WO2015096658A1 - 芳香胺化合物、发光元件材料及发光元件 - Google Patents

芳香胺化合物、发光元件材料及发光元件 Download PDF

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WO2015096658A1
WO2015096658A1 PCT/CN2014/094227 CN2014094227W WO2015096658A1 WO 2015096658 A1 WO2015096658 A1 WO 2015096658A1 CN 2014094227 W CN2014094227 W CN 2014094227W WO 2015096658 A1 WO2015096658 A1 WO 2015096658A1
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group
substituted
light
emitting element
aryl
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PCT/CN2014/094227
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English (en)
French (fr)
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金光男
王鹏
徐芳荣
钟陵智
石垣刚
田中大作
池田武史
西山卓哉
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东丽先端材料研究开发（中国）有限公司
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Priority to KR1020167018779A priority Critical patent/KR102287601B1/ko
Priority to US15/108,126 priority patent/US10700308B2/en
Priority to JP2016542131A priority patent/JP6617706B2/ja
Priority to CN201480070874.2A priority patent/CN105849113B/zh
Priority to EP14875253.8A priority patent/EP3088403B1/en
Publication of WO2015096658A1 publication Critical patent/WO2015096658A1/zh

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Definitions

  • the present invention relates to an aromatic amine compound for an organic light-emitting device, a light-emitting device material containing the aromatic amine compound, and a light-emitting device, and particularly to an aromatic amine compound, a light-emitting device material, and a light-emitting device for an organic light-emitting device having greatly improved light extraction efficiency.
  • the organic light-emitting element is a self-luminous display device, and has characteristics such as light weight, wide viewing angle, low power consumption, and high contrast.
  • the principle of light emission of an organic light-emitting element is that light is generated when holes and electrons injected from an electrode return to a ground state via an excited state by recombination in a light-emitting layer.
  • This light-emitting element has a feature of being thin and capable of high-intensity light emission at a low driving voltage and capable of multi-color light emission by selecting a light-emitting material, and thus has attracted attention.
  • the organic light emitting element may be classified into a bottom emitting organic light emitting element and a top emitting organic light emitting element according to a direction in which light generated by the organic light emitting layer is emitted.
  • the bottom emission organic light-emitting element light is incident on the substrate side, a reflective electrode is formed on the upper portion of the organic light-emitting layer, and a transparent electrode is formed on the lower portion of the organic light-emitting layer.
  • the organic light emitting element is an active matrix element, a thin film is formed The portion of the transistor is opaque, so the light-emitting area is reduced.
  • the transparent electrode is formed on the upper portion of the organic light-emitting layer, and the reflective electrode is formed on the lower portion of the organic light-emitting layer, so that the light is directed in a direction opposite to the substrate side, whereby the light is transmitted.
  • the area is increased and the brightness is increased.
  • an organic coating layer is formed on the upper translucent metal electrode that transmits light of the light-emitting layer, thereby adjusting the optical interference distance and suppressing the external interference.
  • Light reflection and extinction caused by surface plasmon energy movement see Patent Documents 1 to 5).
  • Patent Document 2 discloses that a refractive index of 1.7 or more is formed on an upper translucent metal electrode of a top emission organic light-emitting element.
  • the organic coating layer increases the luminous efficiency of the red and green light-emitting organic light-emitting elements by about 1.5 times.
  • the material of the organic coating layer used is an amine derivative, a quinolol complex or the like.
  • Patent Document 4 discloses that a material having an energy gap of less than 3.2 eV affects a blue wavelength and is not suitable for use in an organic coating layer, and an organic coating material used is an amine derivative having a specific chemical structure or the like.
  • Patent Document 5 discloses that, in order to realize a blue light-emitting element having a low CIEy value, the refractive index change amount of the organic cover layer material at a wavelength of 430 nm to 460 nm is ⁇ n>0.08, and the organic overcoat material used is a germanium derivative having a specific chemical structure. Things and so on.
  • Patent Document 1 WO2001/039554
  • Patent Document 2 JP2006-156390
  • Patent Document 3 JP2007-103303
  • Patent Document 4 JP2006-302878
  • Patent Document 5 WO2011/043083.
  • an amine derivative having a specific structure having a high refractive index or a material satisfying a specific parameter is used as an organic coating material to improve light extraction efficiency and color purity, but the luminous efficiency has not been solved yet. And the problem of color purity, especially in the case of preparing blue light-emitting elements.
  • the present invention provides an aromatic amine compound for improving light extraction efficiency and color purity of an organic light-emitting device, an organic light-emitting device material containing the aromatic amine compound, an organic light-emitting device cover layer material, and an organic light-emitting device.
  • the aromatic amine compound provided by the present invention has a thiophene structure, a furan structure or a pyrrole structure, it has excellent film stability and a high refractive index, and can solve the problem of improving light extraction efficiency and improving color purity.
  • the aromatic amine compound is specifically represented by the following formula (1).
  • X is selected from a sulfur atom, an oxygen atom, or N-R,
  • R may be selected from the group consisting of hydrogen, deuterium, an alkyl group which may be substituted, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl ether group, and an aromatic group.
  • L 1 and L 2 may be the same or different and are respectively selected from an arylene group or a heteroarylene group;
  • Ar 1 and Ar 2 may be the same or different and are respectively selected from an aryl group or a heteroaryl group;
  • Ar 3 and Ar 4 may be the same or different heteroaryl groups
  • R 1 to R 2 may be the same or different and may be independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl group which may be substituted, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group.
  • alkylthio group an alkylthio group, an aryl ether group, an aryl sulfide group, an aryl group, a heteroaryl group, a cyano group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an alkylamino group or a silane group. It is also possible to bond with adjacent substituents to form a ring.
  • L 1 and L 2 are an arylene group.
  • the present invention also provides an organic light-emitting device material comprising a compound represented by the following formula (1).
  • X is selected from a sulfur atom, an oxygen atom, or N-R,
  • R may be selected from the group consisting of hydrogen, deuterium, alkyl group which may be substituted, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, aryl ether group, aryl group One or more of a thioether group, an aryl group, a heteroaryl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an alkylamino group or a silane group;
  • L 1 and L 2 may be the same or different and are respectively selected from an arylene group or a heteroarylene group;
  • Ar 1 and Ar 2 may be the same or different and are respectively selected from an aryl group or a heteroaryl group;
  • Ar 3 and Ar 4 may be the same or different heteroaryl groups
  • R 1 to R 2 may be the same or different and may be independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl group which may be substituted, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group.
  • alkylthio group an aryl ether group, an aryl sulfide group, an aryl group, a heteroaryl group, a cyano group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an alkylamino group or a silane group. It is also possible to bond with adjacent substituents to form a ring. From the standpoint of the simplicity of the synthesis and the cost, it is preferred that L 1 and L 2 are an arylene group.
  • the present invention provides an organic light-emitting element comprising a substrate, a first electrode, one or more organic layer films including a light-emitting layer, and a second electrode element, wherein the light-emitting element further has a cover layer; An organic material containing the above organic light emitting device material.
  • the present invention further provides an organic light-emitting device cover layer material comprising a compound represented by the following formula (1).
  • X is selected from a sulfur atom, an oxygen atom, or N-R,
  • R may be selected from the group consisting of hydrogen, deuterium, an alkyl group which may be substituted, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl ether group, and an aromatic group.
  • L 1 and L 2 may be the same or different and are respectively selected from an arylene group or a heteroarylene group;
  • Ar 1 and Ar 2 may be the same or different and are respectively selected from an aryl group or a heteroaryl group;
  • Ar 3 and Ar 4 may be the same or different heteroaryl groups
  • R 1 to R 2 may be the same or different and may be independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl group which may be substituted, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group.
  • alkylthio group an alkylthio group, an aryl ether group, an aryl sulfide group, an aryl group, a heteroaryl group, a cyano group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an alkylamino group or a silane group. It is also possible to bond with adjacent substituents to form a ring.
  • L 1 and L 2 are an arylene group.
  • the invention finally provides an organic light-emitting element comprising a substrate, a first electrode, a layer of an organic layer film including a light-emitting layer, and a second electrode element, the light-emitting element further having a cover layer;
  • the organic light emitting device contains the above organic light emitting device cover layer material. Since the aromatic amine compound provided by the present invention has a thiophene structure, a furan structure or a pyrrole structure, it has excellent film stability and a high refractive index, and can solve the problem of improving light extraction efficiency and improving color purity.
  • the cover layer material represented by the above formula (1) has a thiophene structure, a furan structure or a pyrrole structure, so has a high glass transition temperature and a steric hindrance effect, thereby having superior film stability, and a thiophene structure, a furan structure or a pyrrole structure.
  • the structure can increase the absorption coefficient and obtain a higher attenuation coefficient, so that the film can obtain a higher refractive index in the ultraviolet/visible range.
  • Further heteroaryl groups have the property of increasing the polarizability, thereby further increasing the refractive index.
  • Ar 3 and Ar 4 are preferably miscellaneous.
  • Ar 3 and Ar 4 have an electron-withdrawing nitrogen atom, that is, a nitrogen atom in the heteroaryl group is bonded to an adjacent atom by a double bond, and the red shift of the absorption wavelength can be suppressed while the refractive index becomes high.
  • Ar 3 and Ar 4 are a pyridyl group, a quinolyl group, a pyrimidinyl group or a quinazolinylquinoxaline group, and a pyridyl group, a quinolyl group or a pyrimidinyl group is still more preferred.
  • the cover layer material used an aromatic amine compound having a high refractive index, thereby obtaining an organic light-emitting element which greatly improved the light-emitting extraction efficiency and had superior color purity.
  • the above alkyl group is preferably a C1-C20 alkyl group; further preferably one of a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group or a t-butyl group; A variety.
  • the above alkyl group may have a substituent or may have no substituent.
  • the above cycloalkyl group is preferably a C3-C20 cycloalkyl group; more preferably one or more of a cyclopropyl group, a cyclohexyl group, a norbornyl group, or a saturated alicyclic hydrocarbon group such as an adamantyl group.
  • the above cycloalkyl group may have a substituent or may have no substituent.
  • the heterocyclic group is preferably a C2-C20 heterocyclic group; more preferably one or more of an aliphatic ring having an atom other than carbon in a ring such as a pyran ring, a piperidine ring or a cyclic amide.
  • the above heterocyclic group may have a substituent or may have no substituent.
  • the above alkenyl group is preferably a C2-C20 alkenyl group; more preferably one or more of an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group or a butadienyl group.
  • the above alkenyl group may have a substituent or may have no substituent.
  • the above cycloalkenyl group is preferably a C3-C20 cycloalkenyl group; more preferably one or more of an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group; kind.
  • the above cycloalkenyl group may have a substituent or may have no substituent.
  • the alkynyl group is preferably a C2-C20 alkynyl group; more preferably an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group.
  • the above alkynyl group may have a substituent or may have no substituent.
  • the alkoxy group is preferably a C1-C20 alkoxy group; more preferably one or more of a functional group such as a methoxy group, an ethoxy group or a propoxy group bonded to an aliphatic hydrocarbon group via an ether bond.
