) 및 제2 전극(50)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 상기 도 2는 본 명세서의 실시상태에 따른 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.2 illustrates a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90, and a second electrode on a substrate 20. A structure of an organic light emitting device in which 50) is sequentially stacked is illustrated. 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공주입층을 포함하고, 상기 정공주입층은 상기 화학식 1로 표시되는 스피로형 화합물을 포함한다.According to the exemplary embodiment of the present specification, the organic material layer includes a hole injection layer, and the hole injection layer includes a spiro type compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공수송층을 포함하고, 상기 정공수송층은 상기 화학식 1로 표시되는 스피로형 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a hole transport layer, the hole transport layer comprises a spiro-type compound represented by the formula (1).
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공조절층을 포함하고, 상기 정공조절층은 상기 화학식 1로 표시되는 스피로형 화합물을 포함한다.According to the exemplary embodiment of the present specification, the organic material layer includes a hole control layer, and the hole control layer includes a spiro type compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 스피로형 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a spiro type compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 스피로형 화합물을 발광층의 도펀트로서 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a spiro-type compound represented by Chemical Formula 1 as a dopant of the light emitting layer.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 하기 화학식 1-A로 표시되는 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by the following Chemical Formula 1-A.
[화학식 1-A][Formula 1-A]
Figure PCTKR2016011184-appb-I000055
Figure PCTKR2016011184-appb-I000055
상기 화학식 1-A에 있어서, In Chemical Formula 1-A,
n1은 1 이상의 정수이고,n1 is an integer of 1 or more,
Ar3은 치환 또는 비치환된 1가 이상의 벤조플루오렌기; 치환 또는 비치환된 1가 이상의 플루오란텐기; 치환 또는 비치환된 1가 이상의 파이렌기; 또는 치환 또는 비치환된 1가 이상의 크라이센기이고,Ar3 is a substituted or unsubstituted monovalent or higher benzofluorene group; Substituted or unsubstituted monovalent or higher fluoranthene group; A substituted or unsubstituted monovalent or higher pyrene group; Or a substituted or unsubstituted monovalent or higher chrysene group,
L1은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이며,L 1 is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴알킬기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있으며,Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted arylalkyl group; Or a substituted or unsubstituted heteroaryl group, or may combine with each other to form a substituted or unsubstituted ring,
n1이 2 이상인 경우, 2 이상의 괄호 안의 구조는 서로 같거나 상이하다.When n1 is 2 or more, the structures in two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1-A로 표시되는 화합물을 발광층의 도펀트로서 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1-A as a dopant of the light emitting layer.
본 명세서의 일 실시상태에 따르면, 상기 L1은 직접결합이다.According to an exemplary embodiment of the present specification, L1 is a direct bond.
본 명세서의 일 실시상태에 따르면, 상기 n1은 2 이다.According to an exemplary embodiment of the present specification, n1 is 2.
본 명세서의 일 실시상태에 있어서, 상기 Ar3은 중수소, 메틸기, 에틸기, 이소프로필기, 또는 tert-부틸기로 치환 또는 비치환된 2가의 파이렌기; 또는 중수소, 메틸기, 에틸기 또는 tert-부틸기로 치환 또는 비치환된 2가의 크라이센기이다In one embodiment of the present specification, Ar3 is a divalent pyrene group unsubstituted or substituted with deuterium, methyl, ethyl, isopropyl, or tert-butyl groups; Or a divalent chrysene group unsubstituted or substituted with deuterium, methyl, ethyl or tert-butyl groups.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 메틸기, 에틸기, 이소프로필기, tert-부틸기, 니트릴기 또는 알킬기로 치환된 실릴기로 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted with a silyl group substituted with a methyl group, ethyl group, isopropyl group, tert-butyl group, nitrile group or alkyl group It is an aryl group.
본 명세서의 일 실시상태에 따르면, Ar4 및 Ar5는 서로 같거나 상이하고 각각 독립적으로 알킬기로 치환된 실릴기로 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same or different from each other, and each independently an aryl group unsubstituted or substituted with a silyl group substituted with an alkyl group.
본 명세서의 일 실시상태에 따르면, Ar4 및 Ar5는 서로 같거나 상이하고 각각 독립적으로 트리메틸실릴기로 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same or different from each other, and each independently an aryl group unsubstituted or substituted with a trimethylsilyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 또는 치환 또는 비치환된 터페닐기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 메틸기, 에틸기, 이소프로필기, tert-부틸기, 니트릴기 또는 트리메틸실릴기로 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a nitrile group, or a trimethylsilyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 메틸기, 에틸기, tert-부틸기, 니트릴기 또는 트리메틸실릴기로 치환 또는 비치환된 비페닐기기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently a biphenyl group unsubstituted or substituted with a methyl group, ethyl group, tert-butyl group, nitrile group or trimethylsilyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 메틸기, 에틸기, tert-부틸기, 니트릴기 또는 트리메틸실릴기로 치환 또는 비치환된 터페닐기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently a terphenyl group unsubstituted or substituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group, or a trimethylsilyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 헤테로아릴기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently represent a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 메틸기, 에틸기, tert-부틸기, 니트릴기, 알킬기로 치환된 실릴기 또는 페닐기로 치환 또는 비치환된 헤테로아릴기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted with a methyl group, an ethyl group, a tert-butyl group, a nitrile group, a silyl group substituted with an alkyl group or a phenyl group It is an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 메틸기, 에틸기, tert-부틸기, 니트릴기, 트리메틸실릴기 또는 페닐기로 치환 또는 비치환된 디벤조퓨란기이다.According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted with a methyl group, ethyl group, tert-butyl group, nitrile group, trimethylsilyl group or phenyl group to be.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1-A는 하기 화합물 중에서 선택된다.According to an exemplary embodiment of the present specification, Formula 1-A is selected from the following compounds.
Figure PCTKR2016011184-appb-I000056
Figure PCTKR2016011184-appb-I000056
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 하기 화학식 2-A로 표시되는 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by the following Chemical Formula 2-A.
[화학식 2-A][Formula 2-A]
Figure PCTKR2016011184-appb-I000057
Figure PCTKR2016011184-appb-I000057
상기 화학식 2-A에 있어서,In Chemical Formula 2-A,
Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 단환의 아릴기; 또는 치환 또는 비치환된 다환의 아릴기이고,Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group,
G1 내지 G8은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 단환의 아릴기; 또는 치환 또는 비치환된 다환의 아릴기이다.G1 to G8 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 2-A로 표시되는 화합물을 발광층의 호스트로서 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Formula 2-A as a host of the light emitting layer.
본 명세서의 일 실시상태에 따르면, 상기 Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 다환의 아릴기이다.According to an exemplary embodiment of the present specification, Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted polycyclic aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 10 내지 30의 다환의 아릴기이다.According to an exemplary embodiment of the present specification, Ar11 and Ar12 are the same as or different from each other, and each independently represent a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 나프틸기이다.According to an exemplary embodiment of the present specification, Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted naphthyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 1-나프틸기이다.According to an exemplary embodiment of the present specification, Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted 1-naphthyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar11 및 Ar12는 1-나프틸기이다.According to an exemplary embodiment of the present specification, Ar11 and Ar12 are 1-naphthyl group.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G8은 수소이다.According to an exemplary embodiment of the present specification, the G1 to G8 is hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 화학식 2-A는 하기 화합물 중에서 선택된다.According to an exemplary embodiment of the present specification, Formula 2-A is selected from the following compounds.
Figure PCTKR2016011184-appb-I000058
Figure PCTKR2016011184-appb-I000058
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1-A로 표시되는 화합물을 발광층의 도펀트로서 포함하며, 상기 화학식 2-A로 표시되는 화합물을 발광층의 호스트로서 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes the compound represented by Formula 1-A as a dopant of the light emitting layer, and the compound represented by Formula 2-A as a host of the light emitting layer Include as.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택되는 1층 이상을 더 포함할 수 있다.According to an exemplary embodiment of the present specification, the organic material layer may further include one 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 and an electron injection layer.
