WO2020175867A1 - 신규한 화합물 및 이를 이용한 유기 발광 소자 - Google Patents

신규한 화합물 및 이를 이용한 유기 발광 소자 Download PDF

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WO2020175867A1
WO2020175867A1 PCT/KR2020/002606 KR2020002606W WO2020175867A1 WO 2020175867 A1 WO2020175867 A1 WO 2020175867A1 KR 2020002606 W KR2020002606 W KR 2020002606W WO 2020175867 A1 WO2020175867 A1 WO 2020175867A1
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group
compound
substituted
unsubstituted
formula
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PCT/KR2020/002606
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French (fr)
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김용욱
배재순
이재철
김영광
김주환
김동윤
조범신
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주식회사 엘지화학
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Priority claimed from KR1020200021512A external-priority patent/KR102372881B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP20763578.0A priority Critical patent/EP3904346A4/en
Priority to JP2021539669A priority patent/JP7250400B2/ja
Priority to US17/421,520 priority patent/US20220085295A1/en
Priority to CN202080007951.5A priority patent/CN113272288B/zh
Publication of WO2020175867A1 publication Critical patent/WO2020175867A1/ko

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Definitions

  • the present invention relates to a novel compound and an organic light-emitting device comprising the same.
  • organic luminescence is a phenomenon that uses organic substances to generate electrical energy.
  • Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, and fast response time, and are excellent in luminance, driving voltage and response speed characteristics, and many studies are being conducted.
  • An organic light-emitting device is generally used between the anode and cathode, and between the anode and the cathode.
  • the organic material layer is made of different materials in order to increase the efficiency and stability of the organic light emitting device.
  • a voltage is applied between the two electrodes, holes from the positive electrode and electrons from the negative electrode will be injected into the organic layer, and the injected holes and electrons will meet.
  • the present invention provides a novel organic light-emitting device material that can be used for an organic light-emitting device and at the same time that can be used in a solution process.
  • Patent Document 0001 Korean Patent Application Publication No. 10-2000-0051826
  • the present invention relates to a novel compound and an organic light-emitting device comprising the same.
  • II ! And II 2 are each independently hydrogen, or II ! Or II 2 bonded to each other to form a substituted or unsubstituted 0 6-60 aromatic ring; a substituted or unsubstituted 0 6-60 non-aromatic ring; Or substituted or unsubstituted 0, 3 and 0 2-60 heterocycles containing any one or more heteroatoms selected from the group consisting of,
  • At least one of II 1 and II 2 is II 1 or II 2 bonded to each other to form the 0 6-60 non-aromatic ring; or the 0 2-60 heterocycle,
  • [25] is substituted or unsubstituted (: 6-6 . arylene; or substituted or unsubstituted 0 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of 0 and 8,
  • X is 0, S, NZ 3 , or 2 4 2 5 ,
  • [27] 1 to 5 are each independently, substituted or unsubstituted 0 !-60 alkyl; substituted or
  • Unsubstituted 0 !_ 60 haloalkyl; substituted or unsubstituted 0 3-60 cycloalkyl; substituted or unsubstituted (: 7-6 ⁇ aralkyl; substituted or unsubstituted (: 6-6 ⁇ aryl; or 0 2-60 containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted 0 and 3
  • [29] 1 and 2 are each independently a single bond; substituted or unsubstituted 0 6-60 arylene; or 2020/175867 1»(:1/10 ⁇ 020/002606
  • the present invention is an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first electrode; and a light emitting layer provided between the first electrode and the second electrode, wherein the light emitting layer is It provides an organic light-emitting device comprising a compound represented by.
  • the compound represented by Formula 1 above can be used as a material for the organic material layer of an organic light emitting device, and can also be used in a solution process, and has improved efficiency, low driving voltage and/or lifespan characteristics in organic light emitting devices. Can be improved. Brief description of the drawing
  • FIG. 1 shows an example of an organic light-emitting device comprising a substrate (1), an anode (2), a light-emitting layer (3), and a cathode (4).
  • FIG. 2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light-emitting layer (7),
  • An example of an organic light-emitting device comprising an electron transport layer (8), an electron injection layer (9) and a cathode (4) is shown.
  • substituted or unsubstituted refers to deuterium; halogen;
  • Cyano group Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Aryl thioxy group; Alkyl sulfoxy group; Aryl sulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group;
  • Alkenyl group Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group;
  • a substituted or unsubstituted four-linked group may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are linked.
  • the number of carbons of the carbonyl group is not particularly limited, but it is preferable that the number of carbons is 1 to 40. Specifically, it may be a compound having the structure as described below, but is not limited thereto.
  • the ester group may be substituted with the oxygen of the ester group with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms.
  • a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms may be a compound of the following structural formula. , It is not limited to this.
  • the number of carbon atoms of the imide group is not particularly limited, but it is preferable that the number of carbon atoms is 1 to 25. Specifically, it may be a compound having the structure as described below, but is not limited thereto. 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • the silyl group is specifically a trimethylsilyl group, a triethylsilyl group,
  • I-butyldimethylsilyl group vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like, but are not limited thereto.
  • the boron group is specifically a trimethyl boron group, a triethyl boron group,
  • I-butyl dimethyl boron group triphenyl boron group, phenyl boron group, etc., but are not limited thereto.
  • halogen groups are fluorine, chlorine, bromine or iodine.
  • the alkyl group may be straight or branched, and the number of carbons is
  • the number of carbon atoms of the alkyl group is 1 to 20. According to another embodiment, the number of carbons of the alkyl group is 1 to 40. Another embodiment According to, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, propyl, isopropyl, butyl, 11-butyl, isobutyl, butyl, 8 -butyl, 1-methyl-butyl,
  • the alkenyl group may be straight chain or branched chain, and the number of carbons is not particularly limited, but it is preferably 2 to 40. According to one embodiment, 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Examples include vinyl, 1 -propenyl, isopropenyl, 1 -butenyl, 2 -butenyl, 3 -butenyl, 1 -pentenyl, 2 -pentenyl, 3 -pentenyl,
  • the cycloalkyl group is not particularly limited, but it is preferable that the number of carbon atoms is 3 to 60, and according to one embodiment, the number of carbons of the cycloalkyl group is 3 to 30. According to another embodiment, the cycloalkyl group is The number of carbon atoms of is 3 to 20. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl,
  • the aralkyl group is not particularly limited, but it is preferably 7 to 60 carbon atoms, and according to one embodiment, the aralkyl group has 7 to 30 carbon atoms. According to, the number of carbon atoms of the aralkyl group is 7 to 20. Specifically, phenylmethyl, 2-methylphenylmethyl, 3-methylphenylmethyl,
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group is naph Tyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc. may be, but are not limited thereto.
  • the fluorenyl group may be substituted, and the two substituents It can be, but it is not limited to this.
  • heteroaryl is a heterogeneous element. At least one of 0, N, Si and S
  • the number of carbons is not particularly limited, but it is preferable that the number of carbons is 2 to 60.
  • heteroaryl include xanthene,
  • the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the examples of the aryl group described above.
  • an aralkyl group, an alkylaryl group, and Among the alkylamine groups, the alkyl groups are the same as those of the aforementioned alkyl groups.
  • heteroaryl among heteroarylamines the above description of heteroaryl may be applied.
  • the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above.
  • arylene is a divalent group
  • the description of heteroaryl as described above can be applied except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, except that two substituents are bonded to each other, except that the aforementioned aryl group or
  • Heterocycle is not a monovalent group, and is formed by bonding of two substituents.
  • the aromatic ring is a condensed monocyclic or condensed polycyclic ring having only carbon as a ring-forming atom and having aromaticity in the entire molecule.
  • the number of carbon atoms in the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto.
  • the aromatic ring is a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and pi Rengori, etc. may be, but is not limited to.
  • a non-aromatic ring refers to a fused monocyclic or fused polycyclic alicyclic ring in which the entire molecule contains only carbon as a ring-forming atom and does not have aromaticity.
  • the number of carbon atoms in the carbon number is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto.
  • the non-aromatic ring may be an indene ring, a fluorene ring, etc., but is not limited thereto.
  • the indene ring, fluorene ring, etc. may be substituted or unsubstituted, and the types of the substituents are referred to above.
  • a heterocyclic ring is a ring-forming atom, including at least one heteroatom among 0, N, Si and S in addition to carbon, and the entire molecule is
  • hetero-condensed monocyclic or hetero-condensed polycyclic ring that has aromaticity or does not have aromaticity.
  • the number of carbon atoms of the heterocycle is 2 to 60, or 2 to 30, or 2 to 20, but is limited thereto.
  • the hetero rings include benzofuran ring, benzothiophene ring, benzosilole ring, dibenzofuran ring, dibenzothiophene ring, dibenzosilole ring, silorane ring, etc. This may be, but is not limited thereto.
  • the benzosilol ring, dibenzosilol ring, etc. may be substituted or unsubstituted, and the types of the substituents are referred to above.
  • the present invention provides a diamine compound represented by Formula 1 above.
  • At least one of R 1 and R 2 is R ! Or R 2 is bonded to each other to form a C 6-60 alicyclic ring; Or any one or more selected from the group consisting of N, 0, S and Si 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • 0 2-60 heterocycles containing 9 heteroatoms are formed, and the rest are hydrogen or II 1 or II 2 are bonded to each other to 0 6-60 aromatic rings; 0 6-60 alicyclic ring; Or 0 2-60 forms a heterocycle containing at least one heteroatom selected from the group consisting of.
  • Ring may be substituted with substituents each independently selected from the consisting of hydrogen, 0, _ 10 alkyl, and 0 6-20 aryl doeneungun.
  • II 1 is bonded to each other to form the 0 6-60 alicyclic ring or the 0 2-60 hetero ring
  • II 2 is all hydrogen, or bonded to each other to form the 0 6-60 aromatic ring, the 0 6-60 Alicyclic ring, or to form the 0 2-60 heterocycle;
  • Form and II ! Are all hydrogen, or combine with each other to form the 0 6-60 aromatic ring, the 0 6-60 alicyclic ring, or the 0 2-60 heterocycle; or
  • Both II 1 and II 2 may be bonded to each other between II 1 or II 2 to form the 0 6-60 aromatic ring, the 0 6-60 alicyclic ring, or the 0 2-60 heterocycle.
  • ⁇ 6 to 9 are each independently, substituted or unsubstituted 0 !-60 alkyl; substituted or
  • [99] * means the position of bonding to the carbon bonded to either 1 or 11 2 .
  • V ! And one of V 2 is a single bond, and the other is 0, ⁇ 0, 0 (0 "alkyl) 2 , or kinaalkyl) 2 ,
  • One of Y 3 and Y 4 is a single bond, and the other is 0, S, C (methyl) 2 , or Si (methyl) 2.
  • silver phenyl or biphenylyl wherein, Silver is unsubstituted or independently selected from the group consisting of deuterium, halogen, cyano, 0 ,_ 10 alkyl, 0 3-10 cycloalkyl, ,_ 10 alkyl) 3 and ((: 6-2 ⁇ aryl) 3 1 or more
  • 1 is phenyl or biphenylyl, where ⁇ deuterium, halogen, cyano, methyl, ethyl, propyl, 1_butyl, cyclopentyl, (methyl) 3 and
  • silver is unsubstituted or is phenylene substituted with 0 140 alkyl. More preferably, it is silver phenylene. Most preferably, silver is 1,4-phenylene.
  • 2 to ⁇ 5 are each independently 0 alkyl; 0 6-20 aryl; or 0 7-20 aralkyl, wherein, ⁇ 2 to ⁇ 5 are unsubstituted or substituted with 0 ,_ 10 alkyl or ,_ 10 alkyl) 3 .
  • ⁇ 2 and ⁇ 3 are each independently, 0 alkyl; unsubstituted, or 0 ,_ 10 0 6-20 aryl substituted with alkyl; or unsubstituted, or 0 ,_ 10 0 7-20 aralkyl substituted with alkyl.
  • 4 and ⁇ 5 are each independently 0 alkyl; or 0 6-60 aryl unsubstituted or substituted with 0 ,_ 10 alkyl.