  • the aliphatic hydrocarbon group may have a substituent or may have no substituent.
  • the above alkylthio group is a group in which an oxygen atom of an alkoxy group is substituted with a sulfur atom. It is preferably a C1-C20 alkylthio group; the alkylthioalkyl group may have a substituent or may have no substituent.
  • the above aryl group is preferably an C6-C60 aryl group; more preferably one or more of an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a benzene terphenyl group or a fluorenyl group.
  • the aryl group may have a substituent or may have no substituent.
  • the above heteroaryl group is preferably a C4-C60 aromatic heterocyclic group; further preferably a furyl group, a thienyl group, a pyrrole group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a pyridine One or more of a group or a quinolinyl group or the like.
  • the aromatic heterocyclic group may have a substituent or may not be taken Daiji.
  • the aryl ether group is preferably a C6-C40 aryl ether group; more preferably a functional group such as a phenoxy group bonded to an aromatic hydrocarbon group via an ether bond.
  • the aryl ether group may or may not have a substituent.
  • the above aryl sulfide group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom.
  • Preferred is a C6-C60 aryl sulfide group.
  • the aromatic hydrocarbon group in the aryl sulfide group may or may not have a substituent.
  • the above halogen atom is selected from fluorine, chlorine, bromine or iodine.
  • the above carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group or alkylamino group may have a substituent or may have no substituent.
  • the number of carbon atoms of the alkylamino substituent is not particularly limited, and is usually in the range of 2 or more and 60 or less.
  • the above silane group is represented by a functional group having a bond to a silicon atom such as a trimethylsilyl group, a triethylsilyl group, a dimethyl tert-butylsilane group or a triphenylsilyl group, and the silane group may have a substituent. It is also possible to have no substituents.
  • the number of carbon atoms of the silane group is not particularly limited, and is usually in the range of 1 or more and 40 or less.
  • the above substituent is selected from the group consisting of hydrazine, halogen, C1-C15 alkyl, C3-C15 cycloalkyl, C3-C15 heterocyclic, C2-C15 alkenyl, C4-C15 cycloalkenyl, C2 - alkynyl group of C15, alkoxy group of C1-C55, alkyl fluorenyl group of C1-C55, aryl ether group of C6-C55, aryl sulfide group of C6-C55, aryl group of C6-C55, C4-C55
  • the aromatic amine compound is not particularly limited, and the following examples are preferred.
  • the synthesis of the aromatic amine compound represented by the above formula (1) can be carried out by a known method.
  • a cross-coupling reaction of a transition metal such as nickel or palladium is used.
  • M is MgBr or the like.
  • the coupling reaction, the Suzuki-Miyaura coupling reaction represented by B(OH)2, etc. is not limited to these methods.
  • Hal is a pseudohalogen such as a halogen atom such as a chlorine atom, a bromine atom or an iodine atom or a trifluoromethanesulfonate group.
  • a pseudohalogen such as a halogen atom such as a chlorine atom, a bromine atom or an iodine atom or a trifluoromethanesulfonate group.
  • the Suzuki-Miyaura coupling reaction is preferred because the raw material is a metal compound having low toxicity, few by-products of the reaction, and easy removal of the unreacted main group metal compound.
  • CN bond formation reaction of a transition metal such as nickel, palladium or copper.
  • a Buchwald-Hartwig reaction using nickel or palladium a Ullman reaction using copper, but not limited to these methods.
  • the above reaction, mild reaction conditions, and superior selectivity of various functional groups are preferred, and a Buchwald-Hartwig reaction is preferred.
  • Ar 1 , Ar 2 or Ar 3 and Ar 4 are synthesized as different substituents, they are synthesized in stages according to the theoretical mixing ratio of the amine and the halide.
  • the aromatic amine compound of the formula (1) in the present invention may be used singly or in combination with other materials in the organic light-emitting device.
  • the present invention is an organic light-emitting device containing an aromatic amine compound, which has a substrate, a first electrode, one or more organic layer films including a light-emitting layer, and a light transmitting the light emitted from the light-emitting layer.
  • the two electrodes and the light extraction efficiency improving layer, the light emitting layer emits light by electric energy.
  • the substrate to be used is preferably a glass substrate such as soda glass or alkali-free glass.
  • the thickness of the glass substrate is not particularly limited as long as it is sufficient to maintain mechanical strength. Therefore, 0.5 mm or more is sufficient.
  • the material of the glass is preferably as small as possible because the amount of ions eluted from the glass is as small as possible.
  • commercially available protective coatings such as SiO 2 may also be used.
  • the substrate does not have to be glass, and for example, an anode may be formed on the plastic substrate.
  • the material used in the first electrode is preferably a metal such as gold, silver or aluminum having a high refractive index property or a metal alloy such as an APC alloy. These metals or metal alloys may also be laminated in multiple layers. Further, a transparent conductive metal oxide such as tin oxide, indium oxide, indium tin oxide (ITO) or indium zinc oxide (IZO) may be laminated on the upper surface and/or the lower surface of the metal, the metal alloy or the laminate thereof.
  • a transparent conductive metal oxide such as tin oxide, indium oxide, indium tin oxide (ITO) or indium zinc oxide (IZO) may be laminated on the upper surface and/or the lower surface of the metal, the metal alloy or the laminate thereof.
  • the material used in the second electrode is preferably a material that forms a translucent or transparent film that transmits light.
  • a material that forms a translucent or transparent film that transmits light For example, silver, magnesium, aluminum, calcium or an alloy of these metals, a transparent conductive metal oxide such as tin oxide, indium oxide, indium tin oxide (ITO) or indium zinc oxide (IZO). These metals, alloys, or metal oxides may also be laminated in multiple layers.
  • the method for forming the above electrode may be, for example, resistance heating deposition, electron beam evaporation, sputtering, ion plating, or gel coating, and the like, and is not particularly limited. Further, the first electrode and the second electrode function as an anode with respect to the organic film layer and the other as a cathode depending on the work function of the material used.
  • the organic layer may be composed of only a light-emitting layer, a hole transport layer/light-emitting layer, 2) a light-emitting layer/electron transport layer, and 3) a hole transport layer/light-emitting layer/electron transport layer, 4)
  • the hole injection layer/hole transport layer/light emitting layer/electron transport layer, and 5) a structure in which a hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer or the like is laminated.
  • each of the above layers may be either a single layer or a plurality of layers.
  • the hole transport layer can be formed by a method of laminating or mixing one or more kinds of hole transport materials, or by a method using a mixture of a hole transport material and a polymer binder.
  • the hole transporting material needs to efficiently transport holes from the positive electrode between the electrodes to which the electric field is applied. Therefore, it is desirable that the hole injection efficiency is high and the injected holes can be efficiently transported. Therefore, the hole transporting material is required to have an appropriate ion potential, and has a large hole mobility, and further, is excellent in stability, and is unlikely to cause impurities which may become traps during production and use.
  • the substance satisfying such conditions is not particularly limited, and may be, for example, 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl (TPD), 4,4'- Bis(N-(1-naphthyl)-N-phenylamino)biphenyl (NPD), 4,4'-bis(N,N-bis(4-biphenylyl)amino)biphenyl (TBDB), Biphenylamine such as bis(N,N-diphenyl-4-phenylamino)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl (TPD232), 4, 4 ',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine (m-MTDATA), 4,4',4"-tris(1-naphthyl(phenyl)amino)triphenylamine ( 1-TNATA)
  • a heterocyclic compound such as an oxadiazole derivative, a phthalocyanine derivative or a porphyrin derivative, or a fullerene derivative
  • a polycarbonic acid having the above monomer in a side chain is also preferable.
  • styrene derivatives, polythiophene, polyaniline, polyfluorene, polyvinylcarbazole and polysilane is also preferable.
  • an inorganic compound such as P-type Si or P-type SiC can also be used.
  • a hole injecting layer may be provided between the anode and the hole transporting layer.
  • the organic light-emitting element can achieve a low driving voltage and improve the durability life.
  • a hole injection layer is usually preferably used A material having a lower ion potential than the material of the hole transport layer. Specifically, for example, a benzidine derivative or a star-type triarylamine material group such as the above TPD232 may be used, and a phthalocyanine derivative or the like may also be used. Further, it is also preferred that the hole injection layer is composed of an acceptor compound alone or that the acceptor compound is doped in another hole transport layer.
  • the acceptor compound examples include metal chlorides such as iron trichloride (III), aluminum chloride, gallium chloride, indium chloride, and cesium chloride, and metal oxides such as molybdenum oxide, vanadium oxide, tungsten oxide, and cerium oxide. , a charge transfer ligand such as tris(4-bromophenyl)hexachloroantimonate (TBPAH). Further, it may be an organic compound having a nitro group, a cyano group, a halogen or a trifluoromethyl group in the molecule, an anthraquinone compound, an acid anhydride compound, a fullerene or the like.
  • metal chlorides such as iron trichloride (III), aluminum chloride, gallium chloride, indium chloride, and cesium chloride
  • metal oxides such as molybdenum oxide, vanadium oxide, tungsten oxide, and cerium oxide.
  • a charge transfer ligand such as tris(4-brom
  • the light-emitting layer may be any one of a single layer and a plurality of layers, and may be formed of a light-emitting material (host material, dopant material), which may be a mixture of the host material and the dopant material, or may be only
  • the main material can be used in either case. That is, in each of the light-emitting layers of the light-emitting element of the present invention, only the host material or only the dopant material may emit light, or the host material and the dopant material may emit light together. From the viewpoint of efficiently utilizing electric energy and obtaining light of high color purity, it is preferable that the light-emitting layer is formed by mixing a host material and a dopant material.
  • the host material and the dopant material may be one type or a combination of a plurality of types, and any of them may be used.
  • the doping material may be added to the entire host material or may be added to a portion, either in any case.
  • the doping material may be either laminated or dispersed, either in any case.
  • the doping material can control the luminescent color.
  • the amount of the dopant material is too large, the concentration extinction phenomenon occurs. Therefore, the amount thereof is preferably 20% by weight or less, and more preferably 10% by weight or less based on the host material.
  • the doping method may be a method of co-evaporation with a host material, or a method of simultaneously vapor-depositing after mixing with a host material.
  • the luminescent material examples include a fused ring derivative such as ruthenium or osmium which is conventionally known as an illuminant, a metal chelating quinolin compound such as tris(8-hydroxyquinoline)aluminum, or dibenzofuran.
  • a fused ring derivative such as ruthenium or osmium which is conventionally known as an illuminant
  • a metal chelating quinolin compound such as tris(8-hydroxyquinoline)aluminum
  • dibenzofuran dibenzofuran.
  • the derivative, the carbazole derivative, the indolocarbazole derivative, the polyphenylenevinylene derivative, the polyparaphenylene derivative, and the polythiophene derivative in the polymer are not particularly limited.
  • the host material contained in the luminescent material is not particularly limited, and ruthenium, phenanthrene, anthracene, benzophenanthrene, tetracene, anthracene, benzo[9,10]phenanthrene, fluoranthene, anthracene, anthracene, etc. may be used.
