TW200920718A - Chrysene derivative and organic electroluminescence device - Google Patents

Abstract

Disclosed is an organic EL device containing a chrysene derivative, which has a larger energy gap than anthracenes, in an electron transport layer. By having such a constitution, electrons can be adequately injected into a light-emitting layer of the organic EL device without requiring a high voltage, even when the light-emitting layer has a large energy gap for shortening the wavelength of blue light emission.

Description

200920718 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a cave derivative and an organic EL element. [Prior Art] It is known that an organic light-emitting layer is provided between an anode and a cathode, and an organic electroluminescence element is obtained by generating exciton energy from a hole in which an electron injecting into the organic light-emitting layer is re-bonded with electrons ( Organic EL element). In view of the advantages of the self-luminous type element, the organic EL element is expected to be a light-emitting element having excellent luminous efficiency, image quality, power consumption, and further thin design. In recent years, in the case of display applications having high color reproducibility, etc., a blue light-emitting element having a shorter wavelength has been pursued. When the wavelength is shortened, it is necessary to increase the energy gap of the light-emitting layer. Here, as the energy gap of the light-emitting layer becomes larger and the affinity level of the light-emitting layer becomes lower, there is a problem that the electron injection barrier to the light-emitting layer becomes large and the driving voltage rises. Therefore, an element that exhibits good short-wavelength blue light emission and has good driving performance is pursued. Further, in order to reduce the driving voltage, a nitrogen-containing heterocyclic derivative compound having high electron transporting property as an electron transporting layer is disclosed in the document 1 (JP-A-2007-153778). However, when the light-emitting layer is widened, the material disclosed in the aforementioned document has insufficient problems. In addition, the colloidal compound 'by using a light-emitting material or a hole transporting material as an organic EL element' can be a blue light-emitting having high luminous efficiency, as disclosed in Japanese Laid-Open Patent Publication No. 2004-75567. However, the cave derivatives of the present invention have not been disclosed. The main object of the present invention is to provide novel cave derivatives.

Further, the use of a light-emitting layer for displaying a short-wavelength blue light-emitting layer as a hole derivative for an electron injecting and transporting material and an organic EL element using the same are provided. In order to solve this problem, the inventors of the present invention have found that an electron transporting layer capable of appropriately injecting electrons is required as a light-emitting layer having a large energy gap, that is, a low affinity level, without requiring a large voltage. Can use the caves. Here, the energy gap means the difference between the conduction energy level and the valence electron energy level, and can be defined, for example, from the enthalpy measured at the absorption end of the absorption spectrum in benzene. Specifically, an absorption spectrum was measured using a commercially available visible ultraviolet spectrophotometer, and the wavelength from the absorption spectrum was calculated. However, it is not necessarily the above-described regulations, and the enthalpy as the energy gap can be defined without departing from the scope of the present invention. Further, the affinity level Af (electron affinity) means that when an electron is given to a material molecule, the energy released or absorbed is defined as positive when released, and negative when absorbed. The affinity level Af is defined by the ionization potential Ip and the optical energy gap Eg as follows. -6- 200920718 A f=Ip-Eg Here, the ionization potential ϊρ refers to the energy required for ionization by taking out electrons from each material compound. For example, in the present invention, an ultraviolet photoelectron spectroscopy analyzer (ac - 3, the rationale (stock) meter)). However, the term "not necessarily in accordance with the above-mentioned provisions" may be defined as an affinity level without departing from the scope of the present invention. The present invention is based on the knowledge. Namely, the characteristics of the cave derivatives of the present invention are represented by the following general formula (1).

Ar1—Ch—Ar2 · · · (ι ) In the general formula (l), ch denotes a substituted or unsubstituted cave, Arl,

Ar2 is independently independent and represents a substituted or unsubstituted aryl group having a core number of 6 to 4 fluorene or a substituted or unsubstituted aryl group having a core number of 5 to 4 Å. However, at least one of 'A, W' is a substituted or unsubstituted aryl group containing 5 to 4 Å. The characteristics of the cave derivatives of the present invention are represented by the following general formula (2). 200920718

In the general formula (2), Ar3 and Ar4 are each independently represented by a substituted or unsubstituted aryl group having a core carbon number of 6 to 40 or a substituted or unsubstituted heteroaryl group having a core number of 5 to 40. However, at least one of Ar3 and Ar4 is a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms. R1 to R1() represent a hydrogen atom or a substituent. An aryl group having a carbon number of 6 to 40, for example, a phenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a butyl group, a fluorenyl group, a phenyl fluorenyl group, and a aryl group. Benzoindenyl, fluoranthenyl, binaphthyl, phenylnaphthyl, phenyl, phenanthryl, benzophene, triphenylene, and the like. Preferred is an aryl group having a core carbon number of 6 to 14, wherein a phenyl group, a biphenyl group, a naphthyl group or a phenanthryl group is preferred. The aryl group may have a substituent, and the substituent may, for example, be an alkyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 1, 2, particularly preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group). , ethyl, isopropyl, t-butyl, η-octyl, η-fluorenyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, particularly preferably an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group, or a chain -8- 200920718 alkynyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, particularly preferably an alkynyl group having a carbon number of 2 to 8, such as a propynyl group, a 3-pentynyl group, etc.) An aryl group (preferably a carbon number of 6 to 20, particularly preferably an aryl group of 6 to 14, such as a phenyl group, a naphthyl group, a phenanthryl group or a fluorenyl group) or a heterocyclic group (preferably having a carbon number of 1 to 30) More preferably, it is a heterocyclic group having a carbon number of 1 to 12, such as imidazolyl, pyridyl, quinolyl, furyl, thienyl, pyridyl, morpholino, benzoxazolinyl, benzimidazole Benzothiazolyl, carbazolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, monobenzothiobenzene Or a substituted or unsubstituted amino group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 12, particularly preferably an amine group having a carbon number of 0 to 6, such as an amine group, a methylamino group, a dimethylamino group, a ~ethylamino group, a diphenylamino group, a dibenzylamino group, etc.), an alkoxy group (preferably a carbon number of 1 to 20, more preferably a carbon number of 1 to I2). It is an oxy group having a carbon number of 1 to 8, such as a methoxy group, an ethoxy group, a butoxy group or the like, an aryloxy group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to I6). An aryloxy group having 6 carbon atoms, such as a phenyloxy group or a 2-naphthyloxy group, or a fluorenyl group (preferably having a carbon number of 1 to 2 Å, more preferably a carbon number of 1 to 16 or more preferably carbon) a fluorenyl group of 1 to 12, for example, an ethylidene group, a benzhydryl group, a decyl group, a neopentyl group, etc.), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 2) 16. Particularly preferred is an alkoxy group having a carbon number of 2 to 12, such as a methoxycarbonyl group or an ethoxycarbonyl group, and an aryloxycarbonyl group (preferably having a carbon number of 7 to 20, more preferably a carbon number of 7). ～16, particularly preferably an aryloxycarbonyl group having a carbon number of 7 to 10, such as a phenyloxycarbonyl group, or a mercaptooxy group (preferably a number of 2 to 20, more preferably a carbon number of 2 to 16, particularly preferably a decyloxy group having a carbon number of 2 to 1 Å, such as an ethyl oxooxy group, a benzyl methoxy group, or the like, and a mercaptoamine group. It is a carbon number of 2 to 2 Torr, more preferably carbon-9-200920718 (preferably a carbon-1 2 amine methyl 2 to 16, particularly preferably a carbon number of 2 to 10 decylamino group, such as acetamide) Alkoxycarbonylamino group (preferably alkoxycarbonylamino group having a carbon number of 2 to 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms) 'E.g. methoxycarbonylamino group, etc.), aryloxycarbonylamino group (preferably, carbon number 7 to 20, more preferably carbon number 7 to 16, and particularly preferably aryloxycarbonylamine having 7 to 12 carbon atoms) a group such as a phenyloxycarbonylamino group, a substituted or unsubstituted sulfonylamino group (preferably having a carbon number of 1 to 2 Å, more preferably a carbon number of 1 to 16 or more preferably a carbon number of 1 to 16) a sulfonylamino group of 12, such as a methanesulfonylamino group, a phenylfluorenylamine group, a substituted or unsubstituted sulfonamide group (preferably having a carbon number of 0 to 20, more preferably a carbon number 〇~) 16. Particularly preferred is a sulfonylamino group having a carbon number of 〇~12, such as a sulfonylamino group, a methylsulfonylamino group, and a second Alkylsulfonylamino group, phenylsulfonylamino group, etc.), substituted or unsubstituted amine carbenyl group number 1 to 20, more preferably carbon number i~16, particularly preferably carbon number 1 fluorenyl group, such as amine formazan a group, a methylamine methyl sulfonyl group, a diethylaminocarbamyl group, etc.), an alkylthio group (preferably a carbon number ”~), more preferably a carbon number of 1 to 16 carbon atoms, particularly preferably a carbon number 丨An alkylthio group of -2, such as a methylthio group or an ethylthio group, or an arylthio group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to 16, and particularly preferably a carbon number) 6 to 12 arylthio group, for example, phenylthio group, etc., substituted or unsubstituted sulfonyl group (preferably having a carbon number of 1 to 2 Å, more preferably a carbon number of 1 to 16, particularly preferably a carbon number) a sulfhydryl group of 1 to 12, such as a methyl group, a fluorenyl group, a substituted or unsubstituted sulfinium sulfonate (preferably having a carbon number of 1 to 2 Å, more preferably a carbon number of 1 to 16), particularly preferably Substituting carbon number i~12 (4) base mouth "sulfonyl ketone phenylsulfinyl, etc., substituted or unsubstituted ureido group (preferably carbon 胄^, more preferably carbon number 164, especially -10- 200920718 A urea group having a carbon number of 1 to 12, such as a urea group, a methyl urea group, a phenyl urea group, etc. a substituted or unsubstituted guanidinium phosphate group (preferably having a carbon number of 1 to 20, more preferably a carbon number) - ", particularly preferably a carbon number" to a molecular weight, such as diethylphosphoric acid. Amidino, phenylphosphonium amide, etc.), hydroxy, thiol, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group a sulfino group, a fluorenyl group, an imido group, a heterocyclic group (preferably a heterocyclic group having a carbon number of 1 to 30, more preferably a carbon number of 1 to 12), for example, a nitrogen atom, an oxygen atom, or a sulfur Atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, pyridyl, morpholino, benzoxazolinyl, benzimidazolyl, benzothiazolyl, carbazolyl , benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, etc.), formylalkyl (preferably having a carbon number of 3 to 40, more preferably a carbon number of 3 to 30, particularly Preferably, it is a methylidene group having a carbon number of 3 to 24, such as a trimethylcarbinyl group or a triphenylcarbenyl group, or the like. These substituents can be substituted. When there are two or more substituents, they may be the same or different. Also, if possible, they can be joined to each other to form a ring. In the above, 'alkyl group, alkenyl group and aryl group are preferred. The heteroaryl group having a nuclear atom number of 5 to 40 is preferably a structure represented by the following general formula (aa). -L-H Ar · (A A ) In the general formula (AA), L represents a direct bond, or a divalent aryl group, a divalent heteroaryl group, and HAr is a heteroaryl group. -11 - 200920718 The aryl group of the divalent group, for example, a phenylene group, a naphthyl group, a phenanthrene group, a fluorenyl group, a biphenylene group, a binaphthyl group, an anthracene group, or the like. Preferred is a phenylene group or a naphthylene group. The divalent heteroaryl group may, for example, be a pyridyl group, a fluorinated D group, a triazine group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a phenanthroline group or the like. Among them, a pyridyl group, a pyrimidyl group, a succinyl group, an exocarbazole group, and a dibenzofuranyl group are preferred. In terms of heteroaryl, for example, imidazolyl, pyridyl, pyrimidinyl, diazinyl, quinolyl, isoquinolinyl, furyl, thienyl, pyridyl, morpholino, benzoxazolinyl, Benzimidazolyl, imidazolidinyl, phenoxy 11 pyridyl, naphthyl imidazolyl, benzothiazolyl, oxazolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzosulfur The fluorene-terminated aryl group such as a phenyl group or a phenanthroline group, a divalent heteroaryl group or a heteroaryl group may have a substituent 'preferably the above substituent. Next, in the cave derivative of the present invention, the heteroaryl group is preferably a nitrogen-containing heterocyclic ring. Further, in the cave derivatives of the present invention, the heteroaryl group is preferably one having a nitrogen-containing five-membered ring-derived organism. Further, in the anthracene derivative of the present invention, the heteroaryl group is preferably a nitrogen-containing 6-membered ring derivative. Next, in the cave derivative of the present invention, the heteroaryl group is preferably a structure having the following general formula (3) to (9). -12- 200920718