  • 1:2 2 is any one selected from the group consisting of:
  • show to show] ⁇ 4 is each independently, phenyl, naphthyl, biphenylyl, or dibenzofuranyl,
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 2--1 to 2-10:
  • ⁇ and V 6 are each independently 0, ⁇ (:(methyl) 2 , or (methyl) 2 .
  • the compound represented by Formula 1 may be selected from the group consisting of:
  • the compound is any one selected from the group consisting of:
  • the compound represented by Chemical Formula 1 is prepared as shown in Reaction Formula 1 below. It can be manufactured by a method. The above manufacturing method may be more specific in the manufacturing example to be described later.
  • Step 1-1 is a step of preparing an intermediate compound INT.1 by introducing a hydroxy group and a compound SM2 to the starting material SM1 by a reduction reaction of the carbonyl group by a strong base
  • the step 1-2 is Friedel -Crafts-type electrophilic substitution reaction is a step of introducing compound SM3 into the hydroxyl group of the intermediate compound INT.1 to prepare intermediate compound INT.2
  • steps 1-3 are steps of the intermediate compound INT.2 and secondary amine.
  • This is a step of preparing the compound represented by Chemical Formula 1 by reacting phosphorus SM4. Such a manufacturing method may be more specific than in Preparation Examples to be described later.
  • the compound according to the present invention can form an organic layer of an organic light-emitting device, especially a light-emitting layer by a solution process.
  • the compound can be used as a dopant material for the light-emitting layer.
  • the present invention is described above. It provides a coating composition comprising a compound and a solvent according to the present invention.
  • the solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the compound according to the present invention, for example, chloroform, methylene chloride, 1,2 -dichloroethane, 1,1,2 -trichloroethane, chlorobenzene And chlorine-based solvents such as 0-dichlorobenzene;
  • Ether solvents such as tetrahydrofuran and dioxane; toluene, xylene, 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • Aromatic hydrocarbon-based solvents such as trimethylbenzene and mesitylene; cyclonucleic acid,
  • Aliphatic hydrocarbon solvents such as methylcyclonucleic acid, 11 pentane, 11 nucleic acid, 11 heptane, 11 octane, 11 nonane, and 11 decane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone;
  • Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-nucleic acid diol, etc. Alcohol and its derivatives; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclonucleic acidol; sulfoxide solvents such as dimethyl sulfoxide; And
  • Amide solvents such as methyl-2-pyrrolidone and N,N-dimethylformamide
  • Benzoate solvents such as butyl benzoate and methyl-2-methoxybenzoate; tetralin;
  • 3-A solvent such as phenoxy toluene can be mentioned.
  • the above-described solvent can be used alone or in combination of two or more solvents.
  • toluene can be used as the solvent.
  • the coating composition may further include a compound used as a host material, and a description of the compound used for the host material will be described later.
  • the viscosity of the coating composition (25 o 0 is preferably 1 acid 5 to acid 5 , and coating is easy in the above range.
  • the concentration of the compound according to the present invention in the coating composition is 0.1) desirable.
  • the solubility of the coating composition in the solvent ( ⁇ %) is based on the solvent toluene.
  • the coating composition containing the compound represented by the above formula 1 is suitable for use in the solution process.
  • the present invention provides a method of forming a light emitting layer using the above-described coating composition.
  • the solution process is to use the coating composition according to the present invention described above, meaning spin coating, dip coating, doctor blading, ink get printing, screen printing, spray method, roll coating, etc., but limited to these It doesn't work.
  • the heat treatment temperature is preferably 150 to 230 ⁇ (: is preferable.
  • the heat treatment time is 1 minute to 3 hours, more preferably minutes to 1 hour.
  • the heat treatment should be performed in an inert gas atmosphere such as argon or nitrogen. desirable.
  • the present invention is organic light-emitting containing a compound represented by the above formula 1
  • the present invention is an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first electrode; and a light emitting layer provided between the first electrode and the second electrode,
  • the light-emitting layer provides an organic light-emitting device comprising a compound represented by Chemical Formula 1.
  • the organic light-emitting device according to the present invention may be a normal type organic light-emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.
  • the organic light-emitting device according to the present invention may be an organic light-emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially increased on a substrate.
  • an organic light-emitting device according to an embodiment of the present invention The structure of the light emitting device is illustrated in FIGS. 1 and 2.
  • FIG. 1 shows an example of an organic light-emitting device comprising a substrate (1), an anode (2), a light-emitting layer (3), and a cathode (4).
  • a compound represented by Formula 1 above is shown.
  • Silver may be included in the light-emitting layer.
  • FIG. 2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7),
  • An example of an organic light-emitting device consisting of an electron transport layer 8, an electron injection layer 9, and a cathode 4 is shown.
  • the compound represented by Formula 1 may be included in the light-emitting layer.
  • the organic light-emitting device according to the present invention may be manufactured with materials and methods known in the art, except that the light-emitting layer contains the compound according to the present invention and is manufactured as described above.
  • the organic light emitting device can be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate.
  • PVD such as sputtering or e-beam evaporation
  • a metal or conductive metal oxide or alloy thereof is deposited on a substrate to form an anode, and an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon.
  • it can be manufactured by depositing a material that can be used as a cathode on it.
  • the organic material layer and the anode material are removed from the cathode material on the substrate.
  • Organic light-emitting devices can be manufactured by depositing them one after the other ( ⁇ 0 2003/012890), but the manufacturing method is not limited to this.
  • an organic material layer and a cathode material are removed from the cathode material on the substrate.
  • Organic light emitting devices can be manufactured by depositing them one after another (WO 2003/012890), but the manufacturing method is not limited to this.
  • the first electrode is a positive electrode
  • the second electrode is a negative electrode
  • the first electrode is a negative electrode
  • the second electrode is a positive electrode
  • the anode material is usually used to facilitate hole injection into an organic layer.
  • anode material includes metals such as vanadum, chromium, copper, zinc, gold, or alloys thereof; zinc oxide, indum oxide, indium tin oxide (ITO), indium zinc oxide ( Metal oxides such as IZO); ZnO: Al or SnO 2: combination of metal peroxides such as Sb; poly (3-methylthiophene),
  • conductive compounds such as poly[3,4-(ethylene- 1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, but they are not limited to these.
  • the cathode material it is generally preferable to use a material with a small work function to facilitate electron injection into the organic material layer.
  • the cathode material include magnesium, calcium, sodium, potassium, titanium, indum, yttrium, lithium, gadolinium, Metals such as aluminum, silver, tin and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but they are not limited to these.
  • the hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that the hole injection effect at the anode, the light emitting layer, or
  • a compound that has an excellent hole injection effect for the luminescent material, prevents the movement of excitons generated in the luminescent layer to the electron injection layer or the electron injection material, and has excellent thin film formation ability is desirable.
  • HOMO (highest) of the hole injection material It is preferable that the occupied molecular orbital is between the work function of the positive electrode material and the HOMO of the surrounding organic material.
  • the hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile nucleus azatriphenyl
  • the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile nucleus azatriphenyl
  • 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, holes are transferred from the anode or the hole injection layer. 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • a material with high mobility for holes is suitable.
  • Specific examples include arylamine-series organics, conductive compounds, and block copolymers with conjugated and non-conjugated parts. It's not as good as these.
  • the light-emitting layer may include a host material and a dopant material.
  • a dopant material a compound represented by the above-described formula (1) may be used.
  • a host material a condensed aromatic ring derivative or a heterocyclic compound may be used. Can be used.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and neluoranthene compounds
  • heterocycle-containing compounds include carbazole derivatives, dibenzoneuran derivatives, and ladder strings.
  • compounds, pyrimidine derivatives, etc. are not limited thereto.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer.
  • a material capable of transferring electrons from the cathode to the light-emitting layer is a material with high mobility for electrons.
  • Suitable include a new complex of 8-hydroxyquinoline; a complex including show 3 ; There are organic radical compounds; hydroxyflavone-metal complexes, etc., but not as good as these.
  • the electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials. Is a common material with a low work function followed by an aluminum or silver layer.
  • alumina or silver layer follows.
  • the electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, and has excellent electron injection effect for the light emitting layer or the light emitting material, and excitons generated from the light emitting layer A compound that prevents migration to the artificial hole injection layer and has excellent thin film formation ability is desirable.
  • 1, mu (: 1, yome, U 2 0, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid ,Preorenylidenemethane, anthrone, etc. and their derivatives, metal complex compounds and nitrogen-containing 5-membered ring derivatives, etc.
  • Examples of the metal complex compound include 8-hydroxyquinolinatortium,
  • the organic light-emitting device may be a front-emitting type, a back-emitting type, or a double-sided light-emitting type depending on the material used.
  • the compound according to the present invention may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.
  • Step 1-7 Synthesis of Compound 1 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • Trifluoromethanesulfonic acid anhydride (5.92 21_01) was added and stirred for 3 hours at room temperature. After that, the organic layer was separated in a separatory funnel, water was removed using MgS04, and the solvent was removed by pressure reduction. The obtained material was subjected to column chromatography to separate and purify compound 04 (7.8 yield: 81%).
  • Wamoic acid 3 ) 4 (1.16 silver, 1 11111101) was added and dissolved in N,N-dimethylformamide (50 11 ⁇ ) and stirred for 18 hours with 130° (:). After that, the organic layer in a separation funnel After separating, water was removed by using it, and the solvent was removed by depressurization. The obtained material was subjected to column chromatography to separate and purify Compound 04 (2.3 yield: 65%).
  • step 5-3 [349] 05 (1.8 is, 5 11111101) and potassium hydroxide (0.56 is, 10 11111101) prepared in step 5-3 were added to ethanol (30 1111) and water (10) and stirred under reflux for 24 hours. Room temperature After cooling with, it was acidified with 0.2 normal hydrochloric acid, and the resulting solid was filtered, washed with nucleic acid, and dried to obtain 06 (for 1.36, yield: 72%).
  • Step 9-1 Synthesis of Compound 03 2020/175867 1»(:1 ⁇ 1 ⁇ 2020/002606
  • a light emitting layer having a thickness of 550 yaw was formed.
  • lithium fluoride ⁇ is deposited on the light-emitting layer to a yaw thickness to form an electron transport and injection layer, and finally, aluminum is deposited to a thickness of 00 yo. Thus, a cathode was formed.
  • the organic light emitting device was manufactured in the same manner as in 1.
  • the organic light-emitting device using the compound of the present invention as a dopant for the light-emitting layer in terms of driving voltage, efficiency, and life. It can be seen that all of them exhibit excellent characteristics. This is because, in general, the luminous efficiency and life characteristics of organic light emitting devices are trade-off with each other (13 ⁇ 4 (1)), considering that the compound of the present invention is used as the dopant of the light emitting layer. This means that the organic light-emitting device adopted as a device exhibits significantly improved device characteristics compared to the comparative device.

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Abstract

본 발명은 신규한 화합물 및 이를 이용한 유기발광 소자를 제공한다.

Description

2020/175867 1»（：1/10公020/002606 명세서
발명의 명칭 :신규한화합물및이를이용한유기발광소자 기술분야
[I] 본출원은 2019년 2월 28일자한국특허출원제 10-2019-0024296호및 2020년 2월 21일자한국특허출원제 10-2020-0021512호에기초한우선권의이익을 주장하며,해당한국특허출원의문헌들에개시된모든내용은본명세서의 일부로서포함된다.
四
[3] 본발명은신규한화합물및이를포함하는유기발광소자에관한것이다. 배경기술
[4] 일반적으로유기발광현상이란유기물질을이용하여전기에너지를
빛에너지로전환시켜주는현상을말한다.유기발광현상을이용하는유기발광 소자는넓은시야각,우수한콘트라스트,빠른응답시간을가지며,휘도,구동 전압및응답속도특성이우수하여많은연구가진행되고있다.