  • a cyclic compound or a derivative thereof an aromatic amine derivative such as N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine, or the like a metal chelate hydroxyquinoline compound such as (8-hydroxyquinoline)aluminum, a pyrrolopyrrole derivative, a dibenzofuran derivative, a carbazole derivative, an indolocarbazole derivative, a triazine derivative,
  • the polymer may, for example, be a polyphenylene vinylene derivative, a polyparaphenylene derivative, a polyfluorene derivative, a polyvinylcarbazole derivative or a polythiophene derivative, and is not particularly limited.
  • the doping material is not particularly limited, and examples thereof include a compound having a condensed aromatic ring such as naphthalene, anthracene, phenanthrene, anthracene, benzophenanthrene, anthracene, benzo[9,10]phenanthrene, fluoranthene, anthracene or anthracene.
  • a phosphorescent material may be doped in the light-emitting layer.
  • the phosphorescent material is a material that can also be phosphorescent at room temperature.
  • a phosphorescent material is used as the dopant, it is required to be substantially capable of phosphorescence at room temperature, but is not particularly limited, and preferably contains an indium, ruthenium, rhodium, palladium, platinum, rhodium, and An organometallic complex compound of at least one metal of cerium. From the viewpoint of having high phosphorescence luminous efficiency at room temperature, an organometallic complex having indium or platinum is more preferable.
  • an anthracene derivative As a host material used in combination with a phosphorescent dopant, an anthracene derivative, a carbazole derivative, an indolocarbazole derivative, a nitrogen-containing aromatic compound derivative having a pyridine, a pyrimidine or a triazine skeleton,
  • An aromatic hydrocarbon compound derivative such as an arylbenzene derivative, a spiroindole derivative, a trimeric europium, a benzo[9,10]phenanthrene, a dibenzofuran derivative, a dibenzothiophene or the like, an oxygen group-containing compound, and a hydroxyl group.
  • An organic metal complex such as a quinoline ruthenium complex can be suitably used, but basically, as long as the triplet energy of the dopant used is larger and electrons and holes can be smoothly injected or transported from the respective layer transport layers, There is no particular limitation. Further, two or more kinds of triplet light-emitting dopants may be contained, or two or more types of host materials may be contained. In addition, more than one triplet luminescent dopant and one or more fluorescent luminescent dopants may also be included.
  • the electron transport layer is a layer in which electrons are injected from the cathode and electrons are transferred.
  • the electron transport layer preferably has high electron injection efficiency and can efficiently transport the injected electrons. Therefore, the electron transport layer is preferably composed of a substance having a large electron affinity and electron mobility and excellent stability, and which is less likely to cause impurities which are traps during production and use.
  • the electron transport layer mainly functions to efficiently prevent holes from the anode from being combined and flowing to the cathode side, even materials having a lower electron transporting ability are not so high.
  • the effect of improving the luminous efficiency is also equivalent to the case of a material having a high electron transporting ability. Therefore, in the electron transport layer in the present invention, the hole blocking layer which can efficiently prevent hole migration is also included as an equivalent.
  • the electron transporting material used in the electron transporting layer is not particularly limited, and examples thereof include a condensed aromatic ring derivative such as naphthalene or an anthracene, and a styrene-based aromatic group represented by 4,4'-di(diphenylvinyl)biphenyl.
  • a cyclic derivative an anthracene derivative such as hydrazine or biphenyl fluorene, a phosphine oxide derivative, or a tris(8-hydroxyquinoline) aluminum or the like a hydroxyquinoline complex, a benzoquinolinoline complex, a hydroxyazole complex, an azomethine complex, a cycloheptatrienol metal complex or a flavonol metal complex, From the viewpoint of driving voltage and high-efficiency luminescence, it is preferred to use a compound having a heteroaromatic ring structure composed of an element selected from the group consisting of carbon, hydrogen, nitrogen, oxygen, silicon, phosphorus, and containing electron-withdrawing Sexual nitrogen.
  • the heteroaryl ring containing an electron-withdrawing nitrogen has high electrophilicity.
  • An electron transporting material having electron-withdrawing nitrogen readily accepts electrons from a cathode having high electrophilicity, so that the driving voltage of the light-emitting element can be lowered. Further, since the electron supply to the light-emitting layer is increased and the probability of recombination in the light-emitting layer is increased, the light-emitting efficiency is improved.
  • heteroaryl ring containing an electron-withdrawing nitrogen examples include a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring, a naphthyridine ring, a pyrimidopyrimidine ring, a benzoquinoline ring, and a phenanthrene ring.
  • a porphyrin ring an imidazole ring, an oxazole ring, an oxadiazole ring, a triazole ring, a thiazole ring, a thiadiazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, or a phenamimidazole ring, etc. .
  • examples of the compound having such a heteroaromatic ring structure include a benzimidazole derivative, a benzoxazole derivative, a benzothiazole derivative, an oxadiazole derivative, a thiadiazole derivative, and a triazole derivative.
  • An oligopyridine derivative such as a pyrazine derivative, a phenanthroline derivative, a quinoxaline derivative, a quinoline derivative, a benzoquinoline derivative, a bipyridine or a terpyridine.
  • the fused aromatic ring skeleton is preferably an anthracene skeleton, an anthracene skeleton or a phenanthroline skeleton.
  • the above electron transporting material may be used singly or in combination of two or more kinds of the above electron transporting materials, or one or more other electron transporting materials may be mixed and used in the above electron transporting material.
  • a donor compound can also be added.
  • the donor compound refers to the improvement of electrons.
  • the donor compound of the present invention include an alkali metal, an alkali metal-containing inorganic salt, an alkali metal-organic complex, an alkaline earth metal, an alkaline earth metal-containing inorganic salt, or an alkaline earth metal and an organic substance.
  • alkali metal or the alkaline earth metal include an alkali metal such as lithium, sodium or barium having a low work function and an effect of improving electron transporting ability, or an alkaline earth metal such as magnesium or calcium.
  • an electron injecting layer may also be provided between the cathode and the electron transporting layer.
  • the electron injecting layer is inserted for the purpose of assisting electron injection from the cathode to the electron transporting layer, and when inserted, a compound having a heteroaromatic ring structure containing electron-withdrawing nitrogen may be used, or a layer containing the above donor compound may be used.
  • an inorganic substance of an insulator or a semiconductor can also be used. By using these materials, it is possible to effectively prevent the short-circuiting of the light-emitting element and to improve the electron injectability, which is preferable.
  • At least one metal compound selected from the group consisting of an alkali metal chalcogenide, an alkaline earth metal chalcogenide, an alkali metal halide, and an alkaline earth metal halide is preferably used. Further, a complex of an organic substance and a metal can also be used favorably.
  • Examples of the method for forming the respective layers constituting the light-emitting element include resistance heating vapor deposition, electron beam evaporation, sputtering, molecular lamination, or coating, and the like, and are not particularly limited, but generally, from the viewpoint of element characteristics It is preferable to use resistance heating vapor deposition or electron beam evaporation.
  • the thickness of the organic layer varies depending on the electric resistance value of the luminescent material, and is not limited, but is preferably 1 to 1000 nm.
  • the film thickness of each of the light-emitting layer, the electron transport layer, and the hole transport layer is preferably 1 nm or more and 200 nm or less, and more preferably 5 nm or more and 100 nm or less.
  • the light extraction efficiency improving layer of the present invention contains the above compound having a thiophene structure, a furan structure or a pyrrole structure.
  • a thiophene structure In order to maximize high luminous efficiency and achieve color reproducibility, it is preferred to have a thiophene structure,
  • the compound having a furan structure or a pyrrole structure is laminated in a thickness of from 20 nm to 120 nm. More preferably, the laminate thickness is from 40 nm to 80 nm. Further, from the viewpoint of maximizing the luminous efficiency, it is more preferable that the light extraction efficiency improving layer has a thickness of 50 nm to 70 nm.
  • the method for forming the light extraction efficiency improving layer is not particularly limited, and examples thereof include resistance heating vapor deposition, electron beam evaporation, sputtering, molecular lamination method, coating method, ink jet method, doctor blade method, and laser transfer method. There are no special restrictions.
  • the light-emitting element of the present invention has a function of converting electric energy into light.
  • the electric energy a direct current is mainly used, and a pulse current or an alternating current can also be used.
  • the current value and the voltage value it should be selected in such a manner that the maximum brightness can be obtained with the lowest possible energy.
  • the light-emitting element of the present invention can be suitably used as a flat display which is displayed in, for example, a matrix and/or a field.
  • the matrix method refers to a two-dimensional arrangement of pixels for display in a checkered or mosaic shape, and displays characters or images by a collection of pixels.
  • the shape and size of the pixel depend on the application. For example, in an image and a character display of a computer, a monitor, and a television, a quadrangular pixel having a side length of 300 ⁇ m or less is generally used, and in the case of a large display such as a display panel, a pixel having a side length of mm is used.
  • monochrome display it is only necessary to arrange pixels of the same color, but in the case of color display, red, green, and blue pixels are arranged to be displayed. In this case, there are typically triangular and striped shapes.
  • the driving method of the matrix may be any one of a line-by-line driving method and an active matrix.
  • the structure of the line-by-line drive is simple, when the operational characteristics are considered, the active matrix may be excellent, and therefore, it is required to be used flexibly depending on the application.
  • the field mode in the present invention refers to forming a pattern and making an area determined by the configuration of the pattern Light, and thus the way in which the predetermined information is displayed.
  • Examples thereof include a digital clock, a time in a thermometer, a temperature display, an operation state display of an audio device, an electromagnetic cooker, and the like, and a panel display of a car.
  • the matrix display and the field display can coexist in the same panel.
  • the light-emitting element of the present invention is preferably used as an illumination light source, and can provide a light source that is thinner and lighter than the prior art and can emit light on the surface.
  • the aromatic amine compound of the present invention is exemplified by the following examples, but is not limited to the aromatic amine compounds exemplified in the examples and the synthesis methods.
  • Dimethylformamide, ethyl acetate, 1,2-xylene, potassium carbonate, dichloromethane, ethanol and sodium carbonate were purchased from Sinopharm; N-methylpyrrole, 2,5-dibromothiophene, etc. were purchased from TCI Corporation; various palladium catalysts, boric acid derivatives and boronic acid ester derivatives were purchased from Aldrich.
  • the 1 H-NMR spectrum was measured using a JEOL (400 MHz) nuclear magnetic resonance apparatus; the HPLC spectrum was measured using a Shimadzu LC-20AD high performance liquid chromatograph.
  • NPD (N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine),
  • TBDB (N, N, N', N'-4(4-biphenyl)biphenyldiamine).
  • 2,5-dibromothiophene 24.2 g (100 mmol), 4-chlorophenylboronic acid 34.4 g (220 mmol), tetrakis(triphenylphosphine)palladium 5.7 g (5.0 mmol), 1.5 M carbonate were added to the reactor under a nitrogen atmosphere.
  • a sodium aqueous solution of 200 ml (300 mmol) and dimethyl ether 100 ml (DME) were stirred and heated at 110 ° C overnight. After cooling to room temperature, filtration, the filtrate was separated into an organic layer and a water layer. The obtained solid was washed with ethanol to give 21.3 g of 2,5-bis(4-chlorophenyl)thiophene.