13- • · (8) • · (8)200920718

In the general formulae (3) to (9), Ι^~: ί7 each represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 30, and a to f each represents an integer of 〇~3. R11 to R16 represent a hydrogen atom or a substituent. k is an integer of 1 to 4. Further, when k is 2 or more, R1 1 may be the same or different from each other. 1 is an integer of 1 to 3. Further, when 1 is 2 or more, R12 may be the same or different from each other. m is an integer of 1 to 2. Further, when m is 2, R13 may be the same or different from each other. n is an integer from 1 to 5. Further, when η is 2 or more, R14 may be the same or different from each other. R1 1 to R16 may be bonded to each other with a substituent adjacent thereto to form a saturated or unsaturated ring. An extended aryl group having a core carbon number of 6 to 30, for example, a ternary aryl group of the above L. Specific examples of the substituent may be exemplified by the aforementioned groups. Specific examples of the specific compounds of the general formulae (1) and (2) include, for example, specific examples of the compounds represented by the following general formulae (1 8 ) and (19). The organic EL device of the present invention is characterized in that an organic EL element having an organic thin film layer formed of a layer or a plurality of layers of at least a light-emitting layer is sandwiched between a cathode and an anode, and at least one layer of the organic thin film layer contains the above-mentioned derivative As a component of singly or as a mixture. Next, in the organic EL device of the present invention, the organic thin film layer has an electron injecting layer or an electron transporting layer, and the electron injecting layer or the electron transporting layer is composed of the above-mentioned cave derivatives as a single component or a mixture thereof. It is better. Further, in the organic EL device of the present invention, the light-emitting layer is preferably one having a composition containing the above-mentioned cave derivatives as a single component or a mixture. Further, in the organic EL device of the present invention, the electron injecting layer or the electron transporting layer containing the above-mentioned cave derivative is preferably composed of a reducing dopant, and in the organic EL device of the present invention, the aforementioned reductive doping The agent is a metal, a metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, an alkaline earth metal halide, a rare earth metal oxide, a rare earth The composition of one or two or more selected from the group consisting of a metal halide, an alkali metal organic complex, an alkaline earth metal organic complex, and an organic complex of a rare earth metal is preferred. In the organic EL device of the present invention, the light-emitting layer is preferably formed of a host material represented by the following general formula (10) and a dopant.

-15- 200920718 In the general formula (ίο), R42 to R5 3 represent a hydrogen atom or a substituent. However, at least one of R42 to R53 is independent of each other, and represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 60. The substituent may, for example, be the aforementioned group. Further, examples of the aryl group having a carbon number of 6 to 60 include aryl groups represented by Ar3 and Ar4. The use of such an anthraquinone derivative for an electron transporting material can be electron-injected into a small energy barrier by a bulk material of a wide-gap luminescent layer. That is, the affinity level of the electron transport layer may be made smaller in accordance with the portion where the affinity level of the light-emitting layer becomes smaller. For example, as a main material of a wide-gap luminescent layer, a cave derivative can be exemplified, and the electron transporting layer is also an anthracene derivative, and the conduction energy level can be reduced to the same extent to reduce the electron injection barrier. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described. [Configuration of Organic EL Element] First, the element configuration of the organic EL element will be described. The composition of the elements represented by the organic EL element can be exemplified as follows (1) anode/light-emitting layer/cathode (2) anode/hole injection layer/light-emitting layer/cathode (3) anode/light-emitting layer/electron injection layer/cathode (4) Anode/hole injection layer/light-emitting layer/electron injection layer/yin-16- 200920718 pole (5) anode/organic semiconductor layer/light-emitting layer/cathode (6) anode/organic semiconductor layer/electronic barrier layer/light-emitting layer/ Cathode (7) Anode / Organic Semiconductor Layer / Luminous Layer / Adhesion Improvement Layer / Cathode (8) Anode / Hole Injection Layer / Hole Transport Layer / Luminous Layer / Electron Injection Layer / Cathode (9) Anode / Insulation / Luminescence Layer/Insulation Layer/Cathode (10) Anode/Inorganic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode (11) Anode/Organic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode (1 2) Anode/ Insulation layer/hole injection layer/hole transport layer/light-emitting layer/insulation layer/cathode (13) anode/insulation layer/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode etc. . The organic EL element of the present embodiment is preferably provided with an anode, a hole injection layer, a light-emitting layer, an electron transport layer, and a cathode in at least order. In the above, it is generally preferred to use the configuration of (8), but it is of course not limited thereto. (Translucent Substrate) 17-200920718 The organic EL device is fabricated on a light-transmissive substrate. The light-transmitting substrate is preferably a substrate which supports the organic EL element, and has a light transmittance of 50% or more in the visible region of 400 to 7 Å, and is preferably a smooth substrate. Specifically, there are glass plates, polymer plates, and the like. Specific examples of the glass plate include soda lime glass, bismuth-containing bismuth glass, lead glass, aluminosilicate glass, borosilicate glass, barium boron silicate glass, and quartz. Further, examples of the polymer sheet include polycarbonate, acrylate, polyethylene terephthalate, polyether sulfide, and polyfluorene. (Anode) The anode of the organic EL element has a function of injecting a hole into the hole transport layer or the light-emitting layer, and it is effective to have a work function of 4.5 eV or more. Specific examples of the anode material may be indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, copper or the like. Further, for the purpose of injecting electrons into the electron transport layer or the light-emitting layer, the anode is preferably a material having a small work function. The anode can be produced by forming a thin film by a method such as a vapor deposition method or a sputtering method. When the light emission from the light-emitting layer is taken out from the anode, the light-emitting transmittance to the anode is preferably greater than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω / □ or less. The film thickness of the anode depends on the material, but is generally selected from the range of 10 nm to 1/zm, preferably 10 to 200 nm. -18- 200920718 (Light-emitting layer) The light-emitting layer of the organic EL element has the following functions. That is, it has (1) injection function; when an electric field is applied, a hole can be injected from the anode or the hole injection layer, an electron can be injected from the cathode or the electron injection layer, (2) a conveyor function; and the injected charge (electron and The function of the electric hole to move by the force of the electric field, (3) the function of illuminating; the place where the electron and the hole are re-bonded, and the function of the connection with the illuminating. However, the ease of injecting a hole can be different from the ease of injecting electrons, and the transfer energy expressed by the hole and the degree of electron mobility can be divided into small and small. As a method of forming the light-emitting layer, a known method such as a vapor deposition method, a spin coating method, or an LB method can be used. The light-emitting layer is preferably a molecular deposition film. The molecular deposition film is a film formed by deposition of a material compound in a gas phase state or a film formed by solidification of a material compound in a solution state or a liquid phase state, generally a film formed by the molecular deposition film and a film formed by the LB method (molecular accumulation) The membrane is distinguished by the difference in the agglutination structure, the high-order structure, or the function of the membrane. Further, as disclosed in Japanese Unexamined Patent Application Publication No. Publication No. No. No.---------------- Further, the thickness of the light-emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, most preferably 1 to 50 nm. If it is less than 5 nm, it is difficult to form a light-emitting layer. -19-200920718 It is difficult to adjust the chromaticity, and if it exceeds 5 〇 nm, the driving voltage rises. In the organic EL device of the present embodiment, the light-emitting layer is composed of a host material and a dopant. The cave derivatives of the present invention are also suitable as a host material. Further, specific examples of the host material include a compound represented by the following general formula (11).