[5]
[6] 유기발광소자는일반적으로양극과음극및상기양극과음극사이에
유기물층을포함하는구조를가진다.상기유기물층은유기발광소자의효율과 안정성을높이기위하여각기다른물질로구성된다층의구조로이루어진 경우가많으며,예컨대정공주입층,정공수송층,발광층,전자수송층, 전자주입층등으로이루어질수있다.이러한유기발광소자의구조에서두 전극사이에전압을걸어주게되면양극에서는정공이,음극에서는전자가 유기물층에주입되게되고,주입된정공과전자가만났을
Figure imgf000002_0001
형성되며,이 엑시톤이다시바닥상태로떨어질때빛이나게된다.
[7]
[8] 상기와같은유기발광소자에사용되는유기물에대하여새로운재료의
개발이지속적으로요구되고있다.
[9]
[1이 한편,최근에는공정비용절감을위하여기존의증착공정대신용액공정, 특히잉크겟공정을이용한유기발광소자가개발되고있다.초창기에는모든 유기발광소자층을용액공정으로코팅하여유기발광소자를개발하려 하였으나현재기술로는한계가있어,정구조형태에서 ᄂ EML만을 용액공정으로진행하고추후공정은기존의증착공정을활용하는
하이브리드 (11) 난(1)공정이연구중이다.
[I I]
[12] 이에본발명에서는유기발광소자에사용될수있으면서동시에용액공정에 사용가능한신규한유기발광소자의소재를제공한다. 2020/175867 1»（：1^1{2020/002606
2
[13] [선행기술문헌]
[14] [특허문헌]
[15] （특허문헌 0001）한국특허 공개번호제 10-2000-0051826호
[16]
발명의상세한설명
기술적과제
[17] 본발명은신규한화합물및이를포함하는유기 발광소자에 관한것이다.
[18]
과제해결수단
[19] 본발명은하기화학식 1로표시되는화합물을제공한다:
[2이 [화학식 1]
[21]
Figure imgf000003_0001
[22] 상기화학식 1에서,
[23] II !및 II 2는각각독립적으로,수소이거나,또는 II !또는 II 2끼리서로결합하여 치환또는비치환된 0 6-60방향족고리 ;치환또는비치환된 0 6-60비방향족고리 ; 또는치환또는비치환된 0, 3및 로구성되는군으로부터선택되는어느 하나이상의헤테로원자를포함하는 0 2-60헤테로고리를형성하되，
[24] II 1및 II 2중적어도하나는 II 1또는 II 2끼리서로결합하여 ,상기 0 6-60비방향족 고리 ;또는상기 0 2-60헤테로고리를형성하고,
[25] 은치환또는비치환된（： 6-6。아릴렌;또는치환또는비치환된 0및 8로 구성되는군으로부터선택되는어느하나이상의헤테로원자를포함하는 0 2-60 헤테로아릴렌이고,
[26] X는 0, S, NZ 3，또는 2 42 5이고,
[27] 1내지 5는각각독립적으로,치환또는비치환된 0 !-60알킬;치환또는
비치환된 0 !_60할로알킬 ;치환또는비치환된 0 3-60사이클로알킬 ;치환또는 비치환된（： 7-6。아랄킬;치환또는비치환된（： 6-6。아릴;또는치환또는비치환된 0및 3로구성되는군으로부터선택되는어느하나이상의 헤테로원자를 포함하는 0 2-60
[28] 상기 !^및 2 2;
Figure imgf000003_0002
연결되어 5원-헤테로고리를 형성할수있고,
[29] 1및 2는각각독립적으로,단일결합;치환또는비치환된 0 6-60아릴렌;또는 2020/175867 1»（：1/10公020/002606
3 치환또는비치환된 0및 3로구성되는군으로부터선택되는어느하나 이상의 헤테로원자를포함하는 0 2-60헤테로아릴렌이고,
사 1내지사 4는각각독립적으로,치환또는비치환된 0 6-60아릴 ;또는치환 또는비치환된 0및 3로구성되는군으로부터선택되는어느하나이상의 헤테로원자를포함하는 0 2-60헤테로아릴이다. 또한,본발명은제 1전극;상기제 1전극과대향하여구비된제 2전극;및상기 제 1전극과상기 제 2전극사이에구비된발광층을포함하는유기발광 소자로서,상기 발광층은상기 화학식 1로표시되는화합물을포함하는,유기 발광소자를제공한다.
발명의효과
[33] 상술한화학식 1로표시되는화합물은유기 발광소자의유기물층의 재료로서 사용될수있으며,또한용액공정에사용이가능하며,유기 발광소자에서 효율의 향상,낮은구동전압및/또는수명특성을향상시킬수있다. 도면의간단한설명
도 1은기판 (1),양극 (2),발광층 (3),음극 (4)으로이루어진유기발광소자의 예를도시한것이다.
[36] 도 2는기판 (1),양극 (2),정공주입층 (5),정공수송층 (6),발광층 (7),
전자수송층 (8),전자주입층 (9)및음극 (4)으로이루어진유기 발광소자의 예를 도시한것이다.
발명의실시를위한형태
이하,본발명의 이해를돕기 위하여보다상세히설명한다.
(용어의정의)
본명세서에서, < 는다른치환기에 연결되는결합을의미하고, 1¾는
1—
페닐기를의미하며 , 1)는중수소를의미하고, ：811는16]1 -부틸기를의미한다.
[41]
[42] 본명세서에서 "치환또는비치환된”이라는용어는중수소;할로겐기;
시아노기 ;니트로기 ;히드록시기 ;카보닐기 ;에스테르기 ;이미드기 ;아미노기 ; 포스핀옥사이드기 ;알콕시기 ;아릴옥시기 ;알킬티옥시기 ;아릴티옥시기 ; 알킬술폭시기 ;아릴술폭시기 ;실릴기 ;붕소기 ;알킬기 ;사이클로알킬기 ;
알케닐기 ;아릴기 ;아르알킬기 ;아르알케닐기 ;알킬아릴기 ;알킬아민기 ;
아랄킬아민기;헤테로아릴아민기;아릴아민기;아릴포스핀기;또는 0및 8 원자중 1개 이상을포함하는헤테로아릴로이루어진군에서선택된 1개 이상의 치환기로치환또는비치환되거나,상기 예시된치환기중 2이상의치환기가 2020/175867 1»（：1^1{2020/002606
4 연결된치환또는비치환된것을의미한다.예컨대, "2이상의치환기가연결된 치환기”는비페닐기일수있다.즉,비페닐이기는아릴기일수도있고, 2개의 페닐기가연결된치환기로해석될수도있다.
[43]
[44] 본명세서에서카보닐기의탄소수는특별히 한정되지 않으나,탄소수 1내지 40인것이바람직하다.구체적으로하기와같은구조의화합물이 될수있으나, 이에 한정되는것은아니다.
Figure imgf000005_0001
[47] 본명세서에 있어서,에스테르기는에스테르기의산소가탄소수 1내지 25의 직쇄,분지쇄또는고리쇄 알킬기또는탄소수 6내지 25의 아릴기로치환될수 있다.구체적으로,하기구조식의화합물이 될수있으나,이에 한정되는것은 아니다.
[48]
Figure imgf000005_0002
Figure imgf000005_0003
[49]
[5이 본명세서에 있어서,이미드기의탄소수는특별히 한정되지 않으나,탄소수 1 내지 25인것이 바람직하다.구체적으로하기와같은구조의 화합물이될수 있으나,이에 한정되는것은아니다. 2020/175867 1»（：1^1{2020/002606
5
Figure imgf000006_0001
[52]
[53] 본명세서에 있어서,실릴기는구체적으로트리메틸실릴기,트리에틸실릴기,
I부틸디메틸실릴기,비닐디메틸실릴기,프로필디메틸실릴기,트리페닐실릴기 , 디페닐실릴기,페닐실릴기등이 있으나이에 한정되지 않는다.
[54]
[55] 본명세서에 있어서,붕소기는구체적으로트리메틸붕소기 ,트리에틸붕소기 ,
I부틸디메틸붕소기,트리페닐붕소기,페닐붕소기등이 있으나이에 한정되지 않는다.
[56]
[57] 본명세서에 있어서,할로겐기의 예로는불소,염소,브롬또는요오드가있다.
[58]
[59] 본명세서에 있어서,상기 알킬기는직쇄또는분지쇄일수있고,탄소수는
특별히 한정되지 않으나 1내지 40인것이 바람직하다.일실시상태에 따르면, 상기 알킬기의탄소수는 1내지 20이다.또하나의실시상태에따르면,상기 알킬기의 탄소수는 1내지 이다.또하나의실시상태에 따르면,상기 알킬기의 탄소수는 1내지 6이다.알킬기의구체적인 예로는메틸,에틸,프로필, 프로필, 이소프로필,부틸, 11-부틸,이소부틸, 부틸, 8 -부틸, 1 -메틸-부틸,
1 -에틸-부틸,펜틸, 11-펜틸,이소펜틸,네오펜틸, 1 -펜틸,핵실, 11-핵실,
I -메틸펜틸, 2 -메틸펜틸, 4 -메틸-2 -펜틸, 3,3 -디메틸부틸, 2 -에틸부틸,헵틸,
II-헵틸, 1 -메틸핵실,사이클로펜틸메틸,사이클로핵실메틸,옥틸, II -옥틸,
옥틸, 1 -메틸헵틸, 2 -에틸핵실, 2 -프로필펜틸,！！-노닐, 2, 2 -디메틸헵틸,
1 -에틸-프로필, 1,1 -디메틸-프로필,이소핵실, 2 -메틸펜틸, 4 -메틸핵실,
5 -메틸핵실등이 있으나,이들에 한정되지 않는다.
[6이
[61] 본명세서에 있어서 ,상기 알케닐기는직쇄또는분지쇄일수있고,탄소수는 특별히 한정되지 않으나, 2내지 40인것이바람직하다.일실시상태에따르면, 2020/175867 1»（：1^1{2020/002606
6 상기 알케닐기의탄소수는 2내지 20이다.또하나의실시상태에따르면,상기 알케닐기의 탄소수는 2내지 이다.또하나의실시상태에 따르면,상기 알케닐기의 탄소수는 2내지 6이다.구체적인 예로는비닐, 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,스티레닐기등이 있으나이들에 한정되지 않는다. 본명세서에 있어서,사이클로알킬기는특별히 한정되지 않으나,탄소수 3내지 60인것이바람직하며,일실시상태에따르면,상기사이클로알킬기의탄소수는 3내지 30이다.또하나의실시상태에 따르면,상기사이클로알킬기의 탄소수는 3내지 20이다.또하나의실시상태에 따르면,상기사이클로알킬기의 탄소수는 3내지 6이다.구체적으로사이클로프로필,사이클로부틸,사이클로펜틸,
3 -메틸사이클로펜틸, 2, 3 -디메틸사이클로펜틸,사이클로핵실,
3 -메틸사이클로핵실, 4 -메틸사이클로핵실, 2, 3 -디메틸사이클로핵실,
3, 4, 5 -트리메틸사이클로핵실, 4 - 1631 -부틸사이클로핵실,사이클로헵틸, 사이클로옥틸등이 있으나,이에 한정되지 않는다. 본명세서에 있어서,아랄킬（따산1公1）기는특별히 한정되지 않으나,탄소수 7 내지 60인것이 바람직하며,일실시상태에 따르면,상기아랄킬기의 탄소수는 7 내지 30이다.또하나의실시상태에따르면,상기 아랄킬기의탄소수는 7내지 20이다.구체적으로,페닐메틸, 2 -메틸페닐메틸, 3 -메틸페닐메틸,
4 -메틸페닐메틸, 2 - 1631 -부틸페닐메틸, 3 11-부틸페닐메틸, 4 11-부틸페닐메틸 등이 있으나,이에 한정되지 않는다. 본명세서에 있어서,아릴기는특별히 한정되지 않으나탄소수 6내지 60인 것이 바람직하며 ,단환식아릴기또는다환식 아릴기일수있다.일실시상태에 따르면,상기 아릴기의탄소수는 6내지 30이다.일실시상태에 따르면,상기 아릴기의 탄소수는 6내지 20이다.상기 아릴기가단환식 아릴기로는페닐기, 비페닐이기,터페닐기등이될수있으나,이에 한정되는것은아니다.상기 다환식 아릴기로는나프틸기 ,안트라세닐기 ,페난쓰레닐기 ,파이레닐기 , 페릴레닐기,크라이세닐기,플루오레닐기등이될수있으나,이에 한정되는 것은아니다. 본명세서에 있어서,플루오레닐기는치환될수있고,치환기 2개가서로 등이 될수있다.다만,이에 한정되는것은아니다.