본 명세서의 유기 발광 소자는 유기물층 중 1층 이상이 본 명세서의 스피로형 화합물, 즉, 상기 화학식 1로 표시되는 스피로형 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다.The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes a spiro-type compound of the present specification, that is, a spiro-type compound represented by Formula 1 above. Can be.
상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 명세서의 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시킴으로써 제조할 수 있다. 이 때 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 물리 증착 방법(PVD: physical Vapor Deposition)을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 제1 전극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물층을 형성한 후, 그 위에 제2 전극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 제2 전극 물질부터 유기물층, 제1 전극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. 또한, 상기 화학식 1로 표시되는 스피로형 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD: physical vapor deposition) such as sputtering (e-beam evaporation), by depositing a metal or conductive metal oxide or an alloy thereof on the substrate It can be prepared by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the spiro compound represented by Chemical Formula 1 may be formed of an organic material layer by a solution coating method as well as a vacuum deposition method in manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이다. According to one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.
본 명세서의 또 하나의 실시상태에 따르면, 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다. According to another exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al, Mg/Ag과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, Mg / Ag, and the like, but are not limited thereto.
상기 정공주입층은 정공 주입 물질로는 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 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(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정 되는 것은 아니다. The hole injection layer is a layer for injecting holes from an electrode with a hole injection material, and has a capability of transporting holes with a hole injection material, and thus has a hole injection effect at an anode, and an excellent hole injection effect with respect to a light emitting layer or a light emitting material. The compound which prevents the movement of the excitons produced | generated in the light emitting layer to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 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 is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As a hole transport material, the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
상기 정공조절층은 정공수송층으로부터 정공을 효과적으로 전달 받고, 정공 이동도를 조절하는 역할을 하여 발광층으로 전달되는 정공의 양을 조절하는 역할을 한다. 또한, 발광층으로부터 공급되는 전자가 정공수송층으로 넘어가지 않도록 하는 전자장벽 역할을 동시에 수행할 수 있다. 이는 발광층에서 정공과 전자의 균형을 극대화시켜 발광 효율을 증가시킬 수 있고, 정공조절층의 전자 안정성을 통하여 소자의 수명을 향상시킬 수 있으며, 당 기술 분야에 알려진 재료를 사용할 수 있다.The hole control layer effectively receives holes from the hole transport layer and serves to control hole mobility to adjust the amount of holes transferred to the light emitting layer. In addition, it may simultaneously serve as an electron barrier to prevent electrons supplied from the light emitting layer from falling into the hole transport layer. This can maximize the balance of holes and electrons in the light emitting layer to increase the luminous efficiency, improve the life of the device through the electron stability of the hole control layer, it is possible to use materials known in the art.
상기 발광층의 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로는 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤즈옥사졸, 벤조티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다. The light emitting material of the light emitting layer is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로 고리 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로 고리 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다. The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a hetero ring-containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
상기 도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 시클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.
상기 전자수송층의 전자 수송 물질로는 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transporting material of the electron transporting layer is a layer for receiving electrons from the electron injection layer and transporting electrons to the light emitting layer. The electron transporting material is a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer. This large material is suitable. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 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, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체 등이 있으나, 이에 한정되지 않는다. The electron injection layer is a layer that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer. The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-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, 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) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.
본 명세서에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1로 표시되는 스피로형 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.According to an exemplary embodiment of the present specification, the spiro compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present disclosure is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.
제조예Production Example
Figure PCTKR2016011184-appb-I000059
Figure PCTKR2016011184-appb-I000059
Figure PCTKR2016011184-appb-I000060
Figure PCTKR2016011184-appb-I000060
Figure PCTKR2016011184-appb-I000061
Figure PCTKR2016011184-appb-I000061
Figure PCTKR2016011184-appb-I000062
Figure PCTKR2016011184-appb-I000062
제조예 A-1. 화합물 A-1의 제조Preparation Example A-1. Preparation of Compound A-1
벤조퓨란-2-보로닉산 ( 30g, 185 mmol)과 1-브로모-2-아이오도벤젠 ( 53.2 g, 189 mmol)을 디옥산( 300ml)에 첨가한 후 2M 포타슘카보네이트 수용액( 100ml)을 첨가하고, 테트라키스트리페닐-포스피노팔라듐( 4.28 g, 2mol%)을 넣은 후, 4시간동안 가열 교반하였다. 상온으로 온도를 낮추고 반응을 종결한 후, 포타슘카보네이트 용액을 제거하여 층분리하였다. 용매 제거 후 헥산으로 컬럼하여 상기 화합물 A-1 , 무색 오일(42.7 g, 85 %)을 제조하였다.Benzofuran-2-boronic acid (30 g, 185 mmol) and 1-bromo-2-iodobenzene (53.2 g, 189 mmol) were added to dioxane (300 ml) followed by 2M aqueous potassium carbonate solution (100 ml). Tetrakistriphenyl-phosphinopalladium (4.28 g, 2 mol%) was added thereto, followed by heating and stirring for 4 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate solution was removed to separate the layers. After the solvent was removed, the compound A-1, a colorless oil (42.7 g, 85%) was prepared by column with hexane.
MS[M+H]+= 272.98MS [M + H] + = 272.98
제조예 A-2. 화합물 A-2의 제조Preparation Example A-2. Preparation of Compound A-2
상기 제조예 A-1에서 벤조퓨란-2-보로닉산 대신 벤조퓨란-3-보로닉산을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 A-2를 제조하였다.Compound A-2 was prepared in the same manner as in Preparation Example A-1, except that benzofuran-3-boronic acid was used instead of benzofuran-2-boronic acid.
MS[M+H]+= 272.98MS [M + H] + = 272.98
제조예 A-3. 화합물 A-3의 제조Preparation Example A-3. Preparation of Compound A-3
상기 제조예 A-2에서 1-브로모-2-아이오도벤젠 대신 1-브로모―3-클로로-2-아이오도벤젠을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 A-3를 제조하였다.Compound A-3 was prepared by the same method as Example 1-2 except for using 1-bromo-3-chloro-2-iodobenzene instead of 1-bromo-2-iodobenzene. .
MS[M+H]+= 306.94MS [M + H] + = 306.94
제조예 A-4. 화합물 A-4의 제조Preparation Example A-4. Preparation of Compound A-4
상기 제조예 A-1에서 벤조퓨란-2-보로닉산 대신 벤조티오펜-2-보로닉산을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 A-4를 제조하였다.Compound A-4 was prepared in the same manner as in Preparation Example A-1, except that benzothiophene-2-boronic acid was used instead of benzofuran-2-boronic acid.
MS[M+H]+= 288.96MS [M + H] + = 288.96
제조예 A-5. 화합물 A-5의 제조Preparation Example A-5. Preparation of Compound A-5
상기 제조예 A-1에서 벤조퓨란-2-보로닉산 대신 벤조티오펜-3-보로닉산을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 A-5를 제조하였다.Compound A-5 was prepared in the same manner as in Preparation Example A-1, except that benzothiophene-3-boronic acid was used instead of benzofuran-2-boronic acid.