In the general formula (1 1 ), R42 to R53 represent a hydrogen atom or a substituent. However, at least i of R42 to R53 are each independently, and represent a substituted or unsubstituted aryl group having a core carbon number of 6 to 60. The substituent may, for example, be the aforementioned group. Further, examples of the aryl group having a carbon number of ό60 to 60 include the above-mentioned Ar3, an aryl group represented by Ar4, and the other compounds represented by the general formula (1 1). -20- 200920718

-21 - 200920718

-22 - 200920718

-23- 200920718

In addition to the above-mentioned cave derivatives, a polyphenylene derivative, a mercapto derivative, a naphthalene derivative, a phenanthrene derivative, an anthracene derivative, a mercapto derivative or the like can be used as the organic EL. A luminescent material used with luminescent materials. -24-200920718 Other specific examples of the material of the host material which can be used for the light-emitting layer include, for example, the compounds represented by the following (i) to (ix). The following formula (i) represents an asymmetric enthalpy.

(Formula (υ中' 〗ο is a substituted or unsubstituted condensed aromatic group having a nuclear carbon number of 10 to 50. ArQ()2 is a substituted or unsubstituted nucleophilic group having a core carbon number of 6 to 5 Å. XG ()1~χ〇〇3 each independently, substituted or unsubstituted nucleocarbon number ό~50 square aryl group, substituted or unsubstituted aromatic atomic group 5~5〇 aromatic heterocyclic group, substituted or none Substituted carbon number 丨~5 〇 alkyl, substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, substituted or unsubstituted arylalkyl group having 6 to 50 carbon atoms, substituted or unsubstituted nuclear atom Number of 5 to 5 aryloxy substituted or unsubstituted arylthio groups having 5 to 50 atomic number, substituted or unsubstituted carbon number 1 to 50, (4), residue, halogen atom, cyano group , nitro, fun, ^ c are each an integer of 0 to 4. When η is μ and ^ η is 2 or more, [] can be the same or different) Specifically, as mentioned above The formula (2) is represented by a substituent. The following formula (ii) represents an asymmetric monoterpene derivative. -25- 200920718 p001 p008 r009 R002

^004^005 007

010 (ϋ) (Ar003)m R003-^V_r〇〇6 (Ar004)n are each independently substituted or absent, 11: and η are each 丨~Doo Af is different for the ring bond, m or n is 2 〜4 (in the formula (ii), A r. G 3 and A r 0 0 4 are substituted with an integer of 6 to 50 aromatic carbon groups. However, m=n=l and Ar003 is symmetrical. In the case of an integer of Ar1^3 and Ar004, m and n are different integers. R. 1 to R010 are each independently a hydrogen atom, a substituted or unsubstituted carbon number of 6*~, an aromatic ring group, Substituted or unsubstituted 5 to 5 Å aromatic heterocyclic group, substituted or unsubstituted carbon number 丨~"alkyl, substituted or unsubstituted ring-based, substituted or unsubstituted carbon number 丨~ 二院氧,取(四)Unsubstituted carbon number 6~5() of the aryl group, substituted or unsubstituted core atom number 5~5. The aryloxy group, substituted or unsubstituted nuclear atom number 5~ 5 〇 arylthio, substituted or unsubstituted carbon number 〇 5 〇 氧基 氧基 、, substituted or unsubstituted 甲 院, 竣, halogen, cyano, nitro, fun) Specifically, it can be mentioned in the above-mentioned general formula (2) : Ming represents a group represented by the following formula substituted group (Π i) Asymmetrical pyrene derivatives -26-200920718.

[In the formula (iii), each of Ar^5 and Ar^6 is a substituted or unsubstituted aromatic group having a core carbon number of 6 to 50. Each of L^1 and L^2 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted anthracene group or a substituted or unsubstituted dibenzosilolylene group. m is an integer of 0 to 2, η is an integer of 1 to 4, s is an integer of 0 to 2, and t is an integer of 0 to 4. Further, L^1 or Ar^5 is bonded to any of the 1 to 5 positions of the fluorenyl group, and LQQ2 or Ar^6 is bonded to any of the 6 to 10 positions of the fluorenyl group. However, when n + t is an even number, ArQQ5, ArQ()6, LQ()1, and LQQ2 satisfy the following (1) or (2). (1) At least one of Ar^-Ar1^6 and LGQ1 husband LGG2 (here, the base of the structure is not different) (2) Ar°°5=ArQQ6l ΐ/. 1^]^. . 2 (2-1) m at least one of s and n#t, or (2-2) m=sa n=t, (2-2-1) L^1 and L^2 Or 芘基 each keyed in -27- 200920718

The difference bonding position on ArGQ5 and ArGG6, or (2-2-2) LQ()1 and LQ()2, or the sulfhydryl bond at the same bonding position on Ar005 and ArQQ6 'LG()1 And the substitution position of the thiol group of LQQ2 or ArGG5 and Ar^6 is not the position of the 与 position and the 6-position, or the 2-position and the 7-position], and the specific base may be mentioned as described in the above-mentioned general formula (2). 'Based as a substituent, or a divalent group of such a group. The following formula (iv) represents an asymmetric anthracene derivative.

R〇l4; R' (in the formula (iv), a001 is substituted with a nuclear carbon number of 10 to 20; and A*302 is independently independent of each other, and the condensed aromatic ring group having a carbon number of 10 to 2 Å. 'and ΑΓΜ8 are each independently' are hydrogen atoms, 6 to 50 aromatic ring groups. Represents substitution or no or substitution or no substitution

～50 aromatic ring group, carbon number 6~, substituted or unsubstituted core 50 aromatic heterocyclic group, substituted, substituted or unsubstituted cycloalkyl group, ruthenyl group, substituted or unsubstituted core number Substituted or unsubstituted carbon number I~ alkyl substituted or unsubstituted carbon number i -28-~50 of 200920718 alkoxy, substituted or unsubstituted carbon number 6~5〇 An aryloxy group of 5 to 5 fluorene, a substituted or innumerable 5 to 50 arylthio group, a substituted or unsubstituted carbon number carbonyl group, a substituted or unsubstituted methyroalkyl group, a carboxyl group, a nitro group or a hydroxyl group.

AtQQ7 'Ar〇o8, rG19 and r{)2() can each be a ring structure which forms a saturated or unsaturated. However, in the formula (i v ), the 9-position of the center 蒽 and the symmetry-type base of the X-Y axis shown above are not bonded. The description of the general formula (2) is as shown by the substituent g. The following formula (v) represents an anthracene derivative. 〖Base, substituted or none; substituted nuclear atom: 1~50 of the courtyard oxygen halogen atom, cyano group: number, adjacent to the 1 〇 position' on the 蒽 body, can be cited in R〇23 r〇27

(R022)b (v) (in the formula (v), R02] to R. 3. Each independently, a group, a cycloalkyl group, a substituted aryl group, an alkoxy group, an aryl group, an alkenyl group, an aryl group The amine group or the substituted heterocyclic ring is represented by an integer of 1 to 5, and when they are 2 or more, R0 is the same, and each of them may be the same or different, and R〇2 may be bonded to each other. Ring, RG23 and R〇24, R025 are a hydrogen atom, a hospitaloxy group, a hospital amine group, a and b each 21 or RQ 2 2 】 mutually or R022 R 0 2 6 , R 0 2 7 and -29- 200920718, R〇29 and r()3() may be bonded to each other to form a ring. l〇03 is a single bond, 〇_, -S-, -N(R)- (R is an alkyl group or may be substituted Aryl), alkyl or aryl). Specifically, for example, the description of the above general formula (2) is used as a group represented by a substituent or a divalent group of such a group. The following formula (v i ) represents an anthracene derivative.

(In the formula (vi), R. 31~ is independently a hydrogen atom, an alkyl group, a ring-based group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamine group or an optionally substituted group. a plurality of cyclic groups: c, d, e, and f each represent an integer of 1 to 5, and when they are 2 or more, Rmi, R〇32, R〇36, or rG37 may be the same as each other. Different from each other, RG31 and RG32, rG33 or RG37 can be bonded to each other to form a ring, and R〇33 and 1^34, R1539 and R〇4〇 can be bonded to each other to form a ring. [(4) 4 is a single bond, _〇 _ '-S- ' -N ( R ) - ( r is an alkyl group or an optionally substituted aryl group), an alkyl group or an aryl group. Specifically, it can be exemplified by the above-mentioned general formula (2) -30-200920718, the base represented by the substituent or the divalent group of the following formula (vii) represents a spiro-based derivative.