[70]
[기] 본명세서에 있어서 ,헤테로아릴은이종원소로 0, N, Si및 S중 1개 이상을
포함하는헤테로아릴로서,탄소수는특별히 한정되지 않으나,탄소수 2내지 60인것이바람직하다.헤테로아릴의 예로는잔텐 (xanthene),
티오잔텐 (thioxanthen),티오펜기 ,퓨란기，피롤기,이미다졸기 ,티아졸기 , 옥사졸기，옥사디아졸기，트리아졸기，피리딜기 ,비피리딜기 ,피리미딜기 , 트리아진기,아크리딜기,피리다진기,피라지닐기,퀴놀리닐기,퀴나졸린기, 퀴녹살리닐기,프탈라지닐기,피리도피리미디닐기,피리도피라지닐기, 피라지노피라지닐기 ,이소퀴놀린기，인돌기 ,카바졸기 ,벤즈옥사졸기 , 벤조이미다졸기 ,벤조티아졸기 ,벤조카바졸기 ,벤조티오펜기,디벤조티오펜기 , 벤조퓨라닐기 ,페난쓰롤린기 (phenanthroline),이소옥사졸릴기 ,티아디아졸릴기 , 페노티아지닐기 및디벤조퓨라닐기등이 있으나,이들에만한정되는것은 아니다.
[73] 본명세서에 있어서,아르알킬기,아르알케닐기,알킬아릴기,아릴아민기, 아릴실릴기중의아릴기는전술한아릴기의 예시와같다.본명세서에 있어서, 아르알킬기,알킬아릴기,알킬아민기중알킬기는전술한알킬기의 예시와같다. 74
본명세서에 있어서,헤테로아릴아민중헤테로아릴은전술한헤테로아릴에 관한설명이 적용될수있다.본명세서에 있어서,아르알케닐기중알케닐기는 전술한알케닐기의 예시와같다.본명세서에 있어서 ,아릴렌은 2가기인것을 제외하고는전술한아릴기에 관한설명이 적용될수있다.본명세서에 있어서, 헤테로아릴렌은 2가기인것을제외하고는전술한헤테로아릴에관한설명이 적용될수있다.본명세서에 있어서 ,탄화수소고리는 1가기가아니고, 2개의 치환기가결합하여 형성한것을제외하고는전술한아릴기또는
사이클로알킬기에 관한설명이 적용될수있다.본명세서에 있어서,
헤테로고리는 1가기가아니고, 2개의치환기가결합하여 형성한것을
제외하고는전술한헤테로아릴에 관한설명이 적용될수있다.
[75] 본명세서에 있어서,방향족고리는고리 형성 원자로서탄소만을포함하면서 분자전체가방향족성 (aromaticity)을갖는축합단환또는축합다환고리를 의미한다.상기방향족고리의탄소수는 6내지 60,또는 6내지 30,또는 6내지 20이나,이에한정되는것은아니다.또한,상기방향족고리로는벤젠고리, 나프탈렌고리,안트라센고리,페난쓰렌고리,파이렌고리등이될수있으나, 이에한정되는것은아니다.
P6]
[77] 본명세서에 있어서 ,비방향족고리 (non-aromatic ring)는고리형성원자로서 탄소만을포함하면서분자전체가방향족성을갖지않는축합단환또는 축합다환지환족고리를의미한다.상기비방향족고리의탄소수는 6내지 60, 또는 6내지 30,또는 6내지 20이나,이에한정되는것은아니다.또한,상기 비방향족고리로는인덴고리,플루오렌고리등이될수있으나,이에한정되는 것은아니다.이때,상기인덴고리,플루오렌고리등은치환또는비치환될수 있고,그치환기의종류는상술한바를참조한다.
P8]
[79] 본명세서에 있어서 ,헤테로고리 (heterocyclic ring)는고리형성원자로서탄소 외 0, N, Si및 S중 1개이상의헤테로원자를포함하면서분자전체가
방향족성을갖거나또는방향족성을갖지않는갖지않는헤테로축합단환또는 헤테로축합다환고리를의미한다.상기헤테로고리의탄소수는 2내지 60,또는 2내지 30,또는 2내지 20이나,이에한정되는것은아니다.또한,상기헤테로 고리로는벤조퓨란고리 ,벤조티오펜고리 ,벤조실롤 (benzosilole)고리 , 디벤조퓨란고리,디벤조티오펜고리,디벤조실롤 (dibenzosilole)고리, 실로란 (silolane)고리등이될수있으나,이에한정되는것은아니다.이때,상기 벤조실롤고리,디벤조실롤고리등은치환또는비치환될수있고,그치환기의 종류는상술한바를참조한다.
[8이
[81] (화합물)
[82] 한편,본발명은상기화학식 1로표시되는디아민화합물을제공한다.
[83] 상기화학식 1로표시되는화합물은,이하상세히설명할바와같이 ,
플루오렌계코어의치환기로’ Z /및 'L-X-Z 2’를포함하고, 'Z /과 'L-X-Z 2’는서로 상이하며,서로연결되어있지않은구조를갖는다.구체적으로,상기
플루오렌계코어의치환기가서로동일하거나,또는치환기가서로연결된 구조를갖는화합물은높은결정성을가져유기용매에대한용해도가낮은 문제가있는반면,상기화학식 1로표시되는화합물은이에비해낮은결정성을 가져용액공정에사용되는유기용매에대한증가된용해도를나타내므로,유기 발광소자제조시용액공정에사용되기바람직하다.
[84]
[85] 바람직하게는,상기화학식 1에서,
[86] R 1및 R 2중적어도하나는 R !또는 R 2끼리서로결합하여 , C 6-60지환족고리 ; 또는 N, 0, S및 Si로구성되는군으로부터선택되는어느하나이상의 2020/175867 1»（：1^1{2020/002606
9 헤테로원자를포함하는 0 2-60헤테로고리를형성하고,나머지는수소이거나 또는 II 1또는 II 2끼리서로결합하여 0 6-60방향족고리 ; 0 6-60지환족고리 ;또는 0 및 로구성되는군으로부터선택되는어느하나이상의헤테로원자를 포함하는 0 2-60헤테로고리를형성한다.
87] 이때 ,상기 0 6-60방향족고리 ,상기 0 6-60지환족고리 및상기 0 2-60헤테로
고리는각각독립적으로,수소, 0 ,_10알킬및 0 6-20아릴로구성되는군으로부터 선택되는치환기로치환될수있다. 다시 말하여,
II 1은서로결합하여상기 0 6-60지환족고리또는상기 0 2-60헤테로고리를 형성하고, II 2는모두수소이거나,또는서로결합하여상기 0 6-60방향족고리 , 상기 0 6-60지환족고리 ,또는상기 0 2-60헤테로고리를형성하거나;
[9 II 2가서로결합하여상기 0 6-60지환족고리또는상기 0 2-60헤테로고리를
형성하고, II !는모두수소이거나,또는서로결합하여상기 0 6-60방향족고리 , 상기 0 6-60지환족고리 ,또는상기 0 2-60헤테로고리를형성하거나;또는
II 1및 II 2모두가 II 1또는 II 2끼리서로결합하여상기 0 6-60방향족고리 ,상기 0 6-60지환족고리 ,또는상기 0 2-60헤테로고리를형성할수있다.
[93]
[94] 바람직하게는, 및 11 2중적어도하나는 또는요2끼리서로결합하여하기 화학식 2(1내지 2은로표시되는구조중어느하나를형성하고,나머지는 수소이거나,또는서로결합하여하기화학식 내지 2은로표시되는구조중 어느하나를형성한다:
* *
， ， ， !
90 8 * *
9 9 9 9882751 、、 、 、
Figure imgf000010_0001
2^ 20 2선
少人、
2e 2†
Figure imgf000010_0002
[96] 상기화학식 내지 2은에서 ,
는 0, 02在 7,또는 8å 9이고, 2020/175867 1»（：1^1{2020/002606
10
[98] å 6내지 9는각각독립적으로,치환또는비치환된 0 !-60알킬 ;치환또는
비치환된 0 !_60할로알킬 ;치환또는비치환된 0 3-60사이클로알킬 ;치환또는 비치환된 (： 6-6。아릴;또는치환또는비치환된 0및 8로구성되는군으로부터 선택되는어느하나이상의헤테로원자를포함하는 0 2_60헤테로아릴이고,
[99] *는요1또는 11 2와결합된탄소와의 결합위치를의미한다.
0이
[101] 다시 말하여,
[102] II !은서로결합하여상기화학식 2(1내지 2은로표시되는구조중어느하나를 형성하고, II 2는모두수소이거나,또는서로결합하여상기 화학식
Figure imgf000011_0001
표시되는구조중어느하나를형성하거나;
[103] II 2는서로결합하여상기화학식 2(1내지 2은로표시되는구조중어느하나를 형성하고, II !은모두수소이거나,또는서로결합하여상기 화학식
Figure imgf000011_0002
표시되는구조중어느하나를형성하거나;또는
[104] II !및 II 2모두가 II !끼리또는 II 2끼리서로결합하여상기화학식 2d내지 2은로 표시되는구조중어느하나를형성할수있다.
[105]
[106] 가장바람직하게는,
Figure imgf000011_0003
하나는서로결합하여상기화학식
2(1로표시되는구조를형성하고,나머지는수소이거나,또는서로결합하여상기 화학식
Figure imgf000011_0004
구조를형성한다.
[107]
[108] 예를들어,상기 화학식 1로표시되는화합물은,
[109] II 1모두수소이고, II 2끼리서로결합하여상기 화학식 2(1로표시되는구조를 형성하는경우,하기화학식 1- 1로표시되고,
[110] II 2모두수소이고, II !끼리서로결합하여상기 화학식 2(1로표시되는구조를 형성하는경우,하기화학식 1-2로표시되고,
[111] II !끼리서로결합하여상기화학식 로표시되는구조를형성하고, II 2끼리 서로결합하여상기 화학식 2(1로표시되는구조를형성하는경우,하기 화학식 1-3으로표시되고,
[112] II 1끼리서로결합하여상기화학식 2(1로표시되는구조를형성하고, II 2끼리 서로결합하여상기 화학식 로표시되는구조를형성하는경우,하기화학식
[113]
Figure imgf000011_0005
결합하여상기화학식 2(1로표시되는구조를형성하는 경우,하기 화학식 1-5로표시된다:
[114] [화학식 1- 1] 2020/175867 1»（：1/10公020/002606
11
Figure imgf000012_0001
[116] [화학식 1-2]
[117]
Figure imgf000012_0002
[118] [화학식 1-3]
[119]
Figure imgf000012_0003
[120] [화학식 1-4] [124] 상기화학식 1-1내지 1-5에서,
[125] 足 , , ,：^및사 !내지사4는상기화학식 1에서정의한바와같고,
[126] V !및 V 2중하나는단일결합이고,나머지하나는 0,民 0, 0（0 "알킬） 2, 또는 片나알킬） 2이며 ,
[127] 3및 4중하나는단일결합이고,나머지하나는 0,民 0（0 "알킬） 2,또는
!-4알킬） 2이다.
[128]
[129] 바람직하게는, Y !및 Y 2중하나는단일결합이고,나머지하나는 0, S, C（메틸）
2,또는 Si（메틸） 2이며 ,
[130] Y 3및 Y 4중하나는단일결합이고,나머지하나는 0, S, C（메틸） 2,또는 Si（메틸） 2이다.