MS[M+H]+= 288.96MS [M + H] + = 288.96
제조예 B-1. 화합물 B-1의 제조Preparation Example B-1. Preparation of Compound B-1
화합물 A-1 (30g, 110 mmol) 을 THF (250ml) 에 용해한 후 온도를 -78도로 낮춘 후 2.5M n-BuLi (57ml) 을 적가하고 30분 후 2-브로모-9H-플루오레-9-온 (28.3g, 109mmol) 을 넣어주고 RT로 올린 후 1시간동안 교반하였다. 1N HCl (ml)를 넣어주고 30분간 교반한 후 층분리하여 용매제거 후 헥산으로 재결정하여 화합물 B-1 (47.2g, 95%)를 제조하였다.After dissolving compound A-1 (30 g, 110 mmol) in THF (250 ml), the temperature was lowered to -78 degrees, and then 2.5M n-BuLi (57 ml) was added dropwise, and after 30 minutes, 2-bromo-9H-fluore-9 -On (28.3g, 109mmol) was added and raised to RT and stirred for 1 hour. 1N HCl (ml) was added thereto, stirred for 30 minutes, layer separation, solvent removal, and recrystallization with hexane to prepare Compound B-1 (47.2 g, 95%).
MS[M+H]+= 453.04MS [M + H] + = 453.04
제조예 B-2. 화합물 B-2의 제조Preparation Example B-2. Preparation of Compound B-2
상기 제조예 B-1에서 2-브로모-9H-플루오레-9-온 대신 4-브로모-9H-플루오레-9-온 을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-2를 제조하였다.Compound B-2 was synthesized in the same manner as in Production Example B-1, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
MS[M+H]+= 453.04MS [M + H] + = 453.04
제조예 B-3. 화합물 B-3의 제조Preparation Example B-3. Preparation of Compound B-3
상기 제조예 B-1에서 화합물 A-1 대신 화합물 A-2 을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-3를 제조하였다.Compound B-3 was prepared in the same manner as in Preparation Example B-1, except that Compound A-2 was used instead of Compound A-1.
MS[M+H]+= 453.04MS [M + H] + = 453.04
제조예 B-4. 화합물 B-4의 제조Preparation Example B-4. Preparation of Compound B-4
상기 제조예 B-3의 합성에서 2-브로모-9H-플루오레-9-온 대신 4-브로모-9H-플루오레-9-온을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-4를 제조하였다.Compound B- was synthesized in the same manner as in the synthesis of Preparation Example B-3, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. 4 was prepared.
MS[M+H]+= 453.04MS [M + H] + = 453.04
제조예 B-5. 화합물 B-5의 제조Preparation Example B-5. Preparation of Compound B-5
상기 제조예 B-1에서 화합물 A-1 대신 화합물 A-3 을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-5를 제조하였다.Compound B-5 was prepared in the same manner as in Preparation Example B-1, except that Compound A-3 was used instead of Compound A-1.
MS[M+H]+= 453.04MS [M + H] + = 453.04
제조예 B-6. 화합물 B-6의 제조Preparation Example B-6. Preparation of Compound B-6
상기 제조예 B-1에서 화합물 A-1 대신 화합물 A-4 을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-6를 제조하였다.Compound B-6 was prepared in the same manner as in Preparation Example B-1, except that Compound A-4 was used instead of Compound A-1.
MS[M+H]+= 469.02MS [M + H] + = 469.02
제조예 B-7. 화합물 B-7의 제조Preparation Example B-7. Preparation of Compound B-7
상기 제조예 B-6에서 2-브로모-9H-플루오레-9-온 대신 4-브로모-9H-플루오레-9-온을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-7를 제조하였다.Compound B-7 was synthesized in the same manner as in Production Example B-6, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
MS[M+H]+= 469.02MS [M + H] + = 469.02
제조예 B-8. 화합물 B-8의 제조Preparation Example B-8. Preparation of Compound B-8
상기 제조예 B-1에서 화합물 A-1 대신 화합물 A-5 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-8를 제조하였다Except for using Compound A-5 instead of Compound A-1 in Preparation Example B-1 to prepare a compound B-8 by synthesizing in the same manner
MS[M+H]+= 469.02MS [M + H] + = 469.02
제조예 B-9. 화합물 B-9의 제조Preparation Example B-9. Preparation of Compound B-9
상기 제조예 B-8에서 2-브로모-9H-플루오레-9-온 대신 4-브로모-9H-플루오레-9-온을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-9를 제조하였다.Compound B-9 was synthesized in the same manner as in Preparation Example B-8, except that 4-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
MS[M+H]+= 469.02MS [M + H] + = 469.02
제조예 B-10. 화합물 B-10의 제조Preparation Example B-10. Preparation of Compound B-10
상기 제조예 B-8에서 2-브로모-9H-플루오레-9-온 대신 1-브로모-9H-플루오레-9-온을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 B-10를 제조하였다.Compound B-10 was synthesized in the same manner as in Example B-8, except that 1-bromo-9H-fluoren-9-one was used instead of 2-bromo-9H-fluoren-9-one. Prepared.
MS[M+H]+= 469.02MS [M + H] + = 469.02
제조예 C-1. 화합물 C-1의 제조Preparation Example C-1. Preparation of Compound C-1
화합물 B-1 (30g, 66.4 mmol) 을 아세트산(250ml) 에 넣은 후 트리플루오로아세트산 10ml를 적가하고 교반 환류하였다. 상온으로 온도를 낮추고 물로 중화한 후 걸러진 고체를 에틸아세테이트로 재결정하여 화합물 C-1 (20g, 70%)를 제조하였다. Compound B-1 (30 g, 66.4 mmol) was added to acetic acid (250 ml), and then 10 ml of trifluoroacetic acid was added dropwise and stirred under reflux. The mixture was cooled to room temperature, neutralized with water, and the filtered solid was recrystallized with ethyl acetate to obtain compound C-1 (20 g, 70%).
MS[M+H]+= 435.03MS [M + H] + = 435.03
제조예 C-2. 화합물 C-2의 제조Preparation Example C-2. Preparation of Compound C-2
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-2을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-2를 제조하였다.Compound C-2 was prepared in the same manner as in Preparation Example C-1, except that Compound B-2 was used instead of Compound B-1.
MS[M+H]+= 435.03MS [M + H] + = 435.03
제조예 C-3. 화합물 C-3의 제조Preparation Example C-3. Preparation of Compound C-3
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-3을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-3를 제조하였다.Compound C-3 was prepared in the same manner as in Preparation Example C-1, except that Compound B-3 was used instead of Compound B-1.
MS[M+H]+= 435.03MS [M + H] + = 435.03
제조예 C-4. 화합물 C-4의 제조Preparation Example C-4. Preparation of Compound C-4
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-4을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-4를 제조하였다.Compound C-4 was prepared in the same manner as in Preparation Example C-1, except that Compound B-4 was used instead of Compound B-1.
MS[M+H]+= 435.03MS [M + H] + = 435.03
제조예 C-5. 화합물 C-5의 제조Preparation Example C-5. Preparation of Compound C-5
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-5을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-5를 제조하였다.Compound C-5 was prepared in the same manner as in Preparation Example C-1, except that Compound B-5 was used instead of Compound B-1.
MS[M+H]+= 391.08MS [M + H] + = 391.08
제조예 C-6. 화합물 C-6의 제조Preparation Example C-6. Preparation of Compound C-6
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-6을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-6를 제조하였다.Compound C-6 was prepared by the same method as the preparation method C-1 except that compound B-6 was used instead of compound B-1.
MS[M+H]+= 451.01MS [M + H] + = 451.01
제조예 C-7. 화합물 C-7의 제조Preparation Example C-7. Preparation of Compound C-7
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-7을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-7를 제조하였다.Compound C-7 was prepared in the same manner as in Preparation Example C-1, except that Compound B-7 was used instead of Compound B-1.
MS[M+H]+= 451.01MS [M + H] + = 451.01
제조예 C-8. 화합물 C-8의 제조Preparation Example C-8. Preparation of Compound C-8
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-8을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-8를 제조하였다.Except for using the compound B-8 instead of compound B-1 in Preparation Example C-1 was synthesized in the same manner to prepare a compound C-8.