(In the formula (vii), A°Q5 to AQQ8 are each independently substituted with a biphenyl group or a substituted or unsubstituted naphthyl group). In the above description of the general formula (2), the following formula (viii), which is a substituent, represents a group in which the condensed ring contains the compound '. (νϋ) indicates a substitution or a non-substituent such as; A〇14

(viii) (In the formula (viii), AQli to AQl3 represent the same divalent group as the former wing, and A014 to A016 represent a substituent of the formula (1). R"141 to 1^43 are each independently a hydrogen atom, a group having a carbon number of 3 to 6 and a carbon number of 1 to 6 (1), a Ra of the same carbon number of 1 to 6 carbon, a carbon number of 5 -31 - 200920718 - a aryloxy group, At least 1 of an aralkyloxy group having a carbon number of 7 to u, a quinone group having a carbon number of 5 to u, an nitro group, a cyano group, a carboxylic acid group or a halogen atom of A 〇1* 〜A 〇1 6 Each is a group having a condensed aromatic ring of 3 or more rings. Specifically, the description of the above-mentioned general formula (2) can be cited as the basis of the substituent. The following formula (ix) represents a mercapto compound.

And R: (1X), 'R 51 and R° 52 represent a hydrogen atom, a substituted or unsubstituted: a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or an unsubstituted heterocyclic group, a substitution Amine, cyano or ruthenium atoms. The rG51 bonded to the different sulfhydryl groups may be the same or different from each other, and the R, 51 and R 〇 52 of the bond may be the same or different. R. 53 and R〇54 a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, bonded Η: fluorenyl group ... 3 , Μ" can be the same or different from each other, the bond _ base Μ" and R ° 54 can be the same or different. Ar. " and Ar〇l2 :: condensed polycyclic ring of three or more substituted or unsubstituted groups in total of the ring: a total of three or more substituted or unsubstituted carbon bonds in the total of aroma group or a benzene ring and a hetero ring The condensed polycyclic heterocyclic group of the fluorenyl group, Ar() 11 and or different. 11 is an integer of ~1()).具体'; The specific group may, for example, be -32 - 丄 200920718 The description of the above general formula (2) is shown as a substituent. When a phosphorescent dopant is used, specific examples of the host material compound include, for example, a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, and a polyarylalkane derivative. , pyrazoline derivatives, pyrazolone derivatives, phenylene diamine derivatives, arylamine derivatives, amine substituted chalcone derivatives, styrylpurine derivatives, anthrone derivatives, anthracene derivatives a substance, an anthracene derivative, a decazane derivative, an aromatic third amine compound, a styrylamine compound, an aromatic dimethylene compound, a phthalocyanine compound, an anthraquinodimethane derivative, Heterocyclic ketone derivatives, diphenyl hydrazine derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, methylene methane derivatives, distyryl pyrazine derivatives, naphthyl fluorenyl groups, etc. Various carboxylic acid anhydrides, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives or metal phthalocyanines, benzoxazoles or metal complexes with benzothiazole as a ligand Metal complex polyalkylene compound, poly(N a conductive polymer oligomer such as a vinylcarbazole derivative, an aniline copolymer, a thiophene oligomer or a polythiophene, a polythiophene derivative, a polyphenylene derivative, or a polyphenylene vinylene A polymer compound such as a derivative or a polyfluorenyl derivative. The host material compound may be used singly or in combination of two or more. Specific examples include the following compounds. -33- 200920718

In the organic EL element of the present invention, at least one of a phosphorescent dopant and a fluorescent dopant is preferably used as the host material of the light-emitting material in the light-emitting layer. Further, a light-emitting layer containing the dopant of the cave derivative of the present invention may be laminated. Phosphorescent dopants are compounds that can be illuminated by triple term excitons. Although there is no particular limitation on the triplet exciton luminescence, a metal complex of at least one metal selected from the group consisting of Ir, RU, Pd, Pt, Os, and Re is a good 'D brun metal wrong. The compound or ortho-metalated metal complex is preferred. The phosphorescent compound may be used singly or in combination of two or more. The porphyrin metal complex is preferably a porphyrin platinum complex. -34- 200920718 The ligand forming the ortho-metalated metal complex may be various, and preferred ligands may, for example, be a phenylpyridine skeleton, a bipyridine skeleton or a compound having a phenanthroline skeleton, or 2_ A phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2-(2-thienyl)pyridine derivative, a 2-(1-naphthyl)pyridine derivative, a 2-phenylquinoline derivative or the like. These ligands may have substituents in response thereto. In particular, it is preferred to introduce a fluoride or a trifluoromethyl group as a blue dopant. Further, the ligand may be further provided with a ligand other than the above ligand such as acetyl acetonat or picric acid. Specific examples of such a metal complex compound include the compounds shown below. Further, in the present invention, it is particularly preferred to combine with a phosphorescent dopant which emits light in the red region. Not limited to this, an appropriate complex can be selected from the desired luminescent color, element properties, and host material compound used. 35- 200920718

-36- 200920718

Λ A , Ν-Ν, /Ν-Ν lr(ppy)3

, /Β\ Ν~Ν Ν~Ν

-37- 200920718

-38- 200920718

The content of the light-emitting layer of the phosphorescent dopant is not particularly limited, and may be appropriately selected depending on the purpose, for example, 1 to 70% by mass, preferably 1 to -39 to 200920718 30% by mass. When the content of the phosphorescent compound is less than 0.1% by mass, the light emission is weak, and the effect of the effect is not effectively exhibited. When the content exceeds 70% by mass, the concentration extinction phenomenon is remarkable, and the element performance is deteriorated. In terms of a fluorescent dopant, a honey compound, an aromatic compound, a tris(8-quinolinolate) aluminum complex, or the like, a honey complex, a coumarin derivative, a tetraphenylbutadiene derivative, and a double Styrene-based aryl derivatives, oxadiazole derivatives, etc., preferably with the desired luminescent color-selective compound, with styrylamine compounds, styryldiamine compounds, arylamine compounds, aryldiamine compounds good. Further, a condensed polycyclic aromatic compound of a non-amine compound is also preferable. These fluorescent dopants can be used singly or in combination. The content of the light-emitting layer of the fluorescent dopant is not particularly limited, and may be appropriately selected depending on the purpose, and is, for example, 0.1 to 70% by mass, preferably 1 to 3 % by mass. The styrylamine compound and the styryldiamine compound are preferably those represented by the following formula (A).

(8) (In formula (A), Ar1Q1 is the base of p-valent, which is the base of P valence corresponding to phenyl, Caiji-40-200920718, biphenyl, terphenyl, decyl, distyrylaryl Ar1()2 and ArI()3 are each an aromatic hydrocarbon group having 6 to 20 carbon atoms, and Ar1()1, Ar1()2, and Ar1G3 may be substituted. Any one of Ar1C)1 to Ar1G3 is a styryl group. Replaced. More preferably, at least one of Ar1()2 or Ar1()3 is substituted with a styryl group. P is an integer of 1 to 4, preferably an integer of 1 to 2. Here, examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a triphenylene group. Wait. The arylamine compound and the aryldiamine compound are preferably those represented by the following formula (B).

(B) (In the formula (B), Ar1 1 1 is a q-valent substituted or unsubstituted aromatic group having a core carbon number of 5 to 40, and Ar 112 and Ar1 13 are each a substituted or unsubstituted nucleus carbon number 5~ An aryl group of 40. q is an integer of 1 to 4, preferably an integer of 1 to 2. Here, the aryl group having a core carbon number of 5 to 40, for example, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, a dipyridyl group, a biphenyl group, a triphenylene group, a pyrrolyl group, a furyl group, Thiophenyl, benzothiophenyl, oxadiazolyl, diphenylfluorenyl, fluorenyl, oxazolyl, pyridyl, benzoquinolyl, fluoranthenyl, fluorenyl-41 - 200920718 蒽Base, sulfhydryl, sulfhydryl, sulfhydryl, fluorenyl, triphenylene, ruthenium, benzofluorenyl, phenyl fluorenyl, bisindolyl, naphthyl, anthracenyl, sulfhydryl, fluorenyl It is better.

Ar111 is preferably a group having the above q valence. When Arni is divalent, the group represented by the following formula (c) '(D) is more preferable, and the group represented by the formula (D) is more preferable.

(in the formula (C), r is an integer of 1 to 3). Further, a preferred substituent for the aryl group may, for example, be an alkyl group having 1 to 6 carbon atoms (ethyl, methyl, propyl, η-propyl, s-butyl, t-butyl, pentyl, Alkyloxy group having a carbon number of 1 to 6 (ethoxy group, methoxy group, i-propoxy group, η-propoxy group, s-butoxy group, t-butoxy group) An aryl group having a core carbon number of 5 to 40, an amine group substituted with an aryl group having a core carbon number of 5 to 4 Å, having an aryl group having a nucleus of 5 to 40 or less; A aryl group having an aryl group having 5 to 40 carbon atoms, an ester group having an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom and the like. Further, specific examples of the dopant include a compound containing a benzidine represented by the following general formula (1 2 ). -42- • (12) 200920718

In the general formula (12), Ar21 to Ar24 are each independently an unsubstituted aryl group having a core carbon number of 6 to 14. L ! ! means benzene, naphthalene, anthracene, phenanthrene. The P system is independently an integer of 1 to 6, and L! ! is the same or different from each other. Further, when p is 2 or more, the positions may be the same or different. s is 0 or 1. Further, in the case of a dopant, in place of the above general formula (1, a compound represented by the following general formula (13) can be used, and when a substitution or a substitution or a substitution of p is 2 or more, L 1 f and each other are used. Take the compound of the cave of the cave

• (13) In the general formula (1 3 ), Ar25 to Ar28 are each independently unsubstituted phenyl, naphthyl, and phenanthrene. L12, L13 are each independently or unsubstituted benzene, naphthalene, phenanthrene. The substituent may, for example, be 肓, which represents substitution or standing, and represents a group substituted in the description of the general formula (2-43-200920718). Further, the dopant of the formula (14) to the base of the fluoranthene can be derived from a compound having any of the following structures (17).