[131]
[132] 바람직하게는, 은페닐또는비페닐릴이고,여기서,
Figure imgf000013_0001
은비치환되거나, 또는중수소,할로겐,시아노, 0 ,_10알킬, 0 3-10사이클로알킬, ,_10알킬） 3및 （（： 6-2。아릴） 3로구성되는군으로부터 각각독립적으로선택되는 1개내지
5개의치환기로치환된다. 2020/175867 1»（：1^1{2020/002606
13
[134] 보다바람직하게는, 1은페닐또는비페닐릴이고,여기서 , å 중수소, 할로겐,시아노,메틸,에틸,프로필, 1 _부틸,사이클로펜틸, （메틸） 3및
（페닐） 3로구성되는군으로부터 각각독립적으로선택되는 1개내지 5개의 치환기로치환된다.
[135]
[136] 가장바람직하게는, 1 !은하기로구성되는군으로부터선택되는어느
하나이다:
[137]
Figure imgf000014_0001
[138]
[139] 바람직하게는, 은비치환되거나,또는 0 140알킬로치환된페닐렌이다.보다 바람직하게는, 은페닐렌이다.가장바람직하게는, 은 1,4 -페닐렌이다.
[14이
[141] 바람직하게는, 2내지 å 5는각각독립적으로, 0 알킬; 0 6-20아릴;또는 0 7-20 아랄킬이고,여기서 , å 2내지 å 5는비치환되거나,또는 0 ,_10알킬또는 ,_10 알킬） 3로치환된다.
[142]
[143] 보다바람직하게는, å 2및 å 3는각각독립적으로, 0 알킬;비치환되거나, 또는 0 ,_10알킬로치환된 0 6-20아릴;또는비치환되거나,또는 0 ,_10알킬로 치환된 0 7-20아랄킬이다.또한, 4및 å 5는각각독립적으로, 0 알킬;또는 비치환되거나,또는 0 ,_10알킬로치환된 0 6-60아릴이다.
[144]
[145] 이때,‘상기 !^및 2 2; 2 2및 3;또는 는서로연결되어 5원-헤테로
고리를형성할수있다，라고함은,상기 및 ᄅ끼리, 2및 3끼리,또는 å 4및 å 5끼리서로연결되어 의헤테로원자인 0,民 또는 를함유하는 5원-헤테로 2020/175867 1»（：1^1{2020/002606
14 고리를형성할수있음을의미한다.
[146]
[147] 예를들어,상기 화학식 1에서, 이 1,4 -페닐렌이고, å 2가페닐이고, X가 0인 경우에 ,상기 화합물은하기 화학식 로표시되는구조뿐아니라, 및 å 2가 서로연결되어 의 헤테로원자 0함유 5원-헤테로고리를형성하는하기화학식 의구조또한가능함을의미한다.
Figure imgf000015_0002
[15이
[151] 또한,예를들어,상기 화학식 1에서, 가모두페닐이고, 가 N (페닐)인경우, 즉, å 2및 3가모두페닐인경우에 ,상기 화합물은하기 화학식 로표시되는 구조뿐아니라, 및 3가서로연결되어 의헤테로원자 N함유 5원-헤테로 고리를형성하는하기 화학식 3(1의구조또한가능함을의미한다.
[152] ［화학식 30］［화학식 3(1］
[153]
Figure imgf000015_0001
[154]
[155] 또한,예를들어 ,상기 화학식 1에서 , å 4및 å 5가모두에틸인경우에 ,상기
화합물은하기화학식 36로표시되는구조뿐아니라, 및 å 5가서로연결되어 의 헤테로원자 함유 5원-헤테로고리를형성하는하기 화학식 3의구조 또한가능함을의미한다.
[156] ［화학식 3리［화학식 3幻 2020/175867 1»（：1^1{2020/002606
15
Figure imgf000016_0001
[158]
[159] 예를들어, 1시2 2는하기로구성되는군으로부터선택되는어느하나이다:
[160]
2020/175867 1»（：1^1{2020/002606
16
Figure imgf000017_0001
[162] 상기에서,
[163] II, II’및 II”는각각독립적으로,수소,
Figure imgf000017_0002
（메틸） 3이다.
[164]
[165] 바람직하게는, 1 및 는단일결합이다.
[166]
[167] 바람직하게는,쇼 내지쇼]· 4는각각독립적으로,페닐,나프틸,비페닐릴,또는 디벤조퓨라닐이고,
[168] 여기서,쇼 내지사 4는비치환되거나,또는중수소,할로겐,（ 。알킬및
Figure imgf000017_0003
1-10알킬） 3로구성되는군으로부터각각독립적으로선택되는 1개내지 5개의 2020/175867 1»（：1^1{2020/002606
17 치환기로치환된다.
[169]
[17이 보다바람직하게는,사 !내지사 4는각각독립적으로,페닐,나프틸,비페닐릴, 또는디벤조퓨라닐이고,
[171] 여기서 ,사 1내지사 4는비치환되거나,또는중수소,할로겐,메틸, 1 _부틸, （메틸） 3로구성되는군으로부터 각각독립적으로선택되는 1개내지 5개의 치환기로치환된다.
[172]
[173] 가장바람직하게는,쇼］· !내지사 4는각각독립적으로,하기로구성되는
군으로부터선택되는어느하나이다:
[174]
Figure imgf000018_0001
Figure imgf000018_0002
[175]
[176] 이때 ,바람직하게는쇼］· 1및쇼］· 4는서로동일하고, Ar 2및 Ar 3는서로동일하다.
[177]
[178] 또한,바람직하게는,상기화학식 1로표시되는화합물은하기 화학식 2- 1내지 2- 10중어느하나로표시된다:
2020/175867 1»（：1/10公020/002606
18
Figure imgf000019_0001
[18이 상기화학식 2-1내지 2 0에서,
[181] X, å å 2및사 1내지사 4는상술한바와같고,
[182] ^및 V 6는각각독립적으로, 0,民（：（메틸） 2,또는 （메틸） 2이다.
[183]
[184] 보다바람직하게는,상기화학식 1로표시되는화합물은하기로구성되는 군으로부터선택될수있다:
[186]
[187]
2020/175867 1»（：1^1{2020/002606
21
Figure imgf000022_0001
[188] 상기에서 ,각치환기에 대한정의는앞서설명한바와같다.
[189]
[190] 예를들어,상기 화합물은하기 화합물로구성되는군으로부터선택되는어느 하나이다:
[191]
[192]
[193]
[194]
[195]
[196]
Figure imgf000026_0001
[197]
[198] [199]
[200] [201]
[202]
[203]
[204]
[205]
[206]
[207]
[208]
[209]
[210]
[211]
[212]
[213]
[214]
[215]
[216]
[217]
[218] wo 2020/175867
Figure imgf000048_0001
Figure imgf000048_0002
[220] [221] 2020/175867 1»（：1^1{2020/002606
50
Figure imgf000051_0001
[222]
[223] 이때,상기화합물들의치환기 치환기
Figure imgf000051_0002
Figure imgf000051_0003
의미한다.
[224]
[225] 한편,상기화학식 1로표시되는화합물은일례로하기반응식 1과같은제조 방법으로제조할수있다.상기제조방법은후술할제조예에서보다구체화될 수있다.
Figure imgf000052_0001
[228] 상기반응식 1에서 ,각각의치환기에대한정의는앞서설명한바와동일하다.
[229] 상기단계 1-1은강염기에의한카보닐기의환원반응에의해출발물질 SM1에 하이드록시기및화합물 SM2를도입하여중간체화합물 INT.1을제조하는 단계이고,상기단계 1-2는 Friedel-Crafts type의 electrophilic substitution반응에 의해상기중간체화합물 INT.1의하이드록시기에화합물 SM3를도입하여 중간체화합물 INT.2를제조하는단계이고,상기단계 1-3은상기중간체화합물 INT.2와 2급아민인 SM4를반응시켜상기화학식 1로표시되는화합물을 제조하는단계이다.이러한제조방법은후술할제조예에서보다구체화될수 있다.
[23이
[231] （코팅조성물）
[232] 한편,본발명에따른화합물은용액공정으로유기발광소자의유기물층, 특히발광층을형성할수있다.구체적으로,상기화합물은발광층의도펀트 재료로사용될수있다.이를위하여,본발명은상술한본발명에따른화합물및 용매를포함하는코팅조성물을제공한다.
[233]
[234] 상기용매는본발명에따른화합물을용해또는분산시킬수있는용매이면 특별히제한되지않으며,일례로클로로포름,염화메틸렌, 1,2 -디클로로에탄, 1,1,2 -트리클로로에탄,클로로벤젠, 0-디클로로벤젠등의염소계용매 ;
테트라하이드로퓨란,디옥산등의에테르계용매 ;톨루엔,크실렌, 2020/175867 1»（：1^1{2020/002606
52 트리메틸벤젠,메시틸렌등의방향족탄화수소계용매;시클로핵산,
메틸시클로핵산, 11펜탄, 11핵산, 11헵탄, 11옥탄, 11노난, 11데칸등의지방족 탄화수소계용매;아세톤,메틸에틸케톤,시클로핵사논등의 케톤계용매;
아세트산에틸,아세트산부틸,에틸셀로솔브아세테이트등의 에스테르계용매; 에틸렌글리콜,에틸렌글리콜모노부틸에테르,에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노메틸에테르,디메톡시에탄,프로필렌글리콜,디에톡시메탄, 트리에틸렌글리콜모노에틸에테르,글리세린, 1,2 -핵산디올등의다가알코올및 그의유도체 ;메탄올,에탄올,프로판올,이소프로판올,시클로핵산올등의 알코올계용매;디메틸술폭사이드등의술폭사이드계용매;및
메틸- 2 -피롤리돈, N,N -디메틸포름아미드등의아미드계용매 ;
부틸벤조에이트,메틸- 2 -메톡시벤조에이트등의 벤조에이트계용매;테트랄린;
3 -페녹시톨루엔등의용매를들수있다.또한,상술한용매를 1종단독으로 사용하거나 2종이상의용매를혼합하여사용할수있다.바람직하게는상기 용매로톨루엔을사용할수있다.
[235]
[236] 또한,상기코팅조성물은호스트재료로사용되는화합물을더포함할수있고, 상기호스트재료에사용되는화합물에 대한설명은후술한다.
[237]
[238] 또한,상기코팅조성물의 점도（25ᄋ 0는 1산5내지 산5가바람직하며,상기의 범위에서코팅이용이하다.또한,상기코팅조성물내본발명에따른화합물의 농도는 0.1
Figure imgf000053_0001
바람직하다.
[239]
[24이 또한,상기코팅조성물의용매에 대한용해도（\ %）는용매톨루엔을기준으로
2.5 \ %내지 \ %이고,이에따라상기화학식 1로표시되는화합물을 포함하는코팅조성물은용액공정에사용되기 적합하다.
[241]
[242] 또한,본발명은상술한코팅조성물을사용하여 발광층을형성하는방법을
제공한다.구체적으로,양극상에 ,또는양극상에 형성된정공수송층상에 상술한본발명에 따른발광층을용액공정으로코팅하는단계;및상기코팅된 코팅조성물을열처리하는단계를포함한다.
[243]
[244] 상기용액공정은상술한본발명에 따른코팅조성물을사용하는것으로,스핀 코팅,딥코팅,닥터블레이딩,잉크겟프린팅,스크린프린팅,스프레이법,롤 코팅등을의미하지만,이들만으로한정되는것은아니다.
[245]
[246] 상기 열처리 단계에서 열처리온도는 150내지 230ᄋ（：가바람직하다.또한,상기 열처리시간은 1분내지 3시간이고,보다바람직하게는 분내지 1시간이다. 또한,상기 열처리는아르곤,질소등의불활성 기체분위기에서수행하는것이 바람직하다.
[247]
[248] (유기발광소자)
[249] 또한,본발명은상기화학식 1로표시되는화합물을포함하는유기발광
소자를제공한다.일례로,본발명은제 1전극;상기제 1전극과대향하여구비된 제 2전극;및상기제 1전극과상기제 2전극사이에구비된발광층을포함하는 유기발광소자로서,상기발광층은상기화학식 1로표시되는화합물을 포함하는,유기발광소자를제공한다.