  • Example 2 The same procedure as in Example 1 was carried out except that N-(4-biphenylyl)-3-pyridylamine was used instead of N-phenyl-3-pyridylamine. 1.1 g of compound [5] (light yellow solid) were obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that N-(4-biphenylyl)-3-pyridylamine was used instead of N-phenyl-4-pyridylamine. 2.2 g of compound [6] (light yellow solid) were obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that N-(3-biphenylyl)-3-pyridylamine was used instead of N-phenyl-3-pyridylamine. 1.5 g of compound [8] (light yellow solid) were obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that N-(3-biphenylyl)-3-pyridylamine was used instead of N-naphthyl-3-pyridylamine. 2.5 g of compound [31] (light yellow solid) were obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that N-(3-biphenylyl)-3-pyridylamine was used instead of N-biphenyl-3-pyridylamine. 3.2 g of compound [32] (light yellow solid) were obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that N-phenyl-3-pyridylamine was used instead of N-3-(3'-methylbiphenyl)-4-pyridylamine. 3.6 g of compound [134] (light yellow solid) were obtained.
  • the alkali-free glass substrate (Asahi Glass Co., Ltd., AN100) was subjected to UV ozone washing treatment for 20 minutes, and further installed in a vacuum vapor deposition apparatus to perform evacuation until the degree of vacuum in the apparatus was higher than 1 ⁇ 10 -3 Pa. Under the conditions, the compound [2] was vapor-deposited by a resistance heating vapor deposition method to prepare a film of about 50 nm. The vapor deposition rate was 0.1 nm/s.
  • the refractive index and attenuation coefficient of the film samples prepared above were determined at Toray Research Center (Inc.), and the instrument used was an ellipsometry (J.A. Woollam M-2000).
  • optical constant (refractive index: n, attenuation coefficient: k) is the decimal point 3 digits rounded off
  • Example 9 The same as Example 9 except that the compound [5] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [6] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [8] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same procedure as in Example 9 was carried out except that the compound [11] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [12] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [14] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [15] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [18] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [21] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [140] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [142] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same as Example 9 except that the compound [144] was used instead of the compound [2].
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • the organic light-emitting element was evaluated. The evaluation results are shown in Table 2.
  • Example 9 The same experiment as in Example 9 was carried out. As shown in Table 2, the results of Examples 10 to 24 are as follows.
  • Examples 9-24 have a higher refractive index than Comparative Example 1. Further, the performance of the light-emitting element was tested.
  • the compound [5] (60 nm) was evaporated as a coating layer.
  • the sealing member made of an alkali-free glass was sealed with an epoxy resin adhesive.
  • the light-emitting element was subjected to a direct current of 10 mA/cm 2 at room temperature in the atmosphere, and the light-emitting characteristics were measured from a light-emitting luminescence meter (CS1000, Konica Minolta Co., Ltd.) for light-emitting of the sealing plate.
  • a high-performance light-emitting element having high luminous efficiency and high color purity was obtained.
  • Example 25 The same elements as in Example 25 were evaluated except that the cover layer material was the compound [6], and the evaluation results are shown in Table 3.
  • Example 25 The same elements as in Example 25 were evaluated except that the cover layer material was the compound [8], and the evaluation results are shown in Table 3.
  • Example 25 The same components as in Example 25 were evaluated except that the cover layer material was NPD, and the evaluation results are shown in Table 3.
  • Example 25 The same components as in Example 25 were evaluated except that the cover layer material was TBDB, and the evaluation results are shown in Table 3.
  • Examples 28 to 39, and Comparative Examples 4 to 6 were evaluated in the same manner as in Example 25 except that the compounds were shown in Table 3. The evaluation results are shown in Table 3.
  • Comparative Example 4 Comparative Example 4, Comparative Example 5, and Comparative Example 6 were as follows.
  • the light-emitting elements of Examples 25 to 39 satisfy both high luminous efficiency and high color purity. Further, the light-emitting elements of Comparative Examples 2 to 6 were equivalent to the color purity of the examples, but the luminous efficiency was lower than that of the examples, and high luminous efficiency and high color purity could not be simultaneously satisfied.