• · (14)

• · (15) X37 χ3νΛ^χ36

Χ25"]/^χ27 X26 -44- • · · (16) 200920718

Atom, halogen atom, substitution _ substitution, 吉曰独乂' is the number of carbon atoms of the hydrogen atom number 30, substituted or unsubstituted carbon atom number 1~; 30 alkoxy, or cyclic Know: Xingji, substituted or unsubstituted linear 'circular carbon number 1~3〇 is even better, or (4) one: == = = face 'branch or ring carbon number 2 to 3. a chain of a benzyloxy group, a substituted or unsubstituted linear, branched or cyclic carbon atom having 2 to 3 thiol groups, a substituted or unsubstituted carbon atom number of 7~ _ 万 兀 / 兀, or An unsubstituted aralkyl group having 7 to 30 carbon atoms per | „ Z 兀 / 兀 基 、, substituted or unsubstituted aralkylthio group having 7 to 30 carbon atoms, substituted or unsubstituted carbon atom 〇2〇, substituted or unsubstituted carbon atom number 6~ aryloxy group, substituted or unsubstituted carbon atom number 6~2〇 笮 乙 ethyl thio group, substituted or unsubstituted carbon number 2 to 30 amino group, cyano group, methadone group, hydroxy-COOR group (wherein, Rie represents a hydrogen atom, a substituted or unsubstituted direct bond, a branched or cyclic group of 1 to 30 carbon atoms) , substituted or unsubstituted, linear, branched or cyclic, 2 to 30 carbon chain, substituted -45-200920718 or unsubstituted carbon atom 7 to 30. S: ~^·〇·甄丨 方 、, or substituted or unsubstituted aryl group with 6 to 30 carbon atoms), _c 〇 R 2 e group (in the base, Rae represents a hydrogen atom, a substituted or unsubstituted linear chain, Or a cyclic k-group having 1 to 30 carbon atoms, a substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom number of 7 to 3 Å. a aryl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an amine group), a -OCOR3e group (in the group, a substituted, unsubstituted linear, branched or cyclic carbon atom) 1 to 30 alkyl, substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or not Further, in the X1 to X52, the "adjacent group and the substituent of each group are bonded to each other" to form a substituted or unsubstituted carbocyclic ring. The host material containing the above-mentioned caves, and the dopant containing any of the benzidines and the caves, constitute a light-emitting layer, and the energy gap of the dopant becomes larger. At the same time, the affinity level of the dopant becomes larger than that of the host material. The affinity level is low. Therefore, by using a wide-gap dopant, it is more suitable to shorten the wavelength of the blue emission wavelength and suppress the electron injection to the dopant. Therefore, it is preferable to use the cave derivative of the present invention or the host material of the general formula (10). (Curve injection/transport layer (electron transport region)) The hole injection/transport layer is helpful. The hole in the light-emitting layer is injected, and the layer of the light-emitting region is large in mobility, and the ionization energy is usually as small as 5 · 5 eV or less. In this way, the hole is injected and transported to make the hole with a lower electric field strength. The material to be transported to the light-emitting layer is better, and the mobility of the further hole is -46-200920718, for example, when an electric field of l〇4~l〇6V/cm is applied, at least 10_4 Cm2/Vs is preferred. Such a hole injection layer or hole The material for forming the transport layer, such as a stomach, such as a triazole derivative (refer to the specification of U.S. Patent No. 3,112,197, etc.), an oxadiazole derivative (refer to the specification of U.S. Patent No. 3,1,89,447, etc.), an imidazole derivative (special disclosure) Japanese Patent Publication No. 3-7-6096, et al. Bulletin, the same as 5 1 - 1 0983, special opening Japanese Patent Publication No. 5-93224, No. 55-17105, No. 56-4148, No. 55-108667, No. 55-156953, No. 56-36656, etc., pyrazoline derivatives And a pyrazolone derivative (U.S. Patent No. 3,180,729, the specification of which is the same as the specification of No. 4,278,746, Japanese Patent Laid-Open Publication No. Hei 5-5-8 064, the same as No. 5 5 - 8 8 065, the same as 49-105537 No. 55-51086, the same as No. 56-80051, the same as No. 56-88141, the same as No. 57-45545, the same as No. 54-112637, the same as 55-74 546, etc., benzene A stilbene diamine derivative (U.S. Patent No. 3,61,5,404, Japanese Patent Publication No. 51-10105, the same as No. 46-3 7 1 2, the same as 47-253 3 6 , and a special opening 5 4 - 5 3 4 3 5, the same as 5 4 - 1 1 0 5 3 6 , the same as 5 4 1 1 9925, etc., arylamine derivatives (US Patent No. 3, 5 67, 4 5 No. 0 specification, the same as No. 3, 1 0 0 0, 703, the same as No. 3, 240, 597, the same as No. 3, 65 8, 520, the same as the 4, 232, 1 03, the same as 4, 1 75, 96 1 Japanese Patent Publication No. 4,0 1 2,3 76, Japanese Patent Publication No. Sho 49-3 5 702, and the same as -47-200920718 3 9-275 77, and JP-A-55-1442-50- No. 119132, the same as the specification of No. 56-22437, No. 1, 10, 518, etc.), the amine replaces the specification of the German Patent No. 3,526, 501, and the like, and the specification of the Japanese Patent No. 3, 2, 57, 203, etc. , and the biotechnology (refer to the Japanese Patent Laid-Open No. 5-6 - 4 6 2 3 4, etc.), the Japanese Patent Publication No. 54- 1 1 08 37, etc., and the introduction of the 3rd, 7th, 7th, and 462 specifications. Japanese Patent Publication No. 5 5-52063, the same as Japanese Patent Publication No. 5-5-520, the same as Japanese Patent Publication No. 55-85495, and the same as No. 57-11350, No. 5-7-48749 Japanese Patent Publication No. 2-311591 (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 61-72. Japanese Patent Publication No. 62-36674, the same as the Japanese Patent No. 62-30255, the same as Japanese Patent Publication No. 60-93455, No. 60-94462, the same as the Japanese Patent Publication No. 60-174749, the same publication, and the like. Specification), polydecane system ( Japanese Patent Publication No. Hei No. Hei-2-282263, the conductive polymer oligothiophene oligomer disclosed in Japanese Patent Publication No. Hei 2-282263, and the like. The material of the hole injection layer or the hole transport layer may be, for example, a porphyrin compound (expressed in Japanese Patent Application Laid-Open No. Sho. No. Sho. No. Sho. No. 63-209), an aromatic tertiary amine compound, and a styryl group. The same, West German patent ketone derivative (Mexican derivative (Metrizinyl fluorenone derivative (. US Patent Publication, the same as 55-46760, the same: reference), 芪 1 - 2 2 8 4 5 pp., the same as the publication of the Japanese Patent Publication No. 60-175052, No. 4,950,950, and the aniline cleavage of the aniline compound (in particular, the guanamine compound ( _ -48 - 200920718 National Patent No. 4,12,7,12, and Japanese Patent Laid-Open No. 5-3-2703 No. 3, the same as No. 54-58445, the same as No. 54-149634, the same as No. 54-64299, the same 5 5 - U.S. Patent No. 7,945, the same as the Japanese Patent Publication No. 5-5-1 442, the same as the Japanese Patent Publication No. 56-119132, the same as the Japanese Patent Publication No. 61-295558, the same as the Japanese Patent Publication No. 61-98353, and the like. A tertiary amine compound having two condensed aromatic rings in the molecule as described in U.S. Patent No. 5,0 1,1,5,9,9, For example, 4,4'-bis(N-(1-naphthyl)-N-phenylamine)biphenyl, and the triphenylamine unit described in JP-A-4-30086-8 3 star-exploded 4,4',4"-tris(N-(3-methylphenyl)-N-phenylamine)triphenylamine, etc. Further, Patent Gazette No. 36 1 4405, 3571977 The hexazatriphenylene derivative described in the above-mentioned U.S. Patent No. 4,780,536, or the like, can also be suitably used as a material for hole injection. Further, the above-mentioned aromatic secondary methyl compound as a material of the light-emitting layer can be used. In addition, an inorganic compound such as p-type Si or p-type SiC may be used as the material of the hole injection layer or the hole transport layer. The hole injection layer or the hole transport layer may be formed of one or more of the above materials. One layer is formed, and the hole injection layer or the hole transport layer may be a hole injection layer or a hole transport layer formed by laminating other compounds. The film thickness of the hole injection layer or the hole transport layer is It is not particularly limited, and is preferably 20 to 200 nm. (Organic semiconductor layer) The organic semiconductor layer is a layer that facilitates hole injection or electron injection to the light-emitting layer. The electrical conductivity of 10_1 () s / cm or more. The organic semi-conductive -49 - 200920718 body layer material, the use of thiophene-containing oligomers or the arylamine-containing oligomers described in JP-A-H08-193191 Conductive oligomers such as materials, conductive dendrimers such as arylamine dendrimers, and the like. The film thickness of the organic semiconductor layer is not particularly limited, but is preferably 10 to 1,00 〇 nm. (Electron injection/transport layer (electron transport region)) The electron injecting/transporting layer can be further laminated between the organic light-emitting layer and the cathode. The electron injecting and transporting layer is a layer that assists in the injection of electrons into the light-emitting layer, and the electron mobility is large. Since the light emitted by the organic EL is reflected by the electrode (in this case, the cathode), it is known that the light emitted directly from the anode and the light taken out by the reflection of the electrode are dry. In order to utilize this dry effect efficiently, the electron transport layer is preferably selected to a film thickness of several nm to several ym, especially when the film thickness is thick, in order to avoid voltage rise, an electric field is applied in addition to 1〇4~l〇6V/cm. When the electron mobility is at least 1 (T5cm2/VS or more is preferred. In the organic EL element of the present embodiment, the electron transport layer contains an electric field strength of 2.5x10V/cm, and the electron mobility is 1χ1〇-4~

*· X 1 0 _2 c m 2 / V s compound. Next, a specific example of the electron transport layer may, for example, be a compound represented by the following formula (18).