[25이
[251] 또한,본발명에따른유기발광소자는,기판상에양극, 1층이상의유기물층 및음극이순차적으로적층된구조 (normal type)의유기발광소자일수있다. 또한,본발명에따른유기발광소자는기판상에음극, 1층이상의유기물층및 양극이순차적으로적증된역방향구조 (inverted type)의유기발광소자일수 있다.예컨대,본발명의일실시예에따른유기발광소자의구조는도 1및 2에 예시되어 있다.
[252]
[253] 도 1은기판 (1),양극 (2),발광층 (3),음극 (4)으로이루어진유기발광소자의 예를도시한것이다.이와같은구조에 있어서 ,상기화학식 1로표시되는 화합물은상기발광층에포함될수있다.
[254]
[255] 도 2는기판 (1),양극 (2),정공주입층 (5),정공수송층 (6),발광층 (7),
전자수송층 (8),전자주입층 (9)및음극 (4)으로이루어진유기발광소자의 예를 도시한것이다.이와같은구조에있어서,상기화학식 1로표시되는화합물은 상기발광층에포함될수있다.
[256]
[257] 본발명에따른유기발광소자는,상기발광층이본발명에따른화합물을 포함하고,상술한방법과같이제조되는것을제외하고는당기술분야에알려져 있는재료와방법으로제조할수있다.
[258]
[259] 예컨대,본발명에따른유기발광소자는기판상에양극,유기물층및음극을 순차적으로적층시켜제조할수있다.이때 ,스퍼터링법 (sputtering)이나전자빔 증발법 (e-beam evaporation)과같은 PVD(physical Vapor Deposition)방법을 이용하여 ,기판상에금속또는전도성을가지는금속산화물또는이들의 합금을증착시켜양극을형성하고,그위에정공주입층,정공수송층,발광층및 전자수송층을포함하는유기물층을형성한후,그위에음극으로사용할수 있는물질을증착시켜제조할수있다.
[26이
[261] 이와같은방법외에도,기판상에음극물질로부터유기물층,양극물질을 차례로증착시켜유기발광소자를제조할수있다 (\¥0 2003/012890).다만,제조 방법이이에한정되는것은아니다.
[262]
[263] 이와같은방법외에도,기판상에음극물질로부터유기물층,양극물질을
차례로증착시켜유기발광소자를제조할수있다 (WO 2003/012890).다만,제조 방법이이에한정되는것은아니다.
[264]
[265] 일례로,상기제 1전극은양극이고,상기제 2전극은음극이거나,또는상기제 1 전극은음극이고,상기제 2전극은양극이다.
[266]
[267] 상기양극물질로는통상유기물층으로정공주입이원활할수있도록
일함수가큰물질이바람직하다.상기양극물질의구체적인예로는바나둠, 크롬,구리,아연,금과같은금속또는이들의합금;아연산화물,인둠산화물, 인듐주석산화물 (ITO),인듐아연산화물 (IZO)과같은금속산화물; ZnO:Al또는 SnO 2:Sb와같은금속과산화물의조합;폴리 (3 -메틸티오펜),
폴리 [3, 4-(에틸렌- 1,2 -디옥시)티오펜] (PEDOT),폴리피롤및폴리아닐린과같은 전도성화합물등이 있으나,이들에만한정되는것은아니다.
[268]
[269] 상기음극물질로는통상유기물층으로전자주입이용이하도록일함수가작은 물질인것이바람직하다.상기음극물질의구체적인예로는마그네슘,칼슘, 나트륨,칼륨,티타늄,인둠,이트륨,리튬,가돌리늄,알루미늄,은,주석및납과 같은금속또는이들의합금; LiF/Al또는 LiO 2/Al과같은다층구조물질등이 있으나,이들에만한정되는것은아니다.
[27이
[271] 상기정공주입층은전극으로부터정공을주입하는층으로,정공주입물질로는 정공을수송하는능력을가져양극에서의정공주입효과,발광층또는
발광재료에대하여우수한정공주입효과를갖고,발광층에서생성된여기자의 전자주입층또는전자주입재료에의이동을방지하며,또한,박막형성능력이 우수한화합물이바람직하다.정공주입물질의 HOMO(highest occupied molecular orbital)가양극물질의일함수와주변유기물층의 HOMO사이인것이 바람직하다.정공주입물질의구체적인예로는금속포피린 (porphyrin), 올리고티오펜,아릴아민계열의유기물,핵사니트릴핵사아자트리페닐렌계열의 유기물,퀴나크리돈 (quinacridone)계열의유기물,페릴렌 (perylene)계열의 유기물,안트라퀴논및폴리아닐린과폴리티오펜계열의전도성화합물등이 있으나,이들에만한정되는것은아니다.
[272]
[273] 상기정공수송층은정공주입층으로부터정공을수취하여발광층까지정공을 수송하는층으로,정공수송물질로는양극이나정공주입층으로부터정공을 2020/175867 1»（：1^1{2020/002606
55 수송받아발광층으로옮겨줄수있는물질로정공에대한이동성이큰물질이 적합하다.구체적인예로는아릴아민계열의유기물,전도성화합물,및공액 부분과비공액부분이함께있는블록공중합체등이있으나,이들에만한정되는 것은아니다.
[274]
[275] 상기발광층은호스트재료및도펀트재료를포함할수있다.도펀트재료로는 상술한화학식 1로표시되는화합물이사용될수있다.또한,호스트재료로는 축합방향족환유도체또는헤테로환함유화합물등을사용할수있다.
구체적으로축합방향족환유도체로는안트라센유도체 ,피렌유도체 ,나프탈렌 유도체,펜타센유도체,페난트렌화합물,늘루오란텐화합물등이 있고, 헤테로환함유화합물로는카바졸유도체,디벤조뉴란유도체,래더형뉴란 화합물,피리미딘유도체등이 있으나,이에한정되지않는다.
[276]
[277] 상기전자수송층은전자주입층으로부터전자를수취하여발광층까지전자를 수송하는층으로,전자수송물질로는음극으로부터전자를잘주입받아 발광층으로옮겨줄수있는물질로서,전자에대한이동성이큰물질이
적합하다.구체적인예로는 8 -히드록시퀴놀린의신착물;쇼均 3를포함한착물; 유기라디칼화합물;히드록시플라본-금속착물등이 있으나,이들에만한정되는 것은아니다.전자수송층은종래기술에따라사용된바와같이임의의원하는 캐소드물질과함께사용할수있다.특히,적절한캐소드물질의예는낮은 일함수를가지고알루미늄층또는실버층이뒤따르는통상적인물질이다.
구체적으로세슘,바륨,칼슘,이테르븀및사마륨이고,각경우알루미늄증또는 실버층이뒤따른다.
[278]
[279] 상기전자주입층은전극으로부터전자를주입하는층으로,전자를수송하는 능력을갖고,음극으로부터의전자주입효과,발광층또는발광재료에대하여 우수한전자주입효과를가지며,발광층에서생성된여기자의정공주입층에의 이동을방지하고,또한,박막형성능력이우수한화합물이바람직하다.
구체적으로는 1 , 므, （：1, 요므, U 20, 플루오레논,안트라퀴노다이메탄, 다이페노퀴논,티오피란다이옥사이드,옥사졸,옥사다이아졸,트리아졸, 이미다졸,페릴렌테트라카복실산,프레오레닐리덴메탄,안트론등과그들의 유도체,금속착체화합물및질소함유 5원환유도체등이 있으나,이에
한정되지않는다.
[28이
[281] 상기금속착체화합물로서는 8 -하이드록시퀴놀리나토리튬,
비스（8 -하이드록시퀴놀리나토）아연,비스（8 -하이드록시퀴놀리나토）구리 , 비스（8 -하이드록시퀴놀리나토）망간,트리스（8 -하이드록시퀴놀리나토）알루미늄, 트리스（2 -메틸- 8 -하이드록시퀴놀리나토）알루미늄, 2020/175867 1»（：1^1{2020/002606
56 트리스（8 -하이드록시퀴놀리나토）갈륨,
비스（10 -하이드록시벤조 ]퀴놀리나토）베릴륨,
비스（10 -하이드록시벤조 ]퀴놀리나토）아연,
비스（2 -메틸- 8 -퀴놀리나토）클로로갈륨,
비스（2 -메틸- 8 -퀴놀리나토）（0 -크레졸라토）갈륨,
비스（2 -메틸- 8 -퀴놀리나토）（1 -나프톨라토）알루미늄,
비스（2 -메틸- 8 -퀴놀리나토）（2 -나프톨라토）갈륨등이있으나,이에한정되지 않는다.
[282]
[283] 본발명에따른유기발광소자는사용되는재료에따라전면발광형,후면 발광형또는양면발광형일수있다.
[284]
[285] 또한,본발명에따른화합물은유기발광소자외에도유기태양전지또는 유기트랜지스터에포함될수있다.
[286]
[287] 상기화학식 1로표시되는화합물및이를포함하는유기발광소자의제조는 이하실시예에서구체적으로설명한다.그러나하기실시예는본발명을 예시하기위한것이며,본발명의범위가이들에의하여한정되는것은아니다.
[288]
[289] 제조예 1:화합물 1의제조
[29이
2020/175867 1»（：1^1{2020/002606
57
Figure imgf000058_0001
[291] 단계 1-1:중간체화합물쇼3의합성
[292] 화합물쇼1(17은, 50 11111101),쇼2(15.9은, 75 11111101), (1(?1¾ 3) 4(5.8은, 5 11111101)및 X 2 00 3(20.7 ^ 150 11111101)을톨루엔 (500 )및증류수 (150 )에녹인후, 90ᄋ(：에서 15시간교반하였다.유기층을분리한뒤 이를 MgS0 4를이용하여수분을제거한 후,감압하여용매를제거했다.얻어진물질을컬럼크로마토그래피하여 화합물 쇼3(12 §,수율: 63%)을분리 및정제하였다.
[293] MS:，印+ = 381
[294]
[295] 단계 1-2:중간체화합물쇼4의합성
[296] 상기단계 1-1에서 제조한화합물쇼3(1.52 ^ 4 11111101),수산화나트륨 (0.2 ^ 5 11111101),에탄올 30센을넣고 4 8시간환류교반후실온으로냉각하였다. 2 -노말 염산을적가하고 30분교반후여과하였다.디클로로메탄과노말핵산으로 재결정하여쇼4(1.2 수율: 79%)를얻었다.
[297] MS: +印+ = 367 2020/175867 1»（：1^1{2020/002606
58
[298]
[299] 단계 1-3:중간체화합물쇼5의합성
[30이 상기단계 1-2에서제조한화합물쇼4(1.47 ^ 4 11111101),메탄설폰산 20 를넣고 80ᄋ (:로승은하여 3시간교반후실온으로냉각하였다.반응용액에얼음물 20 에천천히적가후 30분교반하였다.생성된고체는여과후물과메탄올로 씻어주어화합물쇼5를 (1.24용，수율: 89%)얻었다.
[301] MS: +¾+ = 349
[302]
[303] 단계 1-4:중간체화합물쇼6의합성
[304] 상기단계 1-3에서제조한화합물쇼5(1.05은, 3 11111101)를디클로로메탄 30 을 넣고상온교반하였다.브롬 (0.96 6 11^1101)은디클로로메탄 5 에희석하여 적가하였고, 8시간상온교반하였다.반응완료후반응용기에아세톤 30 을 넣고교반하였다.생성된고체는여과후아세톤으로씻어주었다.고체는 모노클로로벤젠으로재결정하여화합물쇼6(0.85 수율: 66%)를얻었다.
[305] MS:，¾+ = 427
[306]
[307] 단계 1-5:중간체화합물쇼8의합성
[308] 화합물쇼7(2.13은, 10 _01)을테트라하이드로퓨란 400 11止에넣고교반하면서 영하 78ᄋ (:로냉각하고,상기제조된용액에 부틸리튬 1.6 5.35 1111, 8.5 11111101)를첨가한뒤 1시간교반하였다.다음으로,상기단계 1-4에서제조한 화합물쇼6(3.21 7.5 _01)을첨가하고 1시간교반한다음실온으로승은한후 두시간을교반하였다.이후,암모늄클로라이드수용액을첨가하고 30분간 교반한다음분별깔때기에서유기층을분리한뒤이를 를이용하여 수분을제거한후,감압하여용매를제거하였다.이로부터얻어진물질을 컬럼크로마토그래피하여화합물쇼8(2.8 ，수율: 50%)을분리및정제하였다.