MS[M+H]+= 451.01MS [M + H] + = 451.01
제조예 C-9. 화합물 C-9의 제조Preparation Example C-9. Preparation of Compound C-9
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-9을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-9를 제조하였다.Compound C-9 was prepared by the same method as the preparation method C-1 except that compound B-9 was used instead of compound B-1.
MS[M+H]+= 451.01MS [M + H] + = 451.01
제조예 C-10. 화합물 C-10의 제조Preparation Example C-10. Preparation of Compound C-10
상기 제조예 C-1에서 화합물 B-1 대신 화합물 B-10을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 C-10를 제조하였다.Compound C-10 was prepared in the same manner as in Preparation Example C-1, except that Compound B-10 was used instead of Compound B-1.
MS[M+H]+= 451.01MS [M + H] + = 451.01
제조예 D-1. 화합물 D-1의 제조Preparation Example D-1. Preparation of Compound D-1
화합물 C-3 (20g, 46mmol)과 4-클로로페닐보로닉산 (7.33g, 47mmol)을 테트라하이드로퓨란( 300ml)에 첨가한 후 2M 포타슘카보네이트 수용액( 100ml)을 첨가하고, 테트라키스트리페닐-포스피노팔라듐(1.06g, 0.92mmol)을 넣은 후, 7시간동안 가열 교반하였다. 상온으로 온도를 낮추고 반응을 종결한 후, 포타슘카보네이트 용액을 제거하여 층분리하였다. 용매 제거 후 테트라하이드로퓨란과 에틸아세테이트로 재결정하여 상기 화합물 D-1 (18.2g, 수율 25%)을 제조하였다.Compound C-3 (20 g, 46 mmol) and 4-chlorophenylboronic acid (7.33 g, 47 mmol) were added to tetrahydrofuran (300 ml), followed by 2M aqueous potassium carbonate solution (100 ml), and tetrakistriphenyl- Phosphinopalladium (1.06 g, 0.92 mmol) was added thereto, followed by heating and stirring for 7 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate solution was removed to separate the layers. After the solvent was removed, the compound D-1 (18.2 g, yield 25%) was prepared by recrystallization with tetrahydrofuran and ethyl acetate.
MS[M+H]+= 467.11MS [M + H] + = 467.11
제조예 D-2. 화합물 D-2의 제조Preparation Example D-2. Preparation of Compound D-2
상기 제조예 D-1에서 화합물 C-3 대신 화합물 C-9을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 D-2를 제조하였다.Compound D-2 was prepared in the same manner as in Preparation Example D-1, except that Compound C-9 was used instead of Compound C-3.
MS[M+H]+= 483.09MS [M + H] + = 483.09
제조예 1. 화합물 1의 제조Preparation Example 1 Preparation of Compound 1
Figure PCTKR2016011184-appb-I000063
Figure PCTKR2016011184-appb-I000063
화합물 C-1 ( 20g, 46mmol)과 , 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린( 16.9g, 47mmol), 소듐-t-부톡사이드( 6.2g, 64.4mmol) 을 tolene에 넣고 가열교반한 뒤 환류시키고 [비스(트라이-t-부틸포스핀)]팔라듐 (1.03mg. 2mmol%) 을 넣었다. 상온으로 온도를 낮추고 반응을 종결한 후, 테트라하이드로퓨란과 에틸아세테이트를 이용해 재결정하여 화합물 1( 28.3g, 65%)을 제조하였다.Compound C-1 (20g, 46mmol) with 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline (16.9g, 47mmol), sodium-t-butoxide (6.2g , 64.4 mmol) were added to tolene, and the mixture was heated and stirred to reflux, followed by [bis (tri-t-butylphosphine)] palladium (1.03 mg. 2 mmol%). After the temperature was lowered to room temperature and the reaction was terminated, Compound 1 (28.3 g, 65%) was prepared by recrystallization using tetrahydrofuran and ethyl acetate.
MS[M+H]+= 716.29MS [M + H] + = 716.29
제조예 2. 화합물 2의 제조Preparation Example 2 Preparation of Compound 2
Figure PCTKR2016011184-appb-I000064
Figure PCTKR2016011184-appb-I000064
상기 제조예 1에서 화합물 C-1 대신 C-2을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 N-페닐-[1, 1':4', 1"-터페닐]아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 2를 제조하였다.In Preparation Example 1, C-2 was used instead of Compound C-1, and 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline was substituted with N-phenyl- [1,1 ′. Compound 2 was prepared in the same manner except for using: 4 ', 1 "-terphenyl] amine.
MS[M+H]+= 676.26MS [M + H] + = 676.26
제조예 3. 화합물 3의 제조Preparation Example 3 Preparation of Compound 3
Figure PCTKR2016011184-appb-I000065
Figure PCTKR2016011184-appb-I000065
상기 제조예 1에서 화합물 C-1 대신 C-3을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 N-(1, 1'-비페닐]-4-일)-[1, 1'-비페닐]-2-아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 3을 제조하였다.In Preparation Example 1, C-3 was used instead of Compound C-1, and N- (1,1′-ratio instead of 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline. Compound 3 was prepared in the same manner except using phenyl] -4-yl)-[1,1'-biphenyl] -2-amine.
MS[M+H]+= 676.26MS [M + H] + = 676.26
제조에 4. 화합물 4의 제조4. Preparation of Compound 4
Figure PCTKR2016011184-appb-I000066
Figure PCTKR2016011184-appb-I000066
상기 제조예 1에서 화합물 C-1 대신 C-3을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 N-(1, 1'-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 4를 제조하였다.In Preparation Example 1, C-3 was used instead of Compound C-1, and N- (1,1′-ratio instead of 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline. Compound 4 was prepared by the same method except that phenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine was used.
MS[M+H]+= 716.29MS [M + H] + = 716.29
제조예 5. 화합물 5의 제조Preparation Example 5 Preparation of Compound 5
Figure PCTKR2016011184-appb-I000067
Figure PCTKR2016011184-appb-I000067
상기 제조예 1에서 화합물 C-1 대신 D-1을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 9,9-디메틸-N-페닐-9H-플루오렌-2-아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 5를 제조하였다.In Preparation Example 1, instead of compound C-1, D-1 was used, and instead of 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline, 9,9-dimethyl-N-phenyl Compound 5 was prepared in the same manner except for using -9H-fluoren-2-amine.
MS[M+H]+= 716.29MS [M + H] + = 716.29
제조예 6. 화합물 6의 제조Preparation Example 6 Preparation of Compound 6
Figure PCTKR2016011184-appb-I000068
Figure PCTKR2016011184-appb-I000068
상기 제조예 1에서 화합물 C-1 대신 C-5을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 디([1,1'-비페닐)-4-일)아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 합물 6 를 제조하였다.In Preparation Example 1, C-5 was used instead of Compound C-1 and 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline was used instead of di ([1,1′-ratio). Synthesis 6 was prepared in the same manner except that phenyl) -4-yl) amine was used.
MS[M+H]+= 676.26MS [M + H] + = 676.26
제조예 7. 화합물 7의 제조Preparation Example 7 Preparation of Compound 7
Figure PCTKR2016011184-appb-I000069
Figure PCTKR2016011184-appb-I000069
상기 제조예 1에서 화합물 C-1 대신 C-6을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 디([1,1'-비페닐)-4-일)아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 7를 제조하였다.In Preparation Example 1, C-6 was used instead of Compound C-1 and 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline was used instead of di ([1,1′-ratio). Compound 7 was prepared in the same manner except using phenyl) -4-yl) amine.