Ar1—Ch—Ar2 * · · (18) In the general formula (18), 'Ch denotes a substituted or unsubstituted cave, -50- 200920718 'Ar is independent, indicating a substituted or unsubstituted nuclear carbon number of 6 to 40 An aryl group, or a substituted or unsubstituted group having 5 to 4 Å of a heteroaryl group. However, at least one of 'Ar1' Ar2 is a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms. Further, the 'electron transport layer' is preferably a compound represented by the above general formula (18), and the compound represented by the following formula (19) is more preferably used.

In the general formula (19), Ar3 and Ar4 are each independently, and represent a substituted or unsubstituted aryl group having 6 to 40 nucleus carbon atoms or a substituted or unsubstituted aryl group having 5 to 40 core atoms. . However, at least one of Ar3 and Ar4 is a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms. Ri~r1〇 — a hydrogen atom or a substituent. Examples of the aryl group having a core carbon number of 6 to 40 and the heteroaryl group having a nuclear atom number of 5 to 4 Å and a substituent include the above-mentioned groups. Next, in the compound represented by the general formula (1 8 ) or (1 9 ), the hetero-51 - 200920718 aryl group may be a nitrogen-containing heterocyclic ring, a nitrogen-containing 5-membered ring derivative, and a nitrogen-containing 6-membered ring derivative. It may have a structure represented by the following general formula (AA) or a configuration of the following general formulas (20) to (26). -L-HAr ** (A A) In the general formula (AA), L and HAr are the same as described above.

• . . . (20) • · · (21) • (22) -52- • · · (23)200920718

• (twenty four)

(26) In the general formulae (20) to (26), Ι^~:ί7 are each substituted or unsubstituted aryl group having a core carbon number of 6 to 30, and a to f are each an integer of 0 to 3. R11 to R16 represent a hydrogen atom or a substituent. k is an integer of 1 to 4. Further, when k is 2 or more, Rn may be the same or different from each other. 1 is an integer of 1 to 3. Further, when 1 is 2 or more, R12 may be the same or different from each other. m is 1~2 -53- 200920718 Integer. Further, when m is 2, R13 may be the same or different from each other. n is an integer from 1 to 5. Further, when η is 2 or more, R14 may be the same or different from each other. Rl1 to R16 may be bonded to each other with a substituent adjacent thereto to form a saturated or unsaturated ring. The exoaryl group having a core carbon number of 6 to 30 may, for example, be a divalent aryl group of 1 in the above general formula (AA). The specific examples of the substituent are also the same as described above. Receiver, the general formula (]8 is shown below. The specific compound represented by (1 9) -54- 200920718

55- 200920718

-56 200920718

57- 200920718

-58-

2009207 IS

-59 - 200920718

s

-60- 200920718

A preferred embodiment of the organic EL element is a member containing a reducing dopant in the field of transporting electrons or in the interface between the cathode and the organic layer. Here, the far-end dopant is defined as a substance which can reduce the electron transporting compound. However, in order to have a certain degree of reducibility, various substances can be used, for example, alkali metal, alkaline earth metal 'rare earth metal, alkali metal oxide-61 - 200920718, alkali metal halide, alkaline earth metal oxidation a halide of a compound, an alkaline earth metal, an oxide of a rare earth metal or a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal The group selected one less material. Further, more specifically, preferred reducing dopants include, for example, Li (work function··2.9 eV), Na (work function·· 2.36 eV), K (work function: 2.28 eV), and Rb (work function). : 2.16eV) and Cs (work function: 1.95eV) of at least one selected alkali metal or Ca (work function: 2.9eV), Sr (work function: 2.0~2_5eV) and Ba (work function) : 2.52 eV) At least one alkaline earth metal selected from the group formed, and the work function is preferably 2.9 eV or less. Among these, a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals are particularly high in reducing ability, and by adding a small amount to the electron injecting region, the luminance of the organic EL element can be improved or the life can be extended. Further, in the case of a reducing dopant having a work function of 2 to 9 eV or less, a combination of two or more kinds of alkali metals is preferable, a combination of a specific system and a Cs, for example, Cs and Na, Cs and K, Cs and Rb. Or Cs combined with Na and K is preferred. By combining the Cs, the reducing power can be effectively utilized, and by adding the electron injecting region, the luminance of the organic EL element can be improved or the life can be extended. An electron injecting layer composed of an insulator or a semiconductor may be further provided between the cathode and the organic layer. In this case, leakage of current can be effectively prevented, and electron injectability can be improved. -62- 200920718 As such an insulator, it is preferred to use at least one metal compound selected from the group consisting of an alkali metal chalcogenide, a soil-based metal chalcogenide, a metal halide, and a soil-based metal halide. When the electron injecting layer is composed of such an alkali metal chalcogen compound or the like, the electron injectability can be further improved, which is preferable. Specifically, preferred alkali metal chalcogenides are, for example, L i 2 〇, K20, Na2S, Na2Se and Na20, preferably alkaline earth metal chalcogenides such as CaO, BaO, SrO, BeO, BaS and CaSe. Further, preferred halides of alkali metals are, for example, LiF, NaF, KF, LiCl, KC1, and NaCl. Further, preferred halides of alkaline earth metals are, for example, fluorides such as so-called CaF2, BaF2, SrF2, MgF2 and BeF2 or halides other than fluorides. (Cathode) In the cathode aspect, a metal having a small work function (4 e V or less) of a metal, an alloy, an electrically conductive compound, or a mixture of these may be used as an electrode material for electron injection electron injection, a transport layer or a light-emitting layer. Specific examples of the electrode material include sodium, sodium potassium alloy, magnesium, lithium, a silver alloy, aluminum/aluminum oxide, an aluminum-lithium alloy, indium, and a rare earth metal. This cathode can be produced by forming a thin film of such an electrode material by vapor deposition or sputtering. Here, when the light emitted from the light-emitting layer is taken out from the cathode, the transmittance to the cathode is preferably greater than 10%. Further, the film resistance of the cathode is preferably several hundred Ω / □ or less, the film thickness is lOnm 〜 l / / m, and the 聿 father is 50 " · 200 ηιη. -63- 200920718 (Insulation Layer) The organic EL element is susceptible to leakage due to leakage or short-circuit due to an electric field applied to the ultra-thin film. In order to prevent this, it is preferable to insert an insulating thin film layer between a pair of electrodes. Materials used for the insulating layer, such as alumina, lithium fluoride, lithium oxide, barium fluoride, barium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, barium oxide, barium oxide , tantalum nitride, boron nitride, molybdenum oxide, antimony oxide, vanadium oxide, and the like. Mixtures or laminates of these may also be used. [Manufacturing Method of Organic EL Element] Next, a method of manufacturing the organic EL element will be described. By the materials and the formation methods exemplified above, the anode, the light-emitting layer, the necessary hole injection layer, and the necessary electron injecting layer are formed, and the organic EL element can be further formed by forming the cathode. Further, an organic EL element can be produced from the cathode to the anode or in the reverse order of the foregoing. In the following description, an example of production of an organic EL device having an anode/hole injection layer/light-emitting layer/electron injection layer/cathode arranged on a light-transmitting substrate is described. First, on a suitable light-transmissive substrate, the film formed by the anode material is formed by a method such as vapor deposition or sputtering, such as a film thickness of 1 #m or less, preferably 10 to 2 〇〇 nm. Make the anode. A hole injection layer is then provided on the anode. -64 - 200920718 The formation of the hole injection layer can be carried out by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The film thickness is preferably in a range selected from 5 nm to 5 /z m. Then, the formation of the light-emitting layer provided on the hole injection layer can be performed by a dry process represented by a vacuum evaporation method using a desired organic light-emitting material, or a wet process such as a spin coating method or a casting method. The material is formed by thinning. Next, an electron injecting layer is provided on the light emitting layer. The formation by a vacuum vapor deposition method is exemplified. Finally, the organic EL element can be obtained by laminating the cathode. Since the cathode is made of metal, a vapor deposition method or a sputtering method can be used. However, in order to protect the underlying organic layer and prevent damage during film formation, vacuum evaporation is preferred. The method of forming each layer of the organic EL element is not particularly limited. A conventionally known method of forming a vacuum vapor deposition method, a spin coating method, or the like, that is, the organic thin film layer is impregnated by a vacuum deposition method, a molecular vapor deposition method (MBE method), or a solution dissolved in a solvent. Coating methods such as spin coating, casting, bar coating, roll coating, and inkjet are formed by a known method. The film thickness of each organic layer of the organic EL device is not particularly limited. However, when the film thickness is too thin, defects such as pinholes are likely to occur. Conversely, when the film thickness is too thick, a high applied voltage is required, so that the efficiency is deteriorated. The range of nm to 1 μ m is preferred. Further, in the case where a DC voltage is applied to the organic EL element, the anode has a polarity of -65 - 200920718 + 'the cathode is -, and when a voltage of 5 to 40 V is applied, light is observed. Further, even if the applied voltage and current do not flow in the opposite polarity, no light is generated at all. Also, in the case where an AC voltage is applied, uniform luminescence can be observed only when the anode is at the polarity of +' cathode. Additional communication can be any waveform. [Embodiment] [Embodiment] Next, an embodiment related to the present invention will be described. [Synthesis of Compound] First, the synthesis of the compound used in the preparation of the sample of the example (synthesis of 2-(4-bromophenyl)-1-phenyl-1 fluorene-benzimidazole) 2-(4-bromophenyl) The synthesis of 1-phenyl-1H-benzimidazole was carried out following the following scheme.