[309] MS: +印+ = 561
[310]
[311] 단계 1-6:중간체화합물쇼10의합성
[312] 상기단계 1-5에서제조한화합물쇼8(2.81은, 5 11111101)을디클로로메탄 200 11止에 넣고교반하면서 0ᄋ (:로냉각한다음,메탄술폰산 (1.2 ， 20 11111101)을 10분간 첨가하고실온으로승온하였다.이후,여기에화합물쇼9(2.68 7.5 11111101)를 첨가하고 30분교반한다음나트륨바이카보네이트수용액을첨가하고 30분간 교반하였다.이후,분별깔때기에서유기층을분리한뒤이를 MgS04를이용하여 수분을제거한후,감압하여용매를제거하였다.이로부터얻어진물질을 컬럼크로마토그래피하여화합물쇼^(4.7 ¾，수율: 94%)를분리및정제하였다.
[313]
Figure imgf000059_0001
901
[314]
[315] 단계 1-7:화합물 1의합성 2020/175867 1»（：1^1{2020/002606
59
[316] 상기단계 1-6에서제조한화합물사0(2.03은, 2.25 _01),화합물사1(1.13은, 5
Figure imgf000060_0001
0.36 11111101)및
내110(0.기은, 7.43 11111101)을톨루엔 (50 )에녹인후, 100ᄋ(：에서 15시간교반 하였다.실온으로냉각하고증류수를넣은후분별깔때기에서유기층을분리한 뒤이를 MgS0 4를이용하여수분을제거한후,감압하여용매를제거했다. 얻어진물질을컬럼크로마토그래피하여화합물 ^1.1은，수율: 41%)을분리및 정제하였다.
[317] MS: +印+ = 1191
[318]
[319] 제조예 2:화합물 2의제조
[32이
Figure imgf000060_0002
[321] 상기제조예 1에서화합물쇼11대신쇼12를사용한것을제외하고는,상기 제조예 1과동일한방법을사용하여화합물 2(1.51 ，수율: 49%)를제조하였다.
[322]
Figure imgf000060_0003
1371
[323]
[324] 제조예 3:화합물 3의제조
[325]
2020/175867 1»（：1/10公020/002606
60
Figure imgf000061_0001
[326] 상기제조예 1에서화합물쇼2대신표1을사용한것을제외하고는,상기제조예 1과동일한방법을사용하여화합물 3을제조하였다.
[327]
Figure imgf000061_0002
1217
[328]
[329] 제조예 4:화합물 4의제조
[33이
Figure imgf000061_0003
2020/175867 1»（：1^1{2020/002606
61
[331] 상기제조예 3에서화합물사1대신사2를사용한것을제외하고는,상기
제조예 3과동일한방법을사용하여화합물 4(1.19용，수율: 38%)를제조하였다.
[332] MS: +印 + = 1397
[333]
[334] 제조예 5:화합물 5의제조
[335]
Figure imgf000062_0001
Figure imgf000062_0002
[336] 단계 5-1:중간체화합물 3의합성
[337] 화합물 0(15.5은, 5011111101), 02 (15.9은, 7511111101), (1(?]¾ 3) 4(5.8은, 511111101)및 X 2 (：0 3(20.걔, 15011111101)을톨루엔 (5001111)및증류수 (150 )에녹인후, 90ᄋ(：에서 15 시간교반하였다.
Figure imgf000062_0003
이용하여수분을제거한 후,감압하여용매를제거했다.얻어진물질을컬럼크로마토그래피하여화합물 03(13.1용，수율: 75%)을분리및정제하였다.
[338] MS:，印 + = 351
[339]
[34이 단계 5-2:중간체화합물 4의합성
[341] 상기단계 5-1에서제조한화합물 03(7.0은, 20 11111101)을넣고디클로로메탄 (100 11止)로녹인후 0ᄋ (:로냉각하였다.피리딘 (1.9은, 24 11111101)에이어 2020/175867 1»（：1^1{2020/002606
62 트리플루오로메탄설폰산무수물 (5.92 21 _01)를넣고실온에서 3시간 교반하였다.이후,분별깔때기에서유기층을분리한뒤 이를 MgS04를이용하여 수분을제거한후,감압하여용매를제거하였다.이로부터 얻어진물질을 컬럼크로마토그래피하여 화합물 04 (7.8 수율: 81%)를분리 및정제하였다.
[342] MS:，印 + = 483
[343]
[344] 단계 5-3:중간체화합물 5의합성
[345] 상기단계 5-2에서 제조한화합물 04(4.82 ^ 10 11111101)과포타슘시아니드 (1.3은,
20 11111101)와모산 3) 4(1.16은, 1 11111101)을넣고 N,N -디메틸포름아미드 (50 11止)에 녹인후 130ᄋ (:로승은하여 18시간교반하였다.이후,분별깔때기에서유기층을 분리한뒤 이를 를이용하여수분을제거한후,감압하여용매를 제거하였다.이로부터 얻어진물질을컬럼크로마토그래피하여화합물 04(2.3 수율: 65%)를분리 및정제하였다.
[346] MS: +印 + = 360
[347]
[348] 단계 5-4:중간체화합물 6의합성
[349] 상기단계 5-3에서 제조한 05 (1.8은, 5 11111101)과포타슘히드록시드 (0.56은, 10 11111101)를에탄올 (30 1111)및물 (10 )에 넣고 24시간환류교반하였다.실온으로 냉각후 0.2노르말염산을이용하여산성화하고생성된고체를여과하고 핵산으로세척한후건조하여 06(1.36용，수율: 72%)을얻었다.
[35이 MS:，印 + = 379
[351]
[352] 단계 5-5:중간체화합물 7의합성
[353] 상기단계 5-4에서 제조한 06(1.9은, 5 11111101)과메탄술폰산 (20 1^)을넣고
120ᄋ(：에서 4시간교반하였다.냉각후물 200센에 반응액을넣어 생성된 침전물을여과하고톨루엔으로세척한후건조하여 07(0.92 수율: 51%)을 얻었다.
[354] MS: +印 + = 361
[355]
[356] 단계 5-6:중간체화합물 8의합성
[357] 상기단계 5-5에서 제조한 07(3.0은, 8.32 11111101)를디클로로메탄 100 11止에 넣고 디클로로메탄 30 1111^에녹인브로민 (4.0은, 25 11111101)을천천히 첨가한후 60시간 동안상온에서교반하였다.침전물을여과하고디클로로메탄및핵산으로 세척한후톨루엔및 메틸피롤리돈으로재결정하여 08(1.4 수율: 32%)을 얻었다.
[358] MS: [^+印 += 517
[359]
[36이 단계 5-7:중간체화합물 9의합성 2020/175867 1»（：1^1{2020/002606
63
[361] 화합물쇼7（1.07용， 5 11111101）을테트라하이드로퓨란 200 11止에 넣고교반하면서 영하 78ᄋ（:로냉각하고,상기 제조된용액에此부틸리튬 1.6 M（2.8 1111, 4.5 11111101）를 첨가한뒤 1시간교반하였다.다음으로,상기단계 5-6에서제조한화합물
08（2.07 ， 4 11111101）을첨가하고 1시간교반한다음실온으로승은한후두시간을 교반하였다.이후,암모늄클로라이드수용액을첨가하고 30분간교반한다음 분별깔때기에서유기층을분리한뒤 이를 MgSO 4를이용하여수분을제거한후, 감압하여용매를제거하였다.이로부터 얻어진물질을컬럼크로마토그래피하여 화합물 09（1.1 §,수율: 42%）을분리 및정제하였다.
[362] MS:，印 + = 651
[363]
[364] 단계 5-8:중간체화합물（：10의합성
[365] 상기단계 5-7에서 제조한화합물 09（3.26은, 5 11111101）를디클로로메탄 200
11止에 넣고교반하면서 0ᄋ（:로냉각한다음,메탄술폰산（1.2 ， 20 11111101）을 10분간 첨가하고실온으로승온하였다.이후,여기에 화합물쇼9（2.68 7.5 11111101）를 첨가하고 30분교반한다음나트륨바이카보네이트수용액을첨가하고 30분간 교반하였다.이후,분별깔때기에서유기층을분리한뒤 이를 MgS0 4를이용하여 수분을제거한후,감압하여용매를제거하였다.이로부터 얻어진물질을 컬럼크로마토그래피하여 화합물（그 0（4.36은，수율: 88%）을분리 및정제하였다.
[366] MS: +印 + = 990
[367]
[368] 단계 5-9:화합물 5의합성
[369] 상기단계 5-8에서 제조한화합물 00（2.23은, 2.25 11111101）,화합물시1（1.13은,
511111101）, （1 2（（¾幻 3（110 0.12 11111101）, 3（73 0.36 11111101）및
내110（0.기은, 7.43 11111101）을톨루엔（50 ）에녹인후, 100ᄋ（：에서 15시간교반 하였다.실온으로냉각하고증류수를넣은후분별깔때기에서유기층을분리한 뒤 이를 MgS0 4를이용하여수분을제거한후,감압하여용매를제거했다.
얻어진물질을컬럼크로마토그래피하여 화합물 5（1.4 수율: 49%）를분리 및 정제하였다.
[370] MS: +印 + = 1281
[371]
[372] 제조예 6:화합물 6의제조
[373] 2020/175867 1»（：1^1{2020/002606
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Figure imgf000065_0001
[374]
[375] 상기제조예 5에서화합물쇼11대신쇼12를사용한것을제외하고는,상기 제조예 5과동일한방법을사용하여화합물 6（1.48용，수율: 45%）을제조하였다.
[376] MS: +印 + = 1461
[377]
Figure imgf000065_0002
[38이 단계 7-1:화합물 01의합성
[381] 상기단계 5-8에서화합물쇼9대신쇼13를사용한것을제외하고는,상기단계 5-8과동일한방법을사용하여화합물 011（2.24 §,수율: 52%）을제조하였다.
[382] MS: +印 + = 859
[383]
[384] 단계 7-2:화합물 7의합성
[385] 상기단계 5-9에서화합물 010대신 01를사용한것을제외하고는,상기단계 5-9와동일한방법을사용하여화합물 7（1.68용，수율: 56 %）을제조하였다.
[386] MS: +印 + = 1150
[387]
[388] 제조예 8:화합물 8의제조
[389] 2020/175867 1»(：1/10公020/002606
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Figure imgf000066_0001
[39이 단계 8-1:화합물 02의합성
[391] 상기단계 5-8에서화합물쇼9대신쇼14를사용한것을제외하고는,상기단계 5-8과동일한방법을사용하여화합물 02（2.67용，수율: 61 %）을제조하였다.
[392] MS: +印 + = 875
[393]
[394] 단계 8-2:화합물 7의합성
[395] 상기단계 5-9에서화합물 010대신 02를사용한것을제외하고는,상기단계 5-9와동일한방법을사용하여화합물 8（1.95용，수율: 55 %）을제조하였다.
[396] MS: +印 + = 1166
[397]
Figure imgf000066_0002
[401] 단계 9-1:화합물 03의합성 2020/175867 1»（：1^1{2020/002606
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[402] 상기단계 5-7에서 화합물쇼7대신쇼15를사용한것을제외하고는,상기 단계 5-7와동일한방법을사용하여화합물 03（1.27용，수율: 38 %）을제조하였다.
[403] MS: +印 + = 667
[404]
[405] 단계 9-2:화합물 04의합성
[406] 상기단계 9-1에서 제조한화합물 03（3.34 5 11111101）을사6（20011止）에 넣고 교반하면서 0ᄋ（:로냉각한다음,메탄술폰산（1.2 ， 20 11111101）을 10분간첨가하고 80도로승온하였다. 12시간교반한다음실온으로냉각후
나트륨바이카보네이트수용액을첨가하고 30분간교반하였다.이후,분별 깔때기에서유기층을분리한뒤 이를 MgS0 4를이용하여수분을제거한후, 감압하여용매를제거하였다.이로부터 얻어진물질을컬럼크로마토그래피하여 화합물 014（ 1.32 ，수율: 59%）을분리 및정제하였다.