  • the aromatic amine compound of the present invention is suitable for use in an organic light-emitting device material, and a light-emitting element which satisfies both high light-emitting efficiency and high color purity is obtained, and is more suitable for a cover layer material.

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Abstract

本发明提供一种用于改善有机发光元件的光取出效率以及色纯度的如通式(1)所示的芳香胺化合物、含有该芳香胺化合物的有机发光元件材料、有机发光元件覆盖层材料以及有机发光元件。由本发明提供的有机发光元件可实现高发光效率及色再现性，本发明的有机发光元件可用于有机EL显示器、液晶显示器的背光源、照明、计器类等的光源、标示板、标识灯等。大幅度提高发光取出效率而且具有优越色纯度的有机发光元件。

Description

芳香胺化合物、发光元件材料及发光元件 技术领域
本发明涉及有机发光元件用芳香胺化合物、含有该芳香胺化合物的发光元件材料及发光元件，特别是光取出效率得到大幅改善的有机发光元件用芳香胺化合物、发光元件材料及发光元件。
背景技术
有机发光元件是自发光显示装置，具有轻量薄型、广视角、低耗电、高对比等特性。
有机发光元件的发光原理是，在从电极注入的空穴与电子在发光层通过再结合而经由激发态回复到基态时产生光。该发光元件具有薄型且能在低驱动电压下高亮度发光以及能通过选择发光材料而进行多色发光的特征，因此倍受关注。
该研究自从由柯达公司的C.W.Tang等揭示有机薄膜元件能以高亮度发光以来，对于其应用，已有许多研究。有机薄膜发光元件被采用在手机主显示屏等中，其实用化取得切实进展。但是，还存在很多技术课题，其中，元件的高效率化和低耗电是一个很大的课题。
根据有机发光层产生的光所发射的方向，有机发光元件可以分为底发射有机发光元件和顶发射有机发光元件。在底发射有机发光元件中，光射向基板侧，在有机发光层的上部形成有反射电极，在有机发光层的下部形成有透明电极。这种情况下，当有机发光元件为有源矩阵元件时，由于形成有薄膜 晶体管的部分不透光，所以，发光面积减小。另一方面，在顶发射有机元件中，透明电极形成在有机发光层的上部，反射电极形成在有机发光层的下部，所以光射向与基板侧相反的方向，由此，光所透过的面积增加，亮度提高。
现有技术中，为了提高顶发射有机发光元件的发光效率，所采用的方法有在使发光层的光透过的上部半透明金属电极上形成有机覆盖层，以此调节光学干涉距离，抑制外光反射和由表面等离子体能量移动引起的消光等(可参见专利文献1～5)。
例如，专利文献2记载，在顶发射有机发光元件的上部半透明金属电极上形成折射率在1.7以上、膜厚
Figure PCTCN2014094227-appb-000001
的有机覆盖层，使红色发光和绿色发光有机发光元件的发光效率提高了约1.5倍。所用的有机覆盖层的材料是胺衍生物、喹啉醇络合物等。
专利文献4记载，能隙小于3.2eV的材料会影响蓝色波长，不适合用于有机覆盖层，使用的有机覆盖层材料是具有特定化学结构的胺衍生物等。
专利文献5记载，要实现低CIEy值的蓝色发光元件，有机覆盖层材料在波长430nm-460nm的折射率变化量为△n＞0.08，使用的有机覆盖层材料是具有特定化学结构的蒽衍生物等。
专利文献
专利文献1：WO2001/039554
专利文献2：JP2006-156390
专利文献3：JP2007-103303
专利文献4：JP2006-302878
专利文献5：WO2011/043083。
非专利文献
Journal of Applied Physics，96，19(2004)。
Journal of Applied Physics Letters，76，1650(2000)。
发明内容
如上所述，在现有技术中，使用具有高折射率的特定结构的胺衍生物或使用符合特定参数要求的材料作为有机覆盖层材料来改善光取出效率和色纯度，但是尚未解决兼顾发光效率和色纯度的问题，特别是在制备蓝光发光元件的情况下。
本发明提供一种用于提高有机发光元件的光取出效率以及改善色纯度的芳香胺化合物、含有该芳香胺化合物的有机发光元件材料、有机发光元件覆盖层材料以及有机发光元件。
本发明提供的芳香胺化合物因为具有噻吩结构、呋喃结构或吡咯结构，从而具有优越的薄膜稳定性和高折射率，能够解决兼顾提高光取出效率与改善色纯度的问题。
在本发明中，芳香胺化合物具体地如下通式(1)所示。
Figure PCTCN2014094227-appb-000002
其中，X选自硫原子、氧原子、或N-R，
其中，R可以选自氢，氘，可被取代的烷基、环烷基、杂环基、链烯基、环烯基、炔基、烷氧基、烷硫基、芳基醚基、芳基硫醚基、芳基、杂芳基、羰基、羧基、氧羰基、氨基甲酰基、烷氨基或硅烷基中的一种或多种；
L1、L2可以相同或不同，分别选自亚芳基或亚杂芳基；
Ar1、Ar2可以相同或不同，分别选自芳基或杂芳基；
Ar3、Ar4可以为相同或不同的杂芳基；
其中，R1～R2可以相同或不同，分别可以选自氢，氘，卤素，可被取代的烷基、环烷基、杂环基、链烯基、环烯基、炔基、烷氧基、烷硫基、芳基醚基、芳基硫醚基、芳基、杂芳基、氰基、羰基、羧基、氧羰基、氨基甲酰基、烷氨基或硅烷基中的一种或多种，也可以与相邻的取代基键合而形成环。
从合成的简单性和成本角度考虑，优选L1和L2为亚芳基。
本发明还提供一种有机发光元件材料，含有如下通式(1)所示的化合物。
Figure PCTCN2014094227-appb-000003
其中，X选自硫原子、氧原子、或N-R，
其中R可以选自氢，氘，可被取代的烷基、环烷基、杂环基、链烯基、环烯基、炔基、烷氧基、烷硫基、芳基醚基、芳基硫醚基、芳基、杂芳基、羰基、羧基、氧羰基、氨基甲酰基、烷氨基或硅烷基中的一种或多种；
L1、L2可以相同或不同，分别选自亚芳基或亚杂芳基；
Ar1、Ar2可以相同或不同，分别选自芳基或杂芳基；
Ar3、Ar4可以为相同或不同的杂芳基；
其中，R1～R2可以相同或不同，分别可以选自氢，氘，卤素，可被取代的烷基、环烷基、杂环基、链烯基、环烯基、炔基、烷氧基、烷硫基、芳基醚基、芳基硫醚基、芳基、杂芳基、氰基、羰基、羧基、氧羰基、氨基甲酰基、烷氨基或硅烷基中的一种或多种，也可以与相邻的取代基键合而形成环。从 合成的简单性和成本角度考虑，优选L1和L2为亚芳基。
本发明提供一种有机发光元件，其包含基板、第一电极、包括发光层在内的一层以上有机层膜、第二电极元件，所述发光元件还具有覆盖层；所述覆盖层中含有有机材料，该有机发光元件含有上述有机发光元件材料。
本发明另外还提供一种有机发光元件覆盖层材料，含有如下通式(1)所示的化合物。
Figure PCTCN2014094227-appb-000004
其中，X选自硫原子、氧原子、或N-R，
其中，R可以选自氢，氘，可被取代的烷基、环烷基、杂环基、链烯基、环烯基、炔基、烷氧基、烷硫基、芳基醚基、芳基硫醚基、芳基、杂芳基、羰基、羧基、氧羰基、氨基甲酰基、烷氨基或
Figure PCTCN2014094227-appb-000005
硅烷基中的一种或多种；
L1、L2可以相同或不同，分别选自亚芳基或亚杂芳基；
Ar1、Ar2可以相同或不同，分别选自芳基或杂芳基；
Ar3、Ar4可以为相同或不同的杂芳基；
其中，R1～R2可以相同或不同，分别可以选自氢，氘，卤素，可被取代的烷基、环烷基、杂环基、链烯基、环烯基、炔基、烷氧基、烷硫基、芳基醚基、芳基硫醚基、芳基、杂芳基、氰基、羰基、羧基、氧羰基、氨基甲酰基、烷氨基或硅烷基中的一种或多种，也可以与相邻的取代基键合而形成环。
从合成的简单性和成本角度考虑，优选L1和L2为亚芳基。
本发明最后还提供一种有机发光元件，其包含基板、第一电极、包括发光层在内的一层以上有机层膜、第二电极元件，所述发光元件还具有覆盖层； 该有机发光元件含有上述有机发光元件覆盖层材料。本发明提供的芳香胺化合物因为具有噻吩结构、呋喃结构或吡咯结构，从而具有优越的薄膜稳定性和高折射率，能够解决兼顾提高光取出效率与改善色纯度的问题。
上述通式(1)所示覆盖层材料具有噻吩结构、呋喃结构或吡咯结构，所以具有高的玻璃化温度和空间位阻效应，从而具有优越的薄膜稳定性，而且噻吩结构、呋喃结构或吡咯结构，可以提高吸光系数以及得到更高的衰减系数，从而薄膜在紫外·可见光范围内能得到更高的折射率。进一步杂芳基具有提高极化率的性能，从而进一步能提高折射率。另外，因为Ar1～Ar2全部为芳基时，虽然能得到高的折射率，但是由于存在吸收波长红移、造成吸收蓝光导致发光效率变低的可能，所以优选Ar3以及Ar4为杂芳基。优选Ar3以及Ar4具有吸电子的氮原子，即杂芳基中的氮原子以双键与相邻的原子连接，能抑制吸收波长的红移的同时折射率变高。进一步优选Ar3以及Ar4为吡啶基、喹啉基、嘧啶基或喹唑啉基喹喔啉基，更进一步优选吡啶基、喹啉基或嘧啶基。
以上结果得出，覆盖层材料使用具有高折射率的芳香胺化合物，从而得到大幅度提高发光取出效率而且具有优越色纯度的有机发光元件。
上述烷基优选为C1-C20的烷基；进一步优选为甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基等饱和脂肪族烃基中的一种或多种。上述烷基可以具有取代基也可以没有取代基。
上述环烷基优选为C3-C20的环烷基；进一步优选为环丙基、环己基、降冰片基、或金刚烷基等饱和脂环式烃基中的一种或多种。上述环烷基可以具有取代基也可以没有取代基。
上述杂环基优选为C2-C20的杂环基；进一步优选为吡喃环、哌啶环、或环状酰胺等环内具有碳以外的原子的脂肪族环中的一种或多种。上述杂环基可以具有取代基也可以没有取代基。
上述链烯基优选为C2-C20的链烯基；进一步优选为乙烯基、烯丙基、或丁二烯基等包含双键的不饱和脂肪族烃基中的一种或多种。上述链烯基可以具有取代基也可以没有取代基。
上述环烯基优选为C3-C20的环烯基；进一步优选为环戊烯基、环戊二烯基、或环己烯基等包含双键的不饱和脂环式烃基中的一种或多种。上述环烯基可以具有取代基也可以没有取代基。
上述炔基优选为C2-C20的炔基；进一步优选为乙炔基等包含三键的不饱和脂肪族烃基。上述炔基可以具有取代基也可以没有取代基。
上述烷氧基优选为C1-C20的烷氧基；进一步优选为甲氧基、乙氧基、或丙氧基等介由醚键键合脂肪族烃基的官能团中的一种或多种。该脂肪族烃基可以具有取代基也可以没有取代基。
上述烷硫基是烷氧基的氧原子被置换为硫原子的基团。优选为C1-C20的烷硫基；烷硫基的烷基可以具有取代基也可以没有取代基。
上述芳基优选为C6-C60的芳基；进一步优选为苯基、萘基、联苯基、菲基、苯三联苯基或芘基等芳香族烃基中的一种或多种。芳基可以具有取代基也可以没有取代基。
上述杂芳基优选为C4-C60的芳香族杂环基；进一步优选为呋喃基、噻吩基、吡咯、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、吡啶基或喹啉基等中的一种或多种。芳香族杂环基可以具有取代基也可以没有取 代基。
上述芳基醚基优选为C6-C40的芳基醚基；进一步优选为苯氧基等介由醚键键合芳香族烃基的官能团。芳基醚基可以具有取代基也可以没有取代基。
上述芳基硫醚基是芳基醚基的醚键的氧原子被置换为硫原子的基团。优选为C6-C60的芳基硫醚基。芳基硫醚基中的芳香族烃基可以具有取代基也可以没有取代基。
上述卤素原子选自于氟、氯、溴、或碘。
上述羰基、羧基、氧羰基、氨基甲酰基、烷氨基可以具有取代基也可以没有取代基。对于烷氨基取代基的碳数没有特别限制，通常为2以上60以下的范围。