3.0 g (15 mmol) of 4-bromobenzoic acid was suspended in 1,2-dichloroethane 30 mL '2.7 g (23 mmol) of chlorosulfite, 3 drops of N,N-dimethylmethyl 66 - 200920718 indole to The benzoic acid of the raw material disappeared, and heating and stirring were carried out for 1 hour, 3 minutes, and about 50 °C. After completion of the reaction, the solvent and excess sulfoxide chloride were distilled off. The obtained acid chloride was dissolved in N-methylpyrrolidinium 30 mL, and N-phenyl-1,2-phenylene was added. Diamine 2.8 g (15 mmol) was stirred at room temperature for 1 night. After completion of the reaction, water was added thereto, and the precipitated solid was filtered, and further washed with water and dried under reduced pressure to give 5.2 g of 4-bromo-N-(2-phenylamine-phenyl)-phenylamine. The phenylguanamine was heated and stirred under reduced pressure (about 20 mm H g ) at about 300 ° C for 3 Torr. After the completion of the reaction, it was dissolved in dichloromethane and purified by sand column chromatography to obtain 2 - ( 4 - bromophenyl) - 1 -phenyl - 1 - benzopyrene 3.5 g (yield 80%) . (Synthesis of 5-bromo-1,2-diphenyl-1H-benzimidazole) The synthesis of 5-bromo-1,2-diphenyl-1H-benzimidazole was carried out in accordance with the following scheme. -ΝΗ; Br AcONa ΒΓΧΧ^2 Na2S2〇4

p-TsOH --->

2,5-dibromonitrobenzene 1 〇g ( 35·6_〇1 ), sodium acetate 8.8 g (10 〇 7 mmol), aniline 6.6 g (hmmol) were heated at 160 ° C for 9 hours under nitrogen atmosphere. Stir. The reaction solution was allowed to cool to room temperature, diluted with ethyl acetonitrile, and dried. After concentrating the filtrate, it was purified by silica gel column chromatography to give 9.9 g of 4-bromo-2-nitrodiphenylamine (yield: 3%). -67- 200920718 Dissolve 9.9 g (33.8 mm 〇l) of 4-bromo-2-nitrodiphenylamine in 75 mL of tetrahydrofuran, and dilute the sodium dithionite 30 g (170) under nitrogen atmosphere at room temperature. Methyl) / water 100 mL solution. Further, methanol 10 mL· was added and stirred for 3 hours. Next, 75 mL of ethyl acetate was added, and a solution of 5.7 g (67.8 mmol) of sodium hydrogencarbonate / 60 mL of water was added. Further, a solution of 4.8 g (34 mmol) of ethyl benzamidine chloride / 25 mL of ethyl acetate was added dropwise and stirred at room temperature for 5 hours. The extract was extracted with ethyl acetate. After washing with water, 10% aqueous potassium carbonate solution and saturated brine, the mixture was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 5-bromo-2-phenyl. Ampicillin 5.6 g (yield 45%). 5.6 g (15 mmol) of 5-bromo-2-phenylamine benzamide was suspended in 60 mL of xylene, and P-toluenesulfonic acid 1 water and 0.88 g (4.6 mmol) were added thereto, followed by heating for 5 hours. Azeotropic dehydration at reflux. The reaction solution was allowed to cool to room temperature. The solvent was evaporated under reduced pressure. The obtained solid was washed with ethanol to give 5-bromo-1,2-diphenyl-1 fluorene-benzimidazole 2.5 g (yield 46%). (Synthesis of 1-(4-bromophenyl)-2-phenyl-1H-benzimidazole) Synthesis of 1-(4-bromophenyl)-2-phenyl-1H-benzimidazole follows the following flow chart Implementation.

No2 NH Na2S2〇4

-68-200920718 2-Bromonitrobenzene l〇〇g (495 mmol), ethylene g 1.63 mol), and 4-bromoaniline 100 g (590 mmol) were stirred and stirred for 8 hours at ί °C. The reaction solution was cooled to ethyl acetate and diluted. After the filtrate was concentrated, the residue was obtained (yield: 2 2%) of (4-bromophenyl)-(2-nitrophenyl)amine. 38 g of (4-bromophenyl)-(2-nitrophenyl)amine (dissolved in 300 mL of tetrahydrofuran, stirred at room temperature under stirring at room temperature, sodium thiosulfate ll 〇 g ( 640 mmol) / water 300 mL Thereafter, a solution of 200 mL of ethyl acetate and a solution of 1 260 mmol of carbonic acid / 200 mL of water was added. Further, a solution of benzene (1 80 mmol) / ethyl acetate 10 mL was added dropwise while in the chamber. The extract was extracted with ethyl acetate, washed with 1% by weight of aqueous carbonated water and brine, and then evaporated to dryness over anhydrous sodium sulfate to give N-[2-(4-bromophenylamine)phenyl. ] (yield 4 5 %). N-[2-(2-bromophenylamine)phenyl]benzoquinone 2) was suspended in 300 mL of xylene, and p-toluenesulfonic acid (29 mmol) was added thereto, followed by azeotropic heating under reflux for 3 hours. Ethyl acetate and dichloromethane were added to the reaction solution, and the mixture was filtered. The organic layer was extracted with a mother liquid, and the mixture was dried over anhydrous sodium sulfate and evaporated. Purification by galvanic column chromatography to obtain 1 - (4-bromophenyl)-2 g sodium 1 30 g (at room temperature, 180 ° room temperature, washed with acetonitrile, phytochrome (: 1 3 0 mm) ο 1 ), drop the second Asian. 5 hours to stir the sodium 22g (: formazan chlorine 25g warm stirring 1 small potassium aqueous solution, dry, so that the solvent benzoguanamine 21 g 1 g (5 7mmol 1 water and 6g dehydrated. In the case of cold water, the insoluble water is washed to obtain a white crystallization of phenyl-1H-benzene-69- 200920718 imidazole 10 g (yield 5 2 %). (Synthesis of 2-bromo-6-phenylpyridine) 2 - Desert-6 - The synthesis of the base shame D疋 follows the following flow chart. b(oh)2

Na2C03 NaN02 2-Ethyl-6-bromopyridine 10g (58mm〇l), phenylboronic acid 8.5g (70 mmol), tetrakis(triphenylphosphine)IE 1.3g (1.2mmol) dissolved in 1,2-dimethyl 60 mL of oxyethane was added to 30 mL of a 2.0 M sodium carbonate aqueous solution, and the mixture was heated under reflux for 8 hours under an argon atmosphere. After the reaction is completed, the aqueous layer is removed. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated. The residue was purified by silica gel column chromatography to give EtOAc (yield: 70%) of 2-amine-6-phenylpyridine. Stirring was carried out by adding 6.9 g (40 mmol) of 2-amine-6-phenylindole to 48% HBr 50 mL. The solution was cooled to -20 ° C, and bromine 7.7 g (48 mmol) was added dropwise. Further, 2.8 g (40 mmol) of sodium nitrite was added dropwise. Stir for 3 hours while warming to room temperature. After completion of the reaction, extraction was carried out with ethyl acetate to remove the aqueous layer. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated. The residue was purified by silica gel column chromatography to give 2-bromo-6-phenylpyridine 7.5 g (yield: 80%). -70-200920718 (Synthesis of 2-bromo-4,6-diphenylpyrimidine) The synthesis of 2-bromo-4,6-diphenylpyrimidine was carried out in accordance with the following scheme.