[407] MS: +印 + = 745
[408]
[409] 단계 9-3:화합물 9의합성
[41이 상기단계 5-9에서 화합물 010대신 04를사용한것을제외하고는,상기단계 5-9와동일한방법을사용하여화합물 9（1.13용，수율: 62 %）를제조하였다.
[411] MS: +印 + = 1046
[412]
[413] 실험예 1:용해도실험
[414] 상기제조예에서 제조한화합물 1내지 6및하기화합물 61）를각각톨루엔에 용해시켜상온/상압에서의톨루엔에 대한용해도를측정하였고,그결과를표 1에 나타내었다.
[415] [화합물 BD]
[416]
Figure imgf000067_0001
[417]
[418] 2020/175867 1»（：1^1{2020/002606
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[표 1]
Figure imgf000068_0001
[419]
[42이 상기표 1에나타난바와같이，본발명의상기 화학식 1로표시되는플루오렌 코어의치환기가비대칭인화합물은,상기화합물 81）에 비하여톨루엔에 대한 용해도가현저히높음을알수있다.
[421]
[422] 실시예 1:유기발광소자의제조
[423] 미 · 1111（« 句가 500요의두께로박막증착된유리 기판을세제를녹인 증류수에 넣고초음파로세척하였다.이때,세제로는피셔사（1¾11 （：0.）제품을 사용하였으며,증류수로는밀리포어사（Millipore（¾.）제품의 필터로 2차로 걸러진증류수를사용하였다.상기 111）를 30분간세척한후,증류수로 2회 반복하여초음파세척을 분간진행하였다.증류수세척이끝난후,아세톤, 증류수,이소프로필알콜용제로초음파세척을하고건조하여,세정된 500入 두께의 111）유리기판을준비하였다.
[424]
[425] 상기 110투명 전극위에하기화합물 1과하기 화합물 2를 8:2의중량비로 혼합하여톨루엔에 2%의중량비로녹인조성물을스핀코팅하고질소분위기 하에 핫플레이트에서 220°0및 30분조건으로경화시켜 400人두께의 정공주입층을형성하였다.상기정공주입층위에 ,하기화합물 3을톨루엔에 1%의중량비로녹인조성물을스핀코팅하고핫플레이트에서 200ᄋ（:, 30분 조건에서 열처리하여 200入두께의 정공수송층을형성하였다.
[426] 상기정공수송층위에하기 화합물 4과상기제조예 1에서제조한화합물 1을 94:6의중량비로녹인 2 \ %톨루엔용액을제조하여 5000伴111으로스핀 코팅하고, 80ᄋ（：에서 2분베이킹 053닌1¾）하고, 120ᄋ（：에서 30분베이킹 053닌1¾）하여 2020/175867 1»（：1^1{2020/002606
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550요두께의 발광층을형성하였다.
[427] 이것을질소분위기하에 130ᄋ（：에서 분간건조시킨후,상기 발광층상에 리튬플로라이드山田）를 요두께로증착하여 전자수송및주입층을형성하고, 마지막으로알루미늄을 00요두께로증착하여음극을형성하였다.
[428]
Figure imgf000069_0001
Figure imgf000069_0002
[429]
[43이 상기과정에서 리튬플로라이드는 0.3入 ,알루미늄은 2人 의증착속도를 유지하였으며,증착시 진공도는 2x10 7 5x10 6 10]1·를유지하여,유기 발광 소자를제작하였다.
[431]
[432] 실시예 2내지 9및비교예 1
[433] 화합물 1대신하기표 2에 기재된화합물을사용한것을제외하고는,실시예 2020/175867 1»（：1^1{2020/002606
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1과동일한방법으로유기발광소자를제조하였다.
Figure imgf000070_0002
Figure imgf000070_0001
[437]
[438] 실험예 2:유기발광소자특성평가 2020/175867 1»(：1^1{2020/002606
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[439] 상기실시예 1내지 9및비교예 1에서제조한유기발광소자에전류를
인가하였을때, 10 111쇼/011 2의전류밀도에서의구동전압,전류효율,발광효율, 양자효율및수명을측정한결과를하기표 2에나타내었다.이때,수명 90）은 휘도가초기휘도（1000 1止）에서 90%로감소되는데소요되는시간을의미한다.
[440]
[441] [표 2]
Figure imgf000071_0001
[442]
[443] 상기표 2에나타난바와같이，본발명의화합물을발광층의도펀트로사용한 유기발광소자는,비교예화합물 61）를발광층의도펀트로사용한유기발광 소자에비하여,구동전압,효율및수명측면모두에서매우우수한특성을 나타냄을알수있다.이는일반적으로유기발광소자의발광효율및수명 특성은서로트레이드-오프（1¾（1 （났0관계를갖는점을고려할때본발명의 화합물을발광층의도펀트로채용한유기발광소자가비교예소자대비현저히 향상된소자특성을나타냄을의미한다.
[444]
[445] [부호의설명]
[446] 1:기판 2:양극
[447] 3:발광층 4:음극
[448] 5:정공주입층 6:정공수송층
[449] 7:발광층 8:전자수송층
[45이 9:전자주입층

Claims

2020/175867 1»（：1/10公020/002606
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[청구항 1] 하기화학식 1로표시되는화합물:
[화학식 1]
Figure imgf000072_0001
상기화학식 1에서,
IIᅳ및 II 2는각각독립적으로,수소이거나,또는 II !또는 II 2끼리서로 결합하여치환또는비치환된 0 6_60방향족고리 ;치환또는비치환된 0 6_60 비방향족고리 ;또는치환또는비치환된 0, 3및 로구성되는 군으로부터선택되는어느하나이상의헤테로원자를포함하는 0 2_60 헤테로고리를형성하되 ,
II I및 II 2중적어도하나는 II 1또는 II 2끼리서로결합하여 ,상기 0 6-60 비방향족고리 ;또는상기 0 2_60헤테로고리를형성하고, 은치환또는비치환된（： 6-6。아릴렌;또는치환또는비치환된 0및 3로구성되는군으로부터선택되는어느하나이상의헤테로원자를 포함하는 0 2-60헤테로아릴렌이고,
는 0, NZ 3,또는 4å 5이고,
å 1내지 å 5는각각독립적으로,치환또는비치환된 0 !_60알킬 ;치환또는 비치환된 0 !_60할로알킬 ;치환또는비치환된 0 3-60사이클로알킬 ;치환 또는비치환된｛： 7-6。아랄킬;치환또는비치환된（： 6-6。아릴;또는치환 또는비치환된 0및 3로구성되는군으로부터선택되는어느하나 이상의헤테로원자를포함하는 0 2-60헤테로아릴이고,
상기 1^및2 2; 2 2및2 3;
Figure imgf000072_0002
연결되어 5원-헤테로 고리를형성할수있고,
1및 2는각각독립적으로,단일결합;치환또는비치환된 0 6-60아릴렌; 또는치환또는비치환된 0및 3로구성되는군으로부터선택되는 어느하나이상의헤테로원자를포함하는 0 2-60헤테로아릴렌이고, 사 1내지사 4는각각독립적으로,치환또는비치환된 0 6-60아릴 ;또는 치환또는비치환된 0및 3로구성되는군으로부터선택되는어느 하나이상의헤테로원자를포함하는 0 2-60헤테로아릴이다.
[청구항 2] 제 1항에 있어서,
Figure imgf000072_0003
및요2중적어도하나는 또는 11 2끼리서로결합하여하기화학식 2020/175867 1»（：1/10公020/002606
72
2(1내지 2은로표시되는구조중어느하나를형성하고,나머지는 수소이거나,또는서로결합하여하기화학식
Figure imgf000073_0001
중어느하나를형성하는,
화합물:
Figure imgf000073_0003
상기화학식 2&내지 2은에서 ,
는 0, 0å 6å 7,또는 8å 9이고,
å 6내지 9는각각독립적으로, 0 ,_10알킬,또는 0 6-20아릴이고,
*는 II 또는 II 2와결합된탄소와의결합위치를의미한다.
3] 제 2항에 있어서,
상기 화학식 1로표시되는화합물은하기화학식 1-1내지 1-5중어 하나로표시되는,
화합물:
[화학식 1-1]
Figure imgf000073_0002
[화학식 1-2] 2020/175867 1»（：1^1{2020/002606
73
Figure imgf000074_0001
[화학식 1-5] \¥0 2020/175867 1»（：1^1{2020/002606
74
4
2
상기화학식 1-1내지 1-5에서,
15 2및사 1내지사 4는제 1항에서정의한바와같고, 하나는단일결합이고,나머지하나는 0, 0（0 "알킬） 2, 알킬） 2이며 ,
하나는단일결합이고,나머지하나는 0, 0（0 "알킬） 2,
Figure imgf000075_0001
알킬） 2이다.
[청구항 4] 제 1항에 있어서久,
은페닐또는비페닐릴이고,
여기서 , å 비치환되거나,또는중수소,할로겐,시아노, 0 !_10알킬, 0 3-10 사이클로알킬, 81（0 !-10알킬） 3및 81（0 6-20아릴） 3로구성되는군으로부터 각각 /3、독립적으로선택되는 1개내지 5개의치환기로치환되는, 화합물.
[청구항 5] 제 1항에 있어서,
은하기로구성되는군으로부터선택되는어느하나인, 화합물:
Figure imgf000075_0002
\¥0 2020/175867
75
[청구항 6] 제 1항에 있어서,
1시å 2는하기로구성되는군으로부터선택되는어느하나인, 화합물:
Figure imgf000076_0001
상기에서,
II, II’및 II”는각각독립적으로,수소,메틸, 부틸,또는 （메틸） 3이다. [청구항 7] 제 1항에 있어서,
및 는단일결합인,
화합물.
[청구항 8] 제 1항에 있어서 ,
쇼 내지사4는각각독립적으로,페닐,나프틸,비페닐릴,또는
디벤조퓨라닐이고, 2020/175867 1»（：1^1{2020/002606
76 여기서 ,사 1내지사 4는비치환되거나,또는중수소,할로겐, 0 140알킬및 81（0 14。알킬） 3로구성되는군으로부터각각독립적으로선택되는 1개 내지 5개의치환기로치환되는,
화합물.
［청구항 9］ 제 1항에 있어서,
쇼］· 내지사 4는각각독립적으로,하기로구성되는군으로부터선택되는 어느하나인,
화합물:
Figure imgf000077_0001
［청구항 1이 제 1항에 있어서,
사 1및사 4는서로동일하고,
사 2및사 3는서로동일한,
화합물.
［청구항 11］ 제 1항에 있어서,
상기화학식 1로표시되는화합물은하기화학식 2-1내지 2-10중어느 하나로표시되는,
화합물:
2020/175867 1»（：1^1{2020/002606
77
Figure imgf000078_0001
상기화학식 2-1내지 2 0에서,
ᄂ X, å 15 å 2및사 내지사 4는제 1항에서정의한바와같고,
V 5및 V 6는각각독립적으로, 0, （：（메틸） 2,또는 （메틸） 2이다. [청구항 12] 제 1항에있어서,
상기화합물은하기화합물로구성되는군으로부터선택되는어느 하나인,
화합물:
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
WO 2020/175867
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000097_0001
Figure imgf000100_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
() 2020/175867 1 1710公020/002606
106
Figure imgf000107_0001
[청구항 13] 제 1전극;상기제 1전극과대향하여구비된제 2전극;및상기제 1전극과 상기제 2전극사이에구비된발광층을포함하는유기발광소자로서, 상기발광층은제 1항내지제 12항중어느하나의항에따른화합물을 포함하는것인,유기발광소자.
PCT/KR2020/002606 2019-02-28 2020-02-24 신규한 화합물 및 이를 이용한 유기 발광 소자 WO2020175867A1 (ko)

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