MS[M+H]+= 692.23MS [M + H] + = 692.23
제조예 8. 화합물 8의 제조Preparation Example 8 Preparation of Compound 8
Figure PCTKR2016011184-appb-I000070
Figure PCTKR2016011184-appb-I000070
상기 제조예 1에서 화합물 C-1 대신 C-7을, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 N-페닐-[1, 1':4', 1"-터페닐]아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 8 를 제조하였다.C-7 instead of compound C-1 in Preparation Example 1, and N-phenyl- [1,1 ′: 4 instead of 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline Compound 8 was prepared in the same manner except that 1′-terphenyl] amine was used.
MS[M+H]+= 692.23MS [M + H] + = 692.23
제조예9. 화합물 9의 제조Preparation Example 9. Preparation of Compound 9
Figure PCTKR2016011184-appb-I000071
Figure PCTKR2016011184-appb-I000071
상기 제조예 1에서 화합물 C-1 대신 D-2을 사용하고, N-(1, 1'-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 9를 제조하였다.In Preparation Example 1, using D-2 instead of compound C-1, and using N- (1,1′-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine Except for the synthesis in the same manner to prepare compound 9.
MS[M+H]+= 808.30MS [M + H] + = 808.30
제조예 10. 화합물 10의 제조Preparation Example 10 Preparation of Compound 10
Figure PCTKR2016011184-appb-I000072
Figure PCTKR2016011184-appb-I000072
상기 제조예 1에서 화합물 C-1 대신 C-10을 사용하고, 4-(9,9-디메틸-9H-플루오렌-2-일)-N-페닐아닐린 대신 N.9-디페닐-9H-카바졸-3-아민을 사용한 것을 제외하고는 동일한 방법으로 합성하여 화합물 10을 제조하였다C-10 was used instead of Compound C-1 in Preparation Example 1, and N (9,9-diphenyl-9H-) instead of 4- (9,9-dimethyl-9H-fluoren-2-yl) -N-phenylaniline. Compound 10 was prepared by synthesis in the same manner except that carbazole-3-amine was used.
MS[M+H]+= 705.30MS [M + H] + = 705.30
실시예 1-1Example 1-1
ITO(인듐 주석 산화물)가 1,000Å 두께로 박막 코팅된 유리 기판(corning 7059 glass)을, 분산제를 녹인 증류수에 넣고 초음파로 세척하였다. 세제는 Fischer Co.의 제품을 사용하였으며, 증류수는 Millipore Co. 제품의 필터(Filter)로 2차 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후, 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후 이소프로필알콜, 아세톤, 메탄올 용제 순서로 초음파 세척을 하고 건조시켰다.A glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) with a thickness of 1,000 Å was placed in distilled water in which a dispersant was dissolved, and ultrasonically washed. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.
이렇게 준비된 ITO 투명 전극 위에 헥사니트릴 헥사아자트리페닐렌(hexanitrile hexaazatriphenylene)를 500Å의 두께로 열 진공 증착하여 정공 주입층을 형성하였다. 그 위에 정공을 수송하는 물질인 위 제조예 1에서 합성한 화합물1 (900Å)을 진공증착한 후 이어서 상기 정공수송층 위에 HT2를 막두께 100Å으로 진공증착하여 정공 조절층을 형성하였다. 화합물 발광층으로 호스트 H1과 도판트 D1 화합물(25:1) 을 300Å의 두께로 진공 증착하였다. 그 다음에 E1 화합물(300Å)을 전자주입 및 수송층으로 순차적으로 열 진공 증착하였다. 상기 전자 수송층 위에 순차적으로 12Å 두께의 리튬 플루오라이드(LiF)와 2,000Å 두께의 알루미늄을 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. Compound 1 (900 kPa) synthesized in Preparation Example 1, which is a material for transporting holes thereon, was vacuum deposited, followed by vacuum deposition of HT2 at a film thickness of 100 kPa on the hole transport layer to form a hole control layer. In the compound emitting layer, the host H1 and the dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 kPa. Then, E1 compound (300 kPa) was thermally vacuum deposited sequentially into the electron injection and transport layer. An organic light emitting device was manufactured by sequentially depositing 12 Å thick lithium fluoride (LiF) and 2,000 Å thick aluminum on the electron transport layer to form a cathode.
상기의 과정에서 유기물의 증착속도는 1 Å/sec를 유지하였고, 리튬플루라이드는 0.2 Å/sec, 알루미늄은 3 ~ 7 Å/sec의 증착속도를 유지하였다.In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7 Å / sec.
Figure PCTKR2016011184-appb-I000073
Figure PCTKR2016011184-appb-I000073
실시예 1-2Example 1-2
상기 실시예 1-1에서 정공수송층으로 화합물 1 대신 화합물 3 를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 3 instead of compound 1 as the hole transport layer in Example 1-1 was the same experiment.
실시예 1-3Example 1-3
상기 실시예 1-1에서 정공 수송층으로 화합물 1 대신 화합물 4를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using compound 4 instead of compound 1 as the hole transport layer in Example 1-1 was the same experiment.
실시예 1-4Example 1-4
상기 실시예 1-1에서 정공 수송층으로 화합물 1 대신 화합물 5를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 5 instead of compound 1 as the hole transport layer in Example 1-1 was the same experiment.
실시예 1-5Example 1-5
상기 실시예 1-1에서 정공 수송층으로 화합물 1 대신 화합물 7를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 7 instead of compound 1 as the hole transport layer in Example 1-1 was the same experiment.
실시예 1-6Example 1-6
상기 실시예 1-1에서 정공 수송층으로 화합물 1 대신 화합물 10를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 10 instead of compound 1 as the hole transport layer in Example 1-1 was the same experiment.
비교예 1-1Comparative Example 1-1
상기 실시예 1-1에서 정공 수송층으로 화합물 1 대신 하기 HT1를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the following HT1 instead of compound 1 as the hole transport layer in Example 1-1 was the same experiment.
Figure PCTKR2016011184-appb-I000074
Figure PCTKR2016011184-appb-I000074
상기 실시예 1-1 내지 1-6 및 비교예 1-1의 유기 발광 소자의 소자 평가 결과를 하기 표 1에 나타내었다.Device evaluation results of the organic light emitting diodes of Examples 1-1 to 1-6 and Comparative Example 1-1 are shown in Table 1 below.
50 mA/㎠50 mA / ㎠ 정공수송층 물질Hole transport material 전압(V)Voltage (V) 전류효율(cd/A)Current efficiency (cd / A)
비교예 1-1Comparative Example 1-1 HT1HT1 4.114.11 5.325.32
실시예 1-1Example 1-1 화합물1Compound 1 3.703.70 5.615.61
실시예 1-2Example 1-2 화합물3Compound 3 3.463.46 5.755.75
실시예 1-3Example 1-3 화합물4Compound 4 3.593.59 5.885.88
실시예 1-4Example 1-4 화합물5Compound 5 3.663.66 5.915.91
실시예 1-5Example 1-5 화합물7Compound7 3.713.71 5.555.55
실시예 1-6Example 1-6 화합물10 Compound 10 3.553.55 5.895.89
상기 표 1과 같이 본 명세서의 일 실시상태에 따른 스피로형 화합물을 사용하여 제작한 실시예 1-1 내지 1-6의 유기 발광 소자는 벤지딘 타입의 물질인 비교예 1-1 보다 저전압, 고효율의 특성을 나타내는 것을 알 수 있다.As shown in Table 1, the organic light emitting diodes of Examples 1-1 to 1-6 manufactured by using a spiro type compound according to an exemplary embodiment of the present specification have a lower voltage and higher efficiency than those of Comparative Example 1-1, which are benzidine-type materials. It can be seen that it exhibits characteristics.