上述硅烷基表示为例如三甲基硅烷基、三乙基硅烷基、二甲基叔丁基硅烷基、三苯基硅烷基等具有与硅原子键合的键的官能团，硅烷基可以具有取代基也可以没有取代基。对于硅烷基的碳数没有特别限制，通常为1以上40以下的范围。
上述取代基选自于氘、卤素、C1-C15的烷基、C3-C15的环烷基、C3-C15的杂环基、C2-C15的链烯基、C4-C15的环烯基、C2-C15的炔基、C1-C55的烷氧基、C1-C55的烷巯基、C6-C55的芳基醚基、C6-C55的芳基硫醚基、C6-C55的芳基、C4-C55的芳香族杂环基、羰基、羧基、氧羰基、氨基甲酰基、C1-C55的烷氨基、或C3-C15的硅原子数为1-5的硅烷基中的一种或多种。
所述芳香胺化合物，没有特别限定，优选列举如下的例子。
Figure PCTCN2014094227-appb-000006
Figure PCTCN2014094227-appb-000007
Figure PCTCN2014094227-appb-000008
Figure PCTCN2014094227-appb-000009
Figure PCTCN2014094227-appb-000010
Figure PCTCN2014094227-appb-000011
上述通式(1)所示的芳香胺化合物的合成可以使用已知的方法进行。例如，使用镍、钯等过渡金属的交叉偶合反应。下述反应式中，M为MgBr等 代表的镁化合物的熊田-玉尾偶合反应、ZnCl等代表的锌化合物的根岸偶合反应、SuBu3等代表的锡化合物的小杉-右田-Stille偶合反应、Si(OH)3等代表的硅化合物的桧山偶合反应、B(OH)2等代表的铃木-宫浦偶合反应，但并不限于这些方法。上述Hal表示氯原子、溴原子、碘原子等卤素或三氟甲磺酸基等拟卤素。上述反应中，基于原料为主族金属化合物的毒性低、反应的副产物少、容易除去未反应的主族金属化合物等特点优选铃木-宫浦偶合反应。
Figure PCTCN2014094227-appb-000012
其他合成方法是使用镍、钯或铜等过渡金属的C-N结合生成反应。例如，使用镍或钯的Buchwald-Hartwig反应、使用铜的Ullman反应，但并不限于这些方法。上述反应，反应条件温和、各种官能团的选择性优越等特点，优选Buchwald-Hartwig反应。另外，合成Ar1、Ar2或Ar3、Ar4为不同取代基时，按胺和卤化物的理论混合比，分阶段合成。本发明中的通式(1)的芳香胺化合物，可以单独使用也可以跟其他材料混合使用在有机发光元件中。
下面具体说明本发明的有机发光元件的实施方式。本发明是含有芳香胺化合物的有机发光元件，该有机发光元件是依次具有基板、第一电极、包括发光层在内的一层以上的有机层膜、使前述发光层发出的光透过的第二电极和光取出效率改善层，发光层通过电能而发光。
在本发明的发光元件中，所用的基板优选为钠玻璃或无碱玻璃等玻璃基 板。对于玻璃基板的厚度，只要是足以保持机械强度的厚度即可，因此，0.5mm以上就足够。对于玻璃的材质，由于从玻璃中溶出的离子越少越好，因此，优选无碱玻璃。另外，市场上销售的涂有SiO2等防护涂层的也可以使用。此外，如果第一电极稳定地发挥功能，则基板不必一定为玻璃，例如，也可以在塑料基板上形成阳极。
第一电极中使用的材料优选为具有高折射率特性的金、银、铝等金属或APC系合金之类的金属合金。这些金属或金属合金也可以是多层层叠。此外，可在金属、金属合金或它们的层积体的上面和/或下面层叠氧化锡、氧化铟、氧化锡铟(ITO)、氧化锌铟(IZO)等透明导电性金属氧化物。
第二电极中使用的材料优选为可形成能使光透过的半透明或透明膜的材料。例如，银、镁、铝、钙或这些金属的合金，氧化锡、氧化铟、氧化锡铟(ITO)、氧化锌铟(IZO)等透明导电性金属氧化物。这些金属、合金、或金属氧化物也可以是多层层叠。
上述电极的形成方法可以是电阻加热蒸镀、电子束蒸镀、溅射、离子喷镀、或胶涂布法等，没有特别限制。此外，第一电极与第二电极根据所使用的材料的功函数，其中一方相对于有机膜层起阳极作用，另一方起阴极作用。
有机层除了可以仅由发光层构成以外，还可以是由1)空穴传输层/发光层，2)发光层/电子传输层，3)空穴传输层/发光层/电子传输层，4)空穴注入层/空穴传输层/发光层/电子传输层，5)空穴注入层/空穴传输层/发光层/电子传输层/电子注入层等层叠而成的结构。此外，上述各层可以分别是单层或多层中的任一种。采用1)～5)的结构时，阳极侧电极与空穴输入层或空穴传输层接合，阴极侧电极则与电子输入层或电子传输层接 合。
空穴传输层可通过将空穴传输材料的一种或二种以上层叠或混合的方法，或通过使用空穴传输材料和高分子粘合剂的混合物的方法来形成。空穴传输材料需要在施加了电场的电极之间高效率地传输来自正极的空穴，因此希望空穴注入效率高、能够高效率地传输注入的空穴。因此，要求空穴传输材料具有适当离子势，且空穴迁移率大，进而，稳定性优异，制造及使用时不容易产生会成为陷阱的杂质。对满足这样的条件的物质，没有特别限定，例如可以是4，4’-二(N-(3-甲基苯基)-N-苯基氨基)联苯(TPD)、4，4’-二(N-(1-萘基)-N-苯基氨基)联苯(NPD)、4，4’-二(N，N-二(4-联苯基)氨基)联苯(TBDB)、二(N，N-二苯基-4-苯基氨基)-N，N-二苯基-4，4’-二氨基-1，1’-联苯(TPD232)等联苯胺，4，4’，4”-三(3-甲基苯基(苯基)氨基)三苯胺(m-MTDATA)、4，4’，4”-三(1-萘基(苯基)氨基)三苯胺(1-TNATA)等称作星型三芳胺的材料组，具有咔唑骨架的材料，其中优选咔唑类多聚体，具体可列举二(N-芳基咔唑)或二(N-烷基咔唑)等二咔唑衍生物、三咔唑衍生物、四咔唑衍生物、三苯系化合物、吡唑啉衍生物、芪系化合物、肼系化合物、苯并呋喃衍生物、噻吩衍生物、噁二唑衍生物、酞菁衍生物、卟啉衍生物等杂环化合物、或富勒烯衍生物，在聚合物系中，还优选侧链上具有上述单体的聚碳酸酯或苯乙烯衍生物、聚噻吩、聚苯胺、聚芴、聚乙烯基咔唑和聚硅烷等。此外，还可以使用P型Si、P型SiC等无机化合物。
可在阳极和空穴传输层之间设置空穴注入层。通过设置空穴注入层，可使有机发光元件实现低驱动电压，提高耐久寿命。空穴注入层通常优选使用 比空穴传输层材料的离子势低的材料。具体地，例如可以是上述TPD232之类的联苯胺衍生物、星型三芳胺材料组，另外也可以使用酞菁衍生物等。此外，还优选空穴注入层由受体性化合物单独构成，或受体性化合物掺杂在别的空穴传输层中使用。受体性化合物可列举例如三氯化铁(III)、氯化铝、氯化镓、氯化铟、氯化锑等金属氯化物，氧化钼、氧化钒、氧化钨、氧化钌等金属氧化物，三(4-溴苯基)六氯锑酸铵(TBPAH)等电荷转移配位物。此外，还可以是分子内具有硝基、氰基、卤素或三氟甲基的有机化合物、醌系化合物、酸酐系化合物、富勒烯等。
本发明中，发光层可以是单层、多层中的任一种，可分别用发光材料(主体材料、掺杂材料)形成，其可以是主体材料和掺杂材料的混合物，也可以仅为主体材料，任一情况都可以。即，在本发明发光元件的各发光层中，可以是仅主体材料或仅掺杂材料发光，也可以是主体材料和掺杂材料一起发光。从高效率地利用电能、得到高色纯度的发光的角度考虑，优选发光层由主体材料和掺杂材料混合而成。另外，主体材料和掺杂材料分别可以为一种，也可以为多种的组合，任一情况都可以。掺杂材料可以添加在整个主体材料中，也可以添加在一部分中，任一情况都可以。掺杂材料可以是层叠的，也可以分散的，任一情况都可以。掺杂材料可以控制发光色。掺杂材料的量过多时会发生浓度消光现象，因此，其用量相对于主体材料，优选为20重量％以下，更优选为10重量％以下。掺杂方法可以是与主体材料共蒸镀的方法，也可以是预先与主体材料混合后同时蒸镀的方法。
作为发光材料，具体而言，可使用以往作为发光体而已知的蒽、芘等稠环衍生物，三(8-羟基喹啉)铝等金属螯合类羟基喹啉化合物、二苯并呋喃 衍生物、咔唑衍生物、吲哚并咔唑衍生物，聚合物中的聚亚苯基亚乙烯基衍生物、聚对亚苯基衍生物、以及聚噻吩衍生物等，没有特别限定。
对发光材料中所含有的主体材料没有特别限定，可以使用蒽、菲、芘、苯并菲、并四苯、苝、苯并[9，10]菲、荧蒽、芴、茚等具有稠芳环的化合物或其衍生物、N，N’-二萘基-N，N’-二苯基-4，4’-二苯基-1，1’-二胺等芳香族胺衍生物、三(8-羟基喹啉)铝等金属螯合类羟基喹啉化合物、吡咯并吡咯衍生物、二苯并呋喃衍生物、咔唑衍生物、吲哚并咔唑衍生物、三嗪衍生物，在聚合物中，可以使用聚亚苯基亚乙烯基衍生物、聚对亚苯基衍生物、聚芴衍生物、聚乙烯基咔唑衍生物、聚噻吩衍生物等，没有特别限定。
此外，对掺杂材料没有特别限制，可列举萘、蒽、菲、芘、苯并菲、苝、苯并[9，10]菲、荧蒽、芴、茚等具有稠芳环的化合物或其衍生物(例如2-(苯并噻唑-2-基)-9，10-二苯基蒽等)、呋喃、吡咯、噻吩、噻咯、9-硅杂芴、9，9’-螺二硅杂芴、苯并噻吩、苯并呋喃、吲哚、二苯并噻吩、二苯并呋喃、咪唑并吡啶、菲咯啉、吡啶、吡嗪、萘啶、喹喔啉、吡咯并吡啶、噻吨等具有杂芳环的化合物或其衍生物、硼烷衍生物、二苯乙烯基苯衍生物、氨基苯乙烯基衍生物、吡咯甲川衍生物、二酮基吡咯并[3，4-c]吡咯衍生物、香豆素衍生物、咪唑、噻唑、噻二唑、咔唑、噁唑、噁二唑、三唑等唑衍生物、芳香族胺衍生物等。
另外，发光层中也可以掺杂磷光发光材料。磷光发光材料为室温下也可以磷光发光的材料。使用磷光发光材料作为掺杂剂时，需要基本上能够在室温下磷光发光，但没有特别限定，优选含有选自铟、钌、铑、钯、铂、锇和 铼中的至少一种金属的有机金属络合化合物。从室温下具有高的磷光发光效率的角度考虑，更优选具有铟或铂的有机金属络合物。作为与磷光发光性掺杂剂组合使用的主体材料，吲哚衍生物、咔唑衍生物、吲哚并咔唑衍生物，具有吡啶、嘧啶、三嗪骨架的含氮芳香族化合物衍生物，多芳基苯衍生物、螺芴衍生物、三聚茚、苯并[9，10]菲等芳香烃化合物衍生物，二苯并呋喃衍生物、二苯并噻吩等含有氧族元素的化合物，羟基喹啉铍络合物等有机金属络合物可良好地使用，但基本上只要比使用的掺杂剂的三重态能大、电子和空穴能从各自层输送层顺利地注入或传输，则没有特别限定。另外，可以含有2种以上三重态发光掺杂剂，也可以含有2种以上主体材料。此外，也可以含有一种以上的三重态发光掺杂剂和一种以上的萤光发光掺杂剂。
在本发明中，电子传输层为电子从阴极注入、再将电子传输的层。电子传输层宜具有高的电子注入效率，且能高效率地传输注入的电子。因此，电子传输层优选由电子亲和力和电子迁移率大且稳定性优异、制造及使用时不容易产生会成为陷阱的杂质的物质构成。但是，在考虑空穴和电子的传输均衡时，如果电子传输层主要发挥可以高效率地阻止来自阳极的空穴不再结合而流向阴极侧的作用，则即使由电子传输能力不那么高的材料构成，改善发光效率的效果也会与由电子传输能力高的材料构成的情况同等。因而，在本发明中的电子传输层中，可以高效率地阻止空穴迁移的空穴阻止层作为等同物也包含在内。
对电子传输层中使用的电子传输材料没有特别限定，可列举萘、蒽等稠芳环衍生物、以4，4’-二(二苯基乙烯基)联苯为代表的苯乙烯基系芳环衍生物、蒽醌、联苯醌等醌衍生物、氧化膦衍生物、三(8-羟基喹啉)铝等 羟基喹啉络合物、苯并羟基喹啉络合物、羟基唑络合物、偶氮甲碱络合物、环庚三烯酚酮金属络合物或黄酮醇金属络合物，从降低驱动电压、能够得到高效率发光的角度考虑，优选使用具有杂芳环结构的化合物，所述杂芳环结构由选自碳、氢、氮、氧、硅、磷中的元素构成并且含有吸电子性氮。
含有吸电子性氮的杂芳环具有高亲电子性。具有吸电子性氮的电子传输材料容易接受来自具有高亲电子性的阴极的电子，因而可以降低发光元件的驱动电压。此外，由于向发光层的电子供给增大、在发光层再结合的概率增加，因而发光效率提高。作为含有吸电子性氮的杂芳环，可以列举例如，吡啶环、吡嗪环、嘧啶环、喹啉环、喹喔啉环、萘啶环、嘧啶并嘧啶环、苯并喹啉环、菲咯啉环、咪唑环、噁唑环、噁二唑环、三唑环、噻唑环、噻二唑环、苯并噁唑环、苯并噻唑环、苯并咪唑环、或菲并咪唑环等。