실시예 2-1Example 2-1
ITO(인듐 주석 산화물)가 1,000Å 두께로 박막 코팅된 유리 기판(corning 7059 glass)을, 분산제를 녹인 증류수에 넣고 초음파로 세척하였다. 세제는 Fischer Co.의 제품을 사용하였으며, 증류수는 Millipore Co. 제품의 필터(Filter)로 2차 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후, 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후 이소프로필알콜, 아세톤, 메탄올 용제 순서로 초음파 세척을 하고 건조시켰다.A glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) with a thickness of 1,000 Å was placed in distilled water in which a dispersant was dissolved, and ultrasonically washed. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.
이렇게 준비된 ITO 투명 전극 위에 헥사니트릴 헥사아자트리페닐렌(hexanitrile hexaazatriphenylene)를 500Å의 두께로 열 진공 증착하여 정공 주입층을 형성하였다. 그 위에 정공을 수송하는 물질인 HT1 (900Å)을 진공증착한 후 이어서 상기 정공 수송층 위에 화합물 2를 막두께 100Å으로 진공증착하여 정공조절층을 형성하였다. 발광층으로 호스트 H1과 도판트 D1 (25:1) 을 300Å의 두께로 진공 증착하였다. 그 다음에 E1 (300Å)을 전자주입 및 수송층으로 순차적으로 열 진공 증착하였다. 상기 전자 수송층 위에 순차적으로 12Å 두께의 리튬 플루오라이드(LiF)와 2,000Å 두께의 알루미늄을 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. HT1 (900 kPa), which is a material for transporting holes, was vacuum deposited thereon, and then Compound 2 was vacuum deposited at a film thickness of 100 kPa on the hole transport layer to form a hole control layer. In the light emitting layer, the host H1 and the dopant D1 (25: 1) were vacuum deposited to a thickness of 300 kPa. E1 (300 kPa) was then thermally vacuum deposited sequentially into the electron injection and transport layer. An organic light emitting device was manufactured by sequentially depositing 12 Å thick lithium fluoride (LiF) and 2,000 Å thick aluminum on the electron transport layer to form a cathode.
상기의 과정에서 유기물의 증착속도는 1 Å/sec를 유지하였고, 리튬플루라이드는 0.2 Å/sec, 알루미늄은 3 ~ 7 Å/sec의 증착속도를 유지하였다.In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7 Å / sec.
Figure PCTKR2016011184-appb-I000075
Figure PCTKR2016011184-appb-I000075
실시예 2-2Example 2-2
상기 실시예 2-1에서 정공조절층으로 화합물 2 대신 화합물 6를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 6 instead of compound 2 as the hole control layer in Example 2-1 was the same experiment.
실시예 2-3Example 2-3
상기 실시예 2-1에서 정공조절층으로 화합물 2 대신 화합물 8를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 8 instead of compound 2 as the hole control layer in Example 2-1 was the same experiment.
실시예 2-4Example 2-4
상기 실시예 2-1에서 정공조절층으로 화합물 2 대신 화합물 9를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound 9 instead of compound 2 as the hole control layer in Example 2-1 was the same experiment.
비교예 2-1Comparative Example 2-1
상기 실시예 2-1에서 정공조절층으로 화합물 2 대신 HT2를 사용한 것을 제외하고는 동일하게 실험하였다.Except for using the compound HT2 instead of compound 2 in the hole control layer in Example 2-1 was the same experiment.
Figure PCTKR2016011184-appb-I000076
Figure PCTKR2016011184-appb-I000076
상기 실시예 2-1 내지 2-4 및 비교예 2-1 의 유기 발광 소자의 소자 평가 결과를 하기 표 2에 나타내었다.Device evaluation results of the organic light emitting diodes of Examples 2-1 to 2-4 and Comparative Example 2-1 are shown in Table 2 below.
실험예50 mA/㎠Experimental Example 50 mA / cm 2 정공조절층 물질Hole control layer material 전압(V)Voltage (V) 전류효율(cd/A)Current efficiency (cd / A)
비교예 2-1Comparative Example 2-1 HT2HT2 4.024.02 5.115.11
실시예 2-1Example 2-1 화합물2Compound 2 4.034.03 5.305.30
실시예 2-2Example 2-2 화합물6Compound6 3.563.56 5.765.76
실시예 2-3Example 2-3 화합물8Compound 8 4.014.01 5.025.02
실시예 2-4Example 2-4 화합물9Compound 9 3.613.61 5.985.98
상기 표 2와 같이 본 명세서의 일 실시상태에 따른 화학식 1로 표시되는 스피로형 화합물을 사용하여 제작한 실시예 2-1 내지 2-4의 유기 발광 소자는 카바졸 타입의 물질인 HT2를 사용한 비교예 2-1의 유기 발광 소자 보다 저전압, 고효율의 특성을 나타내는 것을 알 수 있다.As shown in Table 2, the organic light emitting diodes of Examples 2-1 to 2-4 prepared using the spiro type compound represented by Formula 1 according to the exemplary embodiment of the present specification are compared with HT2, which is a carbazole type material. It can be seen that the characteristics of lower voltage and higher efficiency are shown than the organic light emitting element of Example 2-1.
특히, 본 명세서의 일 실시상태에 따른 화학식 1로 표시되는 스피로형 화합물의 분자구조에서 산소족 원소가 상기 화합물 6 및 9와 같이 형성되는 경우, 이는 정공조절층으로 사용한 경우 화합물 6 및 9가 높은 삼중항에너지를 가짐으로써 소자성능을 향상시키는 효과가 있다.In particular, in the molecular structure of the spiro-type compound represented by the formula (1) according to an embodiment of the present disclosure when the oxygen group element is formed as the compounds 6 and 9, which is a triple compound 6 and 9 is high when used as a hole control layer Having a constant energy has the effect of improving device performance.
본 명세서의 일 실시상태에 따른 화학식 1로 표시되는 스피로형 화합물은 유기 발광 소자를 비롯한 유기 전자 소자에서 정공 수송 및 정공 조절 역할을 할 수 있으며, 본 명세서에 따른 유기 발광 소자는 효율, 구동전압, 안정성 면에서 우수한 특성을 나타낸다.The spiro compound represented by Formula 1 according to one embodiment of the present specification may play a role of hole transport and hole control in an organic electronic device including an organic light emitting device, and the organic light emitting device according to the present specification may include efficiency, driving voltage, Excellent properties in terms of stability.
[부호의 설명][Description of the code]
10, 11: 유기 발광 소자10, 11: organic light emitting element
20: 기판20: substrate
30: 제1 전극30: first electrode
40: 발광층40: light emitting layer
50: 제2 전극50: second electrode
60: 정공주입층60: hole injection layer
70: 정공수송층70: hole transport layer
80: 전자수송층80: electron transport layer
90: 전자주입층90: electron injection layer

Claims (18)

  1. 하기 화학식 1로 표시되는 스피로형 화합물:Spiro type compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2016011184-appb-I000077
    Figure PCTKR2016011184-appb-I000077
    상기 화학식 1에 있어서,In Chemical Formula 1,
    X1은 O 또는 S이고,X 1 is O or S,
    R1 내지 R12 중 어느 하나는 하기 화학식 B이고, 나머지 및 R13 내지 R16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 니트릴기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이며,Any one of R1 to R12 is the following Formula B, and the remaining and R13 to R16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
    [화학식 B][Formula B]
    Figure PCTKR2016011184-appb-I000078
    Figure PCTKR2016011184-appb-I000078
    상기 화학식 B에 있어서, In Chemical Formula B,
    L1은 서로 같거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이고,L1 is the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
    Ar1 및 Ar2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 서로 결합하여, 치환 또는 비치환된 고리를 형성한다.Ar1 and Ar2 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, or combine with each other to form a substituted or unsubstituted ring.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1은 하기 화학식 1-1 내지 1-6 중 어느 하나로 표시되는 것인 스피로형 화합물:Formula 1 is a spiro compound represented by any one of the following formula 1-1 to 1-6:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2016011184-appb-I000079
    Figure PCTKR2016011184-appb-I000079
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2016011184-appb-I000080
    Figure PCTKR2016011184-appb-I000080
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2016011184-appb-I000081
    Figure PCTKR2016011184-appb-I000081
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2016011184-appb-I000082
    Figure PCTKR2016011184-appb-I000082
    [화학식 1-5][Formula 1-5]
    Figure PCTKR2016011184-appb-I000083
    Figure PCTKR2016011184-appb-I000083
    [화학식 1-6][Formula 1-6]
    Figure PCTKR2016011184-appb-I000084
    Figure PCTKR2016011184-appb-I000084
    상기 화학식 1-1 내지 1-6에 있어서,In Chemical Formulas 1-1 to 1-6,
    X1 및 R1 내지 R16의 정의는 상기 화학식 1과 동일하고, Definitions of X1 and R1 to R16 are the same as in the above formula (1),
    L1, Ar1 및 Ar2의 정의는 상기 화학식 B와 동일하며,Definition of L1, Ar1 and Ar2 is the same as in the above formula B,
    R101 내지 R103은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 니트릴기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고,R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
    r101, r102 및 r103은 각각 1 내지 3의 정수이며,r101, r102 and r103 are each an integer of 1 to 3,
    r101, r102 및 r103이 각각 2 이상인 경우, 2 이상의 괄호 내의 구조는 서로 같거나 상이하다.When r101, r102 and r103 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1은 하기 화학식 1-7 내지 1-18 중 어느 하나로 표시되는 것인 스피로형 화합물:Formula 1 is a spiro compound represented by any one of the following formula 1-7 to 1-18:
    [화학식 1-7][Formula 1-7]
    Figure PCTKR2016011184-appb-I000085
    Figure PCTKR2016011184-appb-I000085
    [화학식 1-8][Formula 1-8]
    Figure PCTKR2016011184-appb-I000086
    Figure PCTKR2016011184-appb-I000086
    [화학식 1-9][Formula 1-9]
    Figure PCTKR2016011184-appb-I000087
    Figure PCTKR2016011184-appb-I000087
    [화학식 1-10][Formula 1-10]
    Figure PCTKR2016011184-appb-I000088
    Figure PCTKR2016011184-appb-I000088
    [화학식 1-11][Formula 1-11]
    Figure PCTKR2016011184-appb-I000089
    Figure PCTKR2016011184-appb-I000089
    [화학식 1-12][Formula 1-12]
    Figure PCTKR2016011184-appb-I000090
    Figure PCTKR2016011184-appb-I000090
    [화학식 1-13][Formula 1-13]
    Figure PCTKR2016011184-appb-I000091
    Figure PCTKR2016011184-appb-I000091
    [화학식 1-14][Formula 1-14]
    Figure PCTKR2016011184-appb-I000092
    Figure PCTKR2016011184-appb-I000092
    [화학식 1-15][Formula 1-15]
    Figure PCTKR2016011184-appb-I000093
    Figure PCTKR2016011184-appb-I000093
    [화학식 1-16][Formula 1-16]
    Figure PCTKR2016011184-appb-I000094
    Figure PCTKR2016011184-appb-I000094
    [화학식 1-17][Formula 1-17]
    Figure PCTKR2016011184-appb-I000095
    Figure PCTKR2016011184-appb-I000095
    [화학식 1-18][Formula 1-18]
    Figure PCTKR2016011184-appb-I000096
    Figure PCTKR2016011184-appb-I000096
    상기 화학식 1-7 내지 1-18에 있어서,In Chemical Formulas 1-7 to 1-18,
    R1 내지 R16의 정의는 상기 화학식 1과 동일하고, Definitions of R1 to R16 are the same as in the above formula (1),
    L1, Ar1 및 Ar2의 정의는 상기 화학식 B와 동일하며,Definition of L1, Ar1 and Ar2 is the same as in the above formula B,
    R101 내지 R103은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 니트릴기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고,R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amide group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
    r101, r102 및 r103은 각각 1 내지 3의 정수이며,r101, r102 and r103 are each an integer of 1 to 3,
    r101, r102 및 r103이 각각 2 이상인 경우, 2 이상의 괄호 내의 구조는 서로 같거나 상이하다.When r101, r102 and r103 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.
  4. 청구항 1에 있어서, The method according to claim 1,
    상기 L1은 직접결합; 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 바이페닐릴렌기; 또는 치환 또는 비치환된 나프틸렌기인 것인 스피로형 화합물.L1 is a direct bond; Substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylylene group; Or a substituted or unsubstituted naphthylene group.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 Ar1 및 Ar2은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 바이페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 쿼터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 플루오레닐기; 치환 또는 비치환된 스피로비플루오레닐기; 치환 또는 비치환된 트리페닐레닐기; 치환 또는 비치환된 페난트레닐렌기; 치환 또는 비치환된 카바졸릴기; 치환 또는 비치환된 디벤조퓨라닐기; 또는 치환 또는 비치환된 디벤조티오펜기인 것인 스피로형 화합물.Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; A substituted or unsubstituted quarterphenyl group; Substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; Substituted or unsubstituted spirobifluorenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted phenanthrenylene group; Substituted or unsubstituted carbazolyl group; Substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophene group.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 Ar1와 Ar2는 서로 결합하여 하기 화학식 C의 구조로 표시되는 것인 스피로형 화합물:Spiro-type compound wherein Ar1 and Ar2 are bonded to each other represented by the structure of formula (C):
    [화학식 C][Formula C]
    Figure PCTKR2016011184-appb-I000097
    Figure PCTKR2016011184-appb-I000097
    상기 화학식 C에 있어서, In Chemical Formula C,
    X2는 CRR', NR", O 또는 S이고,X2 is CRR ', NR ", O or S,
    R, R', R", R201 및 R202는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기이고,R, R ', R ", R201 and R202 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group,
    r201 및 r202는 각각 1 내지 4의 정수이고,r201 and r202 are each an integer of 1 to 4,
    상기 r201 및 r202가 각각 2 이상인 경우, 2 이상의 괄호 내의 구조는 서로 같거나 상이하며,When r201 and r202 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,
    Figure PCTKR2016011184-appb-I000098
    는 상기 화학식 B의 L1에 결합되는 부위이다.
    Figure PCTKR2016011184-appb-I000098
    Is a moiety bound to L1 of the formula (B).