另外，作为具有这些杂芳环结构的化合物，可以列举出例如苯并咪唑衍生物、苯并噁唑衍生物、苯并噻唑衍生物、噁二唑衍生物、噻二唑衍生物、三唑衍生物、吡嗪衍生物、菲咯啉衍生物、喹喔啉衍生物、喹啉衍生物、苯并喹啉衍生物，联吡啶、三联吡啶等低聚吡啶衍生物。上述衍生物具有稠芳环骨架时，玻璃转化温度提高，且电子迁移率增加，由此，降低发光元件的驱动电压的效果增大，因而优选。此外，从发光元件的耐久寿命提高、合成容易、原料容易购得的角度考虑，优选上述稠芳环骨架为蒽骨架、芘骨架或菲咯啉骨架。
上述电子传输材料可以单独使用，也可以将二种以上的上述电子传输材料混合使用，或将一种以上的其它电子传输材料混合到上述电子传输材料中使用。另外，也可以添加给体化合物。这里，给体化合物是指通过改善电子 注入能障而使电子容易从阴极或电子注入层向电子传输层注入、进而改善电子传输层的电传导性的化合物。作为本发明的给体化合物的优选例，可列举：碱金属、含有碱金属的无机盐、碱金属与有机物的络合物、碱土金属、含有碱土金属的无机盐、或碱土金属与有机物的络合物等。作为碱金属、或碱土金属的优选种类，可列举低功函数且改善电子传输能力的效果大的锂、钠、或铯之类的碱金属或镁、钙之类的碱土金属。
本发明中，也可在阴极和电子传输层之间设置电子注入层。通常，电子注入层是以帮助电子从阴极注入到电子传输层为目的而插入的，插入时，可以使用含有吸电子性氮的杂芳环结构的化合物，也可以使用含有上述给体化合物的层。另外，在电子注入层中，还可以使用绝缘体或半导体的无机物。使用这些材料，可以有效地防止发光元件短路，且可以提高电子注入性，因而优选。作为这些绝缘体，优选使用选自碱金属硫族化物、碱土金属硫族化物、碱金属卤化物及碱土金属卤化物中的至少一种金属化合物。另外，有机物与金属的络合物也可良好地使用。
作为构成发光元件的上述各层的形成方法，可列举电阻加热蒸镀、电子束蒸镀、溅射、分子层叠法、或涂层法等，没有特别限制，但是，通常，从元件特性的角度考虑，优选电阻加热蒸镀或电子束蒸镀。
有机层的厚度视发光物质的电阻值而异，不能限定，但优选为1～1000nm。发光层、电子传输层、空穴传输层的膜厚分别优选为1nm以上200nm以下，更优选为5nm以上100nm以下。
本发明的光取出效率改善层含有上述具有噻吩结构、呋喃结构或吡咯结构的化合物。为了使高发光效率极大化、实现色再现性，优选使噻吩结构、 呋喃结构或吡咯结构的化合物以20nm～120nm的厚度层叠。更优选层叠厚度为40nm～80nm。另外，从可以使发光效率极大化的角度考虑，更优选光取出效率改善层厚度为50nm～70nm。
对光取出效率改善层的形成方法没有特别限定，可列举电阻加热蒸镀、电子束蒸镀、溅射、分子层叠法、涂层法、喷墨法、刮板法、激光转印法等，没有特别限制。
本发明的发光元件具有可以将电能转换为光的功能。这里，作为电能，主要使用直流电流，也可以使用脉冲电流或交流电流。对电流值及电压值没有特别限制，但考虑到元件的耗电量和寿命时，应以能以尽可能低的能量得到最大亮度的方式来选择。
本发明的发光元件可良好地用作以例如矩阵及/或字段方式进行显示的平面显示器。
矩阵方式是指用于显示的像素以方格状或马赛克状等二维配置，通过像素的集合来显示文字或图像。像素的形状、尺寸视用途而定。例如，在计算机、监控器、电视的图像及文字显示中，通常使用边长在300μm以下的四边形的像素，另外，在显示面板那样的大型显示器的情况下，使用边长为mm等级的像素。在单色显示的情况下，只要排列同色的像素即可，但在彩色显示的情况下，将红、绿、蓝色像素排列进行显示。这种情况下，典型的有三角型和条纹型。而且，该矩阵的驱动方法可以是逐线驱动方法和有源矩阵中的任一种。逐线驱动虽然其构造简单，但在考虑操作特性时，有时会有有源矩阵优异的情况，因此，需要根据用途灵活使用。
本发明中的字段方式是指形成图案、使由该图案的配置所确定的区域发 光、从而显示预先确定的信息的方式。可列举例如：数字钟、温度计中的时刻、温度显示，音响设备、电磁灶等的工作状态显示及汽车的面板显示等。而且，所述矩阵显示和字段显示可以共存在同一个面板中。
本发明的发光元件优选用作照明光源，可以提供比现有的薄且轻、可进行面发光的光源。
具体实施方式
本发明的芳香胺化合物用以下实施例举例说明，但并不限于这些实施例举例的芳香胺化合物和合成方法。
二甲基甲酰胺，乙酸乙酯，1，2-二甲苯，碳酸钾，二氯甲烷，乙醇和碳酸钠等购于国药公司；N-甲基吡咯，2，5-二溴噻吩等购于TCI公司；各种钯催化剂，硼酸衍生物和硼酸酯衍生物等购于Aldrich公司。
1H-NMR谱图使用JEOL(400MHz)核磁共振仪来测定；HPLC谱图使用岛津LC-20AD高效液相仪来测定。
实施例和比较例中使用物质为：
化合物[2](2，5-二(4-(N-苯基)-(N-3-吡啶基)氨基苯基)噻吩)、
化合物[5](2，5-二(4-(N-4-联苯基)-(N-3-吡啶基)氨基苯基)噻吩)、
化合物[6](2，5-二(4-(N-4-联苯基)-(N-4-吡啶基)氨基苯基)噻吩)、
化合物[8](2，5-二(4-(N-3-联苯基)-(N-3-吡啶基)氨基苯基)噻吩)、
化合物[87](1-甲基-2，5-二(4-(N-4-联苯基)-(N-3-吡啶基)氨基苯基)-1H-吡咯)、
化合物[31](2，5-二(4-(N-1-萘基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[32](2，5-二(4-(N-3-联苯基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[134](2，5-二(4-(N-3-(3’-甲基)联苯基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[11](2，5-二(4-(N-4-(3-吡啶基)苯基)-(N-3-吡啶氨基)苯基)噻吩)、
化合物[12](2，5-二(4-(N-4-(3-吡啶基)苯基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[13](2，5-二(4-(N-4-(4-吡啶基)苯基)-(N-2-吡啶氨基)苯基)噻吩)、
化合物[14](2，5-二(4-(N-4-(4-吡啶基)苯基)-(N-3-吡啶氨基)苯基)噻吩)、
化合物[15](2，5-二(4-(N-4-(4-吡啶基)苯基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[18](2，5-二(4-(N-3-(3-吡啶基)苯基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[21](2，5-二(4-(N-3-(4-吡啶基)苯基)-(N-4-吡啶氨基)苯基)噻吩)、
化合物[140](2，5-二(4-(N-4-联苯基)-(N-3-喹啉氨基)苯基)噻吩)、
化合物[142](2，5-二(4-(N-4-联苯基)-(N-6-喹啉氨基)苯基)噻吩)、
化合物[143](2，5-二(4-(N-4-联苯基)-(N-2-嘧啶氨基)苯基)噻吩)、
化合物[144](2，5-二(4-(N-4-联苯基)-(N-5-嘧啶氨基)苯基)噻吩)、
化合物[147](2，5-二(4-(N-4-联苯基)-(N-4-苯基氨基)苯基)噻吩)、
化合物[148](2，5-二(4-(N-4-联苯基)-(N-1-萘炔基氨基)苯基)噻吩)、
化合物[149](2，5-二(4-(N-4-联苯基)-(N-2-萘炔基氨基)苯基)噻吩)、
NPD：(N，N’-二苯基-N，N’-二(1-萘基)-1，1’-联苯-4，4’-二胺)、
F4-TCNQ(2，3，5，6-四氟-7，7’，8，8’-四氰二甲基对苯醌)、
BH：(9-(2-萘基)-10-(4-(1-萘基)苯基)蒽)、
BD：(E-7-(4-(二苯基氨基)苯乙烯基)-N，N-二苯基-9，9’-二甲基芴基-2-胺)、
Alq3：(三(8-羟基喹啉)铝)、
TBDB：(N，N，N’，N’-4(4-联苯基)联苯二氨)。
关于本说明书中记载的化合物，在本说明书中同时记载了其化学式命名和结构式的情况下，化合物的结构以结构式为准。
实施例1
化合物[2]的合成
氮气氛围下，反应器中加入2，5-二溴噻吩24.2g(100mmol)、4-氯苯硼酸34.4g(220mmol)、四(三苯基膦)钯5.7g(5.0mmol)、1.5M碳酸钠水溶液200ml(300mmol)和二甲醚100ml(DME)，110℃加热搅拌一晚。冷却至室温，过滤，滤液分层为有机层和水层，有机层减压浓缩。得到的固体用乙醇洗涤，得到21.3g的2，5-双(4-氯苯基)噻吩。
1HNMR(DMSO)：δ7.52～7.51(d，8H)，6.32(s，2H)，3.57(s，3H).
氮气氛围下，反应器中加入2，5-双(4-氯苯基)噻吩2.00g(6.56mmol)、 N-苯基-3-吡啶基胺2.45g(14.4mmol)、双(二亚苄基丙酮)钯189mg(0.328mmol)、四氟硼酸三叔丁基膦190mg(0.656mmol)、叔丁醇钠1.89g(19.7mmol)和1，2-二甲苯60ml，110℃加热搅拌一晚。冷却至室温，过滤，滤液减压浓缩。得到的固体用乙醇洗涤，得到3.5g的粗产品。粗产品在压力3×10-3Pa，温度280℃下升华得到2.2g化合物[2](淡黄色固体)。
1HNMR(CDCl3)：δ7.53～7.51(d，4H)，7.42～7.39(m，2H)，7.32～7.28(t，4H)，7.20(s，2H)，7.19～7.15(m，2H)，7.14～7.07(m，10H).
HPLC(纯度＝97.1％)
实施例2
化合物[5]的合成
除了N-(4-联苯基)-3-吡啶基胺替代N-苯基-3-吡啶基胺使用以外，其余与实施例1相同。得到1.1g化合物[5](淡黄色固体)。
1HNMR(DMSO)：δ8.47～8.46(d，2H)，8.27～8.26(d，2H)，7.57～7.52(m，12H)，7.45～7.41(m，6H)，7.35～7.32(t，2H)，7.25～7.12(m，12H).
HPLC(纯度＝98.1％)
实施例3
化合物[6]的合成
除了N-(4-联苯基)-3-吡啶基胺替代N-苯基-4-吡啶基胺使用以外，其余与实施例1相同。得到2.2g化合物[6](淡黄色固体)。
1HNMR(DMSO)：δ8.26～8.25(d，4H)，7.76～7.67(m，12H)，7.55(s，2H)，7.48～7.45(t，4H)，7.38～7.26(m，10H)，6.78～6.77(m，4H).
HPLC(纯度＝99.02％)
实施例4
化合物[8]的合成
除了N-(3-联苯基)-3-吡啶基胺替代N-苯基-3-吡啶基胺使用以外，其余与实施例1相同。得到1.5g化合物[8](淡黄色固体)。
1HNMR(CDCl3)：δ8.35～8.34(d，2H)，8.27～8.26(d，2H)，7.66～7.64(d，4H)，7.58～7.56(d，4H)，7.53～7.41(m，12H)，7.37～7.34(m，6H)，7.12～7.08(t，6H).HPLC(纯度＝97.8％)
实施例5
化合物[31]的合成
除了N-(3-联苯基)-3-吡啶基胺替代N-萘基-3-吡啶基胺使用以外，其余与实施例1相同。得到2.5g化合物[31](淡黄色固体)。
1HNMR(CDCl3)：δ8.17～8.14(d，4H)，8.05～7.98(m，4H)，7.82～7.79(d，2H)，7.67～7.59(m，6H)，7.57～7.43(m，8H)，7.30～7.27(d，4H)，6.56～6.54(d，4H).
HPLC(纯度＝97.2％)
实施例6
化合物[32]的合成
除了N-(3-联苯基)-3-吡啶基胺替代N-联苯基-3-吡啶基胺使用以外，其余与实施例1相同。得到3.2g化合物[32](淡黄色固体)。
1HNMR(CDCl3)：δ8.17～8.14(d，4H)，8.05～7.98(m，4H)，7.82～7.79(d，2H)，7.67～7.59(m，6H)，7.57～7.43(m，8H)，7.30～7.27(d，4H)，6.56～6.54(d，4H).