  7. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1은 하기 화합물 중에서 선택되는 것인 스피로형 화합물:Formula 1 is a spiro compound is selected from the following compounds:
    Figure PCTKR2016011184-appb-I000099
    Figure PCTKR2016011184-appb-I000099
    Figure PCTKR2016011184-appb-I000100
    Figure PCTKR2016011184-appb-I000100
    Figure PCTKR2016011184-appb-I000101
    Figure PCTKR2016011184-appb-I000101
    Figure PCTKR2016011184-appb-I000102
    Figure PCTKR2016011184-appb-I000102
    Figure PCTKR2016011184-appb-I000103
    Figure PCTKR2016011184-appb-I000103
    Figure PCTKR2016011184-appb-I000104
    Figure PCTKR2016011184-appb-I000104
    Figure PCTKR2016011184-appb-I000105
    Figure PCTKR2016011184-appb-I000105
    Figure PCTKR2016011184-appb-I000106
    Figure PCTKR2016011184-appb-I000106
    Figure PCTKR2016011184-appb-I000107
    Figure PCTKR2016011184-appb-I000107
    Figure PCTKR2016011184-appb-I000108
    Figure PCTKR2016011184-appb-I000108
    Figure PCTKR2016011184-appb-I000109
    Figure PCTKR2016011184-appb-I000109
    Figure PCTKR2016011184-appb-I000110
    Figure PCTKR2016011184-appb-I000110
    Figure PCTKR2016011184-appb-I000111
    Figure PCTKR2016011184-appb-I000111
    Figure PCTKR2016011184-appb-I000112
    Figure PCTKR2016011184-appb-I000112
    Figure PCTKR2016011184-appb-I000113
    Figure PCTKR2016011184-appb-I000113
    Figure PCTKR2016011184-appb-I000114
    Figure PCTKR2016011184-appb-I000114
    Figure PCTKR2016011184-appb-I000115
    Figure PCTKR2016011184-appb-I000115
    Figure PCTKR2016011184-appb-I000116
    Figure PCTKR2016011184-appb-I000116
    Figure PCTKR2016011184-appb-I000117
    Figure PCTKR2016011184-appb-I000117
    Figure PCTKR2016011184-appb-I000118
    Figure PCTKR2016011184-appb-I000118
    Figure PCTKR2016011184-appb-I000119
    Figure PCTKR2016011184-appb-I000119
    Figure PCTKR2016011184-appb-I000120
    Figure PCTKR2016011184-appb-I000120
    Figure PCTKR2016011184-appb-I000121
    Figure PCTKR2016011184-appb-I000121
    Figure PCTKR2016011184-appb-I000122
    Figure PCTKR2016011184-appb-I000122
    Figure PCTKR2016011184-appb-I000123
    Figure PCTKR2016011184-appb-I000123
  8. 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 청구항 1 내지 7 중 어느 한 항의 스피로형 화합물을 포함하는 것인 유기 발광 소자.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, wherein at least one of the organic material layers includes the spiro-type compound of any one of claims 1 to 7. device.
  9. 청구항 8에 있어서,The method according to claim 8,
    상기 유기물층은 정공주입층을 포함하고, 상기 정공주입층은 상기 스피로형 화합물을 포함하는 것인 유기 발광 소자.The organic material layer comprises a hole injection layer, the hole injection layer is an organic light emitting device comprising the spiro-type compound.
  10. 청구항 8에 있어서,The method according to claim 8,
    상기 유기물층은 정공수송층을 포함하고, 상기 정공수송층은 상기 스피로형 화합물을 포함하는 것인 유기 발광 소자.The organic material layer comprises a hole transport layer, the hole transport layer is an organic light emitting device comprising the spiro-type compound.
  11. 청구항 8에 있어서,The method according to claim 8,
    상기 유기물층은 정공조절층을 포함하고, 상기 정공조절층은 상기 스피로형 화합물을 포함하는 것인 유기 발광 소자.The organic material layer comprises a hole control layer, the hole control layer is an organic light emitting device comprising the spiro-type compound.
  12. 청구항 8에 있어서,The method according to claim 8,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 스피로형 화합물을 포함하는 것인 유기 발광 소자.The organic material layer includes an emission layer, and the emission layer includes the spiro-type compound.
  13. 청구항 8에 있어서,The method according to claim 8,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 스피로형 화합물을 발광층의 도펀트로서 포함하는 것인 유기 발광 소자.The organic material layer includes an emission layer, and the emission layer includes the spiro-type compound as a dopant of the emission layer.
  14. 청구항 8에 있어서, The method according to claim 8,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 하기 화학식 1-A로 표시되는 화합물을 포함하는 것인 유기 발광 소자:The organic material layer comprises an emission layer, the emission layer comprises an organic light emitting device comprising a compound represented by the formula 1-A:
    [화학식 1-A][Formula 1-A]
    Figure PCTKR2016011184-appb-I000124
    Figure PCTKR2016011184-appb-I000124
    상기 화학식 1-A에 있어서, In Chemical Formula 1-A,
    n1은 1 이상의 정수이고,n1 is an integer of 1 or more,
    Ar3은 치환 또는 비치환된 1가 이상의 벤조플루오렌기; 치환 또는 비치환된 1가 이상의 플루오란텐기; 치환 또는 비치환된 1가 이상의 파이렌기; 또는 치환 또는 비치환된 1가 이상의 크라이센기이고,Ar3 is a substituted or unsubstituted monovalent or higher benzofluorene group; Substituted or unsubstituted monovalent or higher fluoranthene group; A substituted or unsubstituted monovalent or higher pyrene group; Or a substituted or unsubstituted monovalent or higher chrysene group,
    L1은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이며,L 1 is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
    Ar4 및 Ar5는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴알킬기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있으며,Ar4 and Ar5 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted arylalkyl group; Or a substituted or unsubstituted heteroaryl group, or may combine with each other to form a substituted or unsubstituted ring,
    n1이 2 이상인 경우, 2 이상의 괄호 안의 구조는 서로 같거나 상이하다.When n1 is 2 or more, the structures in two or more parentheses are the same or different from each other.
  15. 청구항 14에 있어서, The method according to claim 14,
    상기 L1은 직접결합이고, Ar3는 2 가의 파이렌기이며, Ar4 및 Ar5는 서로 같거나 상이하고 각각 독립적으로 알킬기로 치환된 실릴기로 치환 또는 비치환된 아릴기이고, n1은 2인 것인 유기 발광 소자.Wherein L1 is a direct bond, Ar3 is a divalent pyrene group, Ar4 and Ar5 are the same or different from each other, and each independently an aryl group unsubstituted or substituted with a silyl group substituted with an alkyl group, and n1 is 2 device.
  16. 청구항 8에 있어서, The method according to claim 8,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 하기 화학식 2-A로 표시되는 화합물을 포함하는 것인 유기 발광 소자:The organic material layer comprises an emission layer, the emission layer comprises an organic light emitting device comprising a compound represented by the formula 2-A:
    [화학식 2-A][Formula 2-A]
    Figure PCTKR2016011184-appb-I000125
    Figure PCTKR2016011184-appb-I000125
    상기 화학식 2-A에 있어서,In Chemical Formula 2-A,
    Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 단환의 아릴기; 또는 치환 또는 비치환된 다환의 아릴기이고,Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group,
    G1 내지 G8은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 단환의 아릴기; 또는 치환 또는 비치환된 다환의 아릴기이다.G1 to G8 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group.
  17. 청구항 16에 있어서,The method according to claim 16,
    상기 Ar11 및 Ar12는 1-나프틸기이고, G1 내지 G8은 수소인 것인 유기 발광 소자.Wherein Ar11 and Ar12 are 1-naphthyl groups, and G1 to G8 are hydrogen.
  18. 청구항 14에 있어서, The method according to claim 14,
    상기 발광층은 하기 화학식 2-A로 표시되는 화합물을 포함하는 것인 유기 발광 소자:The light emitting layer is an organic light emitting device comprising a compound represented by the formula 2-A:
    [화학식 2-A][Formula 2-A]
    Figure PCTKR2016011184-appb-I000126
    Figure PCTKR2016011184-appb-I000126
    상기 화학식 2-A에 있어서,In Chemical Formula 2-A,
    Ar11 및 Ar12는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 단환의 아릴기; 또는 치환 또는 비치환된 다환의 아릴기이고,Ar11 and Ar12 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group,
    G1 내지 G8은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 단환의 아릴기; 또는 치환 또는 비치환된 다환의 아릴기이다.G1 to G8 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted monocyclic aryl group; Or a substituted or unsubstituted polycyclic aryl group.
PCT/KR2016/011184 2015-10-06 2016-10-06 Spiro compound and organic light-emitting device comprising same WO2017061788A1 (en)

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JP2004529937A (en) * 2001-04-27 2004-09-30 エルジー ケミカル エルティーディー． Double spiro-type organic compound and electroluminescent device
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WO2012141229A1 (en) * 2011-04-14 2012-10-18 Canon Kabushiki Kaisha Novel spiro compound and organic light-emitting device having the same
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JP2005531552A (en) * 2002-05-07 2005-10-20 エルジー・ケム・リミテッド New organic light emitting compound and organic light emitting device using the same
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