HPLC(纯度＝95.0％)
实施例7
化合物[134]的合成
除了N-苯基-3-吡啶基胺替代N-3-(3’-甲基联苯基)-4-吡啶基胺使用以外，其余与实施例1相同。得到3.6g化合物[134](淡黄色固体)。
1HNMR(CDCl3)：δ8.25(d，4H)；7.70～7.75(m，8H)；7.54(s，2H)；7.44～7.49(m，4H)；7.15～7.36(m，12H)；6.76(d，4H)；2.37(s，6H)。
.HPLC(纯度＝95.9％)
实施例8
化合物[87]的合成
氮气氛围下，反应器中加入N-甲基吡咯3.24g(40mmol)、4-氯溴苯22.9g(120mmol)、双(二苯基膦)丙烷-氯化钯243mg(0.39mmol)、碳酸钾15.68g(160mmol)和二甲基乙酰胺150ml(DMAC)，110℃加热搅拌一晚。冷却至室温，过滤，滤液减压浓缩。得到的固体用乙醇洗涤，得到4.3g的2，5-双(4-氯苯基)-1-甲基吡咯。
1HNMR(DMSO)：δ7.52～7.51(d，8H)，6.32(s，2H)，3.57(s，3H).
氮气氛围下，反应器中加入2，5-双(4-氯苯基)-1-甲基吡咯1.50g(4.96mmol)、N-(4-联苯基)-3-吡啶基胺3.50g(14.2mmol)、双(二亚苄基丙酮)钯30mg(0.052mmol)、四氟硼酸三叔丁基膦30mg(0.10mmol)、叔丁醇钠2.80g(29.1mmol)和1，2-二甲苯60ml，110℃加热搅拌一晚。冷却至室温，过滤，滤液减压浓缩。得到的固体用乙醇洗涤后，硅胶柱(洗脱液：二氯甲烷/乙酸乙酯＝4/1)纯化，得到2.4g粗产品。粗产品在压力2×10-3Pa，温度320℃下升华得到1.0g化合物[87](淡黄色固体)。
1HNMR(CDCl3)：δ8.48～8.47(d，2H)，8.27～8.26(dd，2H)，7.59～7.57(d，4H)， 7.55-7.53(d，4H)，7.50～7.47(m，2H)，7.45～7.38(m，8H)，7.35～7.31(t，2H)，7.22～7.16(m，10H)，6.31(s，2H)，3.66(s，3H).
HPLC(纯度＝97.8％)
实施例9
薄膜样品的制作方法
无碱玻璃基板(旭硝子株式会社，AN100)进行20分钟的UV臭氧洗涤处理，进而设置在真空蒸镀装置内，进行排气，直至装置内的真空度比1×10-3Pa高的真空度条件下，通过电阻加热蒸镀法，把化合物[2]蒸镀制备约50nm的薄膜。蒸镀速度为0.1nm/s。
上述制备的薄膜样品折射率和衰减系数的测定是在东丽分析研究中心(Toray Research Center.Inc.)，使用仪器是椭圆偏振光谱(J.A.Woollam社M-2000)。
【表1】
Figure PCTCN2014094227-appb-000013
※光学常数(折射率：n、衰减系数：k)是小数点3位数四舍五入
实施例10-24及比较例1
实施例10
除了化合物[5]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例11
除了化合物[6]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例12
除了化合物[8]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例13
除了化合物[87]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例14
除了化合物[11]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例15
除了化合物[12]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例16
除了化合物[13]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例17
除了化合物[14]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例18
除了化合物[15]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例19
除了化合物[18]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例20
除了化合物[21]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例21
除了化合物[140]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例22
除了化合物[142]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例23
除了化合物[143]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
实施例24
除了化合物[144]代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
比较例1
除了NPD代替化合物[2]以外，其余与实施例9相同。
对有机发光元件进行评价。评价结果见表2。
和实施例9进行同样的实验，如表2所示，实施例10-24的结果如下所示。
【表2】
Figure PCTCN2014094227-appb-000014
Figure PCTCN2014094227-appb-000015
Figure PCTCN2014094227-appb-000016
从上述表1和表2所示，实施例9-24比比较例1折射率高。进一步，测试了发光元件性能。
发光元件的评价方法
实施例25
无碱玻璃在异丙醇中15分钟超声波洗涤后，在大气中进行30分钟UV臭氧洗涤处理。利用真空蒸镀法，首先蒸镀铝100nm作成阳极，随后在阳极上空穴注入层(NPD和F4-TCNQ(重量比97∶3)，50nm)，空穴传输层(NPD，80nm)，蓝色发光层(BH和BD(重量比97∶3，20nm)，电子传输层(Alq3，30nm)，电子注入层(LiF，1nm)依次层叠蒸镀后，共蒸镀Mg和Ag(重量比10∶1，15nm)作成半透明阴极。
上述使用化合物如下所示。
Figure PCTCN2014094227-appb-000017
Figure PCTCN2014094227-appb-000018
随后蒸镀化合物[5](60nm)作为覆盖层。
最后在干燥氮气氛围的手套箱里，用环氧树脂粘合剂把无碱玻璃制的封口板封发光元件。
上述发光元件在室温，大气中，加10mA/cm2直流电流，从封口板的发光用分光放射辉度计(CS1000，柯尼卡美能达株式会社)测试了发光特性。使得到发光效率为6.5cd/A，色纯度为CIE(x，y)＝(0.139，0.051)。使用化合物[5]作为覆盖层得到高发光效率，高色纯度的高性能发光元件。
评价结果见表3。
实施例26
除了覆盖层材料为化合物[6]以外，其余与实施例25作成相同的元件进行评价，评价结果见表3。
实施例27
除了覆盖层材料为化合物[8]以外，其余与实施例25作成相同的元件进行评价，评价结果见表3。
比较例2
除了覆盖层材料为NPD以外，其余与实施例25作成相同的元件进行评价，评价结果见表3。
比较例3
除了覆盖层材料为TBDB以外，其余与实施例25作成相同的元件进行评价，评价结果见表3。
实施例28-39，比较例4-6除了化合物为表3中所示以外，其余与实施例25作成相同的元件进行评价，评价结果见表3。
比较例4，比较例5，比较例6用的化合物如下所示。
Figure PCTCN2014094227-appb-000019
【表3】
  化合物 发光效率(cd/A) 色纯度CIE(x，y)
实施例25 [5] 6.5 0.139，0.051
实施例26 [6] 6.8 0.139，0.050
实施例27 [8] 5.8 0.138，0.049
实施例28 [2] 6.6 0.139，0.050
实施例29 [11] 5.9 0.138，0.052
实施例30 [12] 6.2 0.138，0.049
实施例31 [13] 6.6 0.137，0.049
实施例32 [14] 6.8 0.139，0.048
实施例33 [15] 6.1 0.139，0.051
实施例34 [18] 5.9 0.137，0.051
实施例35 [21] 6.0 0.139，0.050
实施例36 [140] 6.5 0.138，0.049
实施例37 [142] 6.5 0.139，0.049
实施例38 [143] 6.1 0.137，0.050
实施例39 [144] 6.1 0.137，0.048
比较例2 NPD 4.5 0.139，0.048
比较例3 TBDB 4.5 0.137，0.051
比较例4 [147] 4.6 0.137，0.053
比较例5 [148] 4.7 0.137，0.050
比较例6 [149] 4.4 0.138，0.052
(TBDB)/比较例3
Figure PCTCN2014094227-appb-000020
从上述表3所示，实施例25～实施例39的发光元件是同时满足高发光效率和高色纯度。另外，比较例2～比较例6的发光元件与实施例的色纯度是同等，但发光效率比实施例低，不能同时满足高发光效率和高色纯度。
以上结果得出，本发明的芳香胺化合物适用于有机发光元件材料，得到同时满足高发光效率和高色纯度得发光元件，更适用于覆盖层材料。
本说明书中提到的所有专利文献、非专利文献均通过引用的方式并入本文。本说明书中提到的“多种”包含大于一种的所有情况，即，“一种或多种”包括一种、两种、三种、……等等。本说明书中针对某数值范围分别记载上限和下限时，或者以上限和下限组合的方式记载某数值范围时，其中记载的各上限和各下限可任意组合为新的数值范围，这与直接明确记载组合而成的数值范围的记载形式应被视为是相同的。在不偏离本发明主旨的情况下，本领域技术人员可对本发明进行改变和改良，这些也包括在本发明的范围内。

Claims (8)

  1. 一种芳香胺化合物，其特征在于：具有下述通式(1)：
    Figure PCTCN2014094227-appb-100001
    其中，X选自硫原子、氧原子、或N-R，R选自氢、氘、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的烷氨基或可被取代的硅烷基；
    L1、L2相同或不同，分别独立选自亚芳基或亚杂芳基；
    Ar1、Ar2相同或不同，分别独立选自芳基或杂芳基；
    Ar3、Ar4相同或不同，分别独立选自杂芳基；
    其中，R1、R2相同或不同，分别独立选自氢、氘、卤素、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的氰基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的烷氨基或可被取代的硅烷基，也可以与相邻的取代基键合而形成环。
  2. 根据权利要求1所述的芳香胺化合物，其特征在于：L1和L2为亚芳基。
  3. 一种有机发光元件材料，其特征在于：该材料含有下述通式(1)所示的化合物：
    Figure PCTCN2014094227-appb-100002
    其中，X选自硫原子、氧原子、或N-R，R选自氢、氘、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的烷氨基或可被取代的硅烷基；
    L1、L2相同或不同，分别独立选自亚芳基或亚杂芳基；
    Ar1、Ar2相同或不同，分别独立选自芳基或杂芳基；
    Ar3、Ar4相同或不同，分别独立选自杂芳基；
    其中，R1、R2相同或不同，分别独立选自氢、氘、卤素、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的氰基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的烷氨基或可被取代的硅烷基，也可以与相邻的取代基键合而形成环。
  4. 根据权利要求3所述的有机发光元件材料，其特征在于：L1和L2为亚芳基。
  5. 一种有机发光元件，其特征在于：包含基板、第一电极、含有一种以上有机层膜的发光层、第二电极、及覆盖层；该有机发光元件含有权利要求3或4所述的有机发光元件材料。
  6. 一种有机发光元件覆盖层材料，其特征在于：该材料含有下述通式(1)所示的化合物：
    Figure PCTCN2014094227-appb-100003
    其中，X选自硫原子、氧原子、或N-R，R选自氢、氘、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的烷氨基或可被取代的硅烷基；
    L1、L2相同或不同，分别独立选自亚芳基或亚杂芳基；
    Ar1、Ar2相同或不同，分别独立选自芳基或杂芳基；
    Ar3、Ar4相同或不同，分别独立选自杂芳基；
    其中，R1、R2相同或不同，分别独立选自氢、氘、卤素、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的氰基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的烷氨基或可被取代的硅烷基，也可以与 相邻的取代基键合而形成环。
  7. 根据权利要求6所述的有机发光元件覆盖层材料，其特征在于：L1和L2为亚芳基。
  8. 一种有机发光元件，其特征在于：包含基板、第一电极、包括发光层在内的一层以上有机层膜、第二电极元件，所述发光元件还具有覆盖层；所述覆盖层含有权利要求6或7所述的有机发光元件覆盖层材料。
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