2-amine-4,6-dichloropyran 9.85 (58〇1111〇1), phenylboronic acid 17g (140mm〇1), tetrakis(triphenylphosphine)palladium 2.7g (2.3mmol) were dissolved in 1, 2 - Dimethoxyethane 1 2 0 m L ' was added to a 2.0 Μ aqueous sodium carbonate solution of 60 μL, and heated under reflux for 8 hours under an argon atmosphere. After the reaction is completed, the aqueous layer is removed. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated evaporated. The residue was purified by column chromatography on silica gel column to afford <RTI ID=0.0>> To the 2-amine-4,6-diphenylpyrimidine 118 (44111111〇1), 48% 118 『50 mL was added and stirred. The solution was cooled to -20 ° C and bromo 8.5 g (5 3 mm ο 1 ) was added dropwise. Further, sodium nitrite 3.1 g (44 mmol) was added dropwise. Stir for 3 hours while warming to room temperature. After completion of the reaction, extraction was carried out with ethyl acetate to remove the aqueous layer. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated. The residue was purified by silica gel column chromatography toield-1 g of 2-bromo-4,6-diphenylpyrimidine (yield 82%). (Synthesis of 4-bromophenyl-2,6-diphenylpyridine) The synthesis of 4-bromophenyl-2,6-diphenylpyridine follows the following flow chart -71 - 200920718

15.0 g (81 mmol) of 4-bromobenzene and 9.7 g (81 mmol) of styrene were dissolved in ethanol 300 mL, and then added to a solution of 16.6 mL (8 lmmol) in 28% sodium methoxide methanol, and stirred at room temperature for 9 hours. After completion of the reaction, the precipitated crystals were filtered and washed with ethanol to obtain a synthetic intermediate (enketone) of 19-6 g (yield: 84%). 9.0 g (31 mmol) of synthetic intermediate (enketone), 8.7 g (31 mmol) of 1-Phenacylpyridinium Bromide, and 9.3 g of ammonium acetate (250 mmol) were suspended in acetic acid 27 mL. , heat reflux for 1 2 hours. The reaction solution was cooled to room temperature, and toluene was added to the mixture, and the organic layer was washed successively with 10% aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. After the organic solvent was evaporated under reduced pressure, 27 mL of ethanol was added, and the precipitated crystals were filtered and washed with ethanol to obtain 4-bromophenyl-2,6-diphenylpyridine 1 0 · 6 g (yield 88%) . (Synthesis of 4-(4-bromophenyl~2,6-diphenylpyrimidine) 4 (Synthesis of 2,6-diphenylpyranoline in accordance with the following procedure -72-200920718).

NaOMe EtOH

NaOH EtOH

4-Bromoethylbenzene 19_9 g (100 mmol) and benzaldehyde 10.6 g (100 mmol) were added, and argon substitution was carried out. Next, 200 mL of ethanol and 1 mL of IN sodium methoxide/methanol solution were added, and the mixture was stirred at room temperature for 5 hours. Thereafter, the temperature was raised in an oil bath of 7 Torr, and the reaction was further carried out for 4 hours while refluxing the ethanol. Next, 9.40 g (60 mmol) of phenylhydrazine hydrochloride and 8.0 g (200 mm) of sodium hydroxide were added, and the mixture was heated in an oil bath at 70 ° C for 5 hours. After completion of the reaction, the precipitate was filtered off and purified by silica gel column chromatography to yield 4-(4-bromophenyl)-2,6-diphenylpyrimidine 13-6 (yield 35%). (Synthesis of 2-(4-bromophenyl)-imidazole [l,2-a]pyridine) Synthesis of 2-(4-bromophenyl)-imidazo[1,2-a]pyridine follows the following scheme Implementation.

N NH2 EtOH -73- 200920718 2,4,-dibromoethyl benzene 15g (54mmol), 2-aminopyridinium D 5.2g (55mmol) dissolved in ethanol 100mL, sodium bicarbonate 7. 〇g' for 6 Heat back to reflux. After completion of the reaction, the resulting crystals were filtered and washed with water to give 2-(4-bromophenyl)-imidazole [l,2-a] as a steepness of 12 to 5 g (yield: 85%). Synthesis of (12-(2-naphthyl)g-6-boronic acid) The synthesis of 12-(2-naphthyl)g-6-boric acid was carried out in accordance with the following scheme.

Pd(PPh3)4 Na2C〇3aq toluene

To a solution of 22.8 g (100 mmol) of DMF 1 L in a solution, a solution of 17.8 g (100 mmol) of DMF 100 mL of N-bromosuccinimide was added and stirred at room temperature for 20 hours. After completion of the reaction, the reaction solution was added to 2 L of water, and the precipitated crystals were collected by filtration. The obtained solid was washed with water, methanol and hexane, and dried under reduced pressure to give 28.5 g (yield: 93%). Under argon atmosphere, 6.14g (20.0mmol), 2-naphthaleneboronic acid, 4.l〇g (24.0mmol), tetrakis(triphenylphosphine)palladium (〇) 〇.4 62g (-74- 200920718)

40 mL of DME 80 mL and 2 M sodium carbonate aqueous solution were added to 0.400 mmol), and the mixture was heated under reflux for 16 hours. After completion of the reaction, the precipitated crystals were collected by filtration, and the obtained crystals were washed with water, methanol and hexane. The obtained solid was recrystallized from toluene to give 6-(2-naphthyl) a 4 to 25 g (yield: 60%). To a solution of 4.25 g (12.0 mmol) of DMF 1 OO mL of 6-bromine, a solution of 2.56 g of N-bromosuccinimide (1.44 mmol) in DMF (10 mL) was added and stirred at room temperature for 20 hours. After completion of the reaction, the reaction solution was added to 20 mL of water, and the precipitated crystals were collected by filtration. The obtained solid was washed with water, methanol and hexane, and dried under reduced pressure to yield 4.68 g (yield: 90%) of 6-bromo-12-( 2-naphthyl). Add 4.68g (l〇_8mmol) of 6-bromo-12-(2-naphthyl) grotto to anhydrous THF lOOmL, and add 1.6M η-butyllithium hexane solution 7.4 m at -10 °C with stirring. L (1 1 . 9 mm ο 1 ). The reaction solution was stirred for 2 hours while warming to 〇 °C. The reaction solution was further cooled to -7 8 ° C, and 6.09 g (32.4 mmol) of triisopropyl borate was added dropwise. The reaction solution was stirred at room temperature for 7 hours. After adding water of 100 ml L' for 1 hour, the precipitated crystals were filtered off. The obtained solid was washed with toluene to obtain 2.56 g (yield: 60%) of 12-(2-naphthyl) s. (Synthesis of Compound 1) The synthesis of Compound 1 was carried out in accordance with the following scheme. -75- 200920718

Under the argon atmosphere, 1.75 g (5_0 mmol) of 2-(4-bromophenyl)-1-phenyl-1H-benzimidazole, 2.38 g (12 0 mm) of 12-(2-naphthyl) -6-borate ο 1 ), tetrakis(triphenylphosphine) pin (0) 0.115 g (0.100 mmol), 10 mL of DME and 10 mL of 2M sodium carbonate aqueous solution were added, and the mixture was heated under reflux for 16 hours. After completion of the reaction, the precipitated crystals were collected by filtration, and the obtained crystals were washed with water, methanol and hexane. The obtained solid was recrystallized from toluene to give 2.49 g of white crystals. This product was analyzed by mass spectrometry to give the object, m/e = 622 for molecular weight 622.24. (Synthesis of Compound 2) The synthesis was carried out in the same manner as in Compound 1 by following the following scheme. This product was analyzed by mass spectrometry and found to be the object. For molecular weight 622.24, m/e = 6 2 2 .

DME (Synthesis of Compound 3) -76- 200920718 The synthesis was carried out in the same manner as in Compound 1 by following the following scheme. This product was analyzed by mass spectrometry and was the target. For the molecular weight of 6 2 2.2 4, m/e = 6 2 2 〇

DME (Synthesis of Compound 4) The synthesis was carried out in the same manner as Compound 1 by following the following scheme. The product was analyzed by mass spectrometry and found to be the target. For molecular weight 5 07.20, m / e = 5 0 7 .

DME (synthesis of compound 5) The synthesis was carried out in the same manner as in the compound 1 according to the following scheme. This product was analyzed by mass spectrometry and found to be the target. For molecular weight 5 84.23, m / e = 5 8 4 . -77- 200920718

DME (synthesis of compound 6) The synthesis was carried out in the same manner as in the compound 1 according to the following scheme. This product was analyzed by mass spectrometry and was the target. For molecular weight 6 5 9.26, m/e = 6 5 9 〇

DME (Synthesis of Compound 7) The synthesis was carried out in the same manner as in Compound 1 by following the scheme below. This product was analyzed by mass spectrometry and was the target. For molecular weight 660.26, m / e = 6 60.

DME-78-200920718 (Synthesis of Compound 8) The synthesis was carried out in the same manner as in Compound 1 by following the following scheme. The mass spectrometry result of this material is 'target'. For molecular weight 546.2 1 , m/e = 546 o

DME

[Composition of Samples] Next, the composition of the samples will be described. (Example 1) A glass substrate (manufactured by Geomatec Co., Ltd.) having an ITO transparent electrode (anode) of 25 mm x 75 mm x 1 mm thick was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. . The glass substrate with the transparent electrode wire after the cleaning is attached to the substrate holder of the vacuum vapor deposition apparatus, and the film thickness of 75 nm is formed by coating the transparent electrode on the surface on the side where the transparent electrode line is formed. Compound A-1. Further, on the A-1 film, the following compound H-1 and the following compound D-1 were formed into a film at a film thickness ratio of 40:2 at a film thickness of 40 nm to form a blue light-emitting layer. The compound Η-1 is a host material, and d-1 is used as an erbium-doping agent. On the film, the compound 1 of the present invention was deposited into a film at a film thickness of 2 〇 n m as an electron transport layer. Thereafter, LiF was formed into a film at a film thickness of 1 nm. On -79-200920718, on the LiF film, metal A1 was vapor-deposited at 150 nm to form a metal cathode to form an organic EL device.

(Example 2) In Example 1, an organic EL element was produced in the same manner using Compound 2 instead of Compound 1. (Example 3) In Example 1, an organic EL device was produced in the same manner using Compound 3 instead of Compound 1. (Example 4) -80 - 200920718 In Example 1, an organic EL device was produced in the same manner by using Compound 4 instead of Compound 1. (Example 5) In Example 1, an organic EL device was produced in the same manner using Compound 5 instead of Compound 1. (Example 6) In Example 1, an organic EL element was produced in the same manner by substituting the compound 1 in the same manner. (Example 7) In Example 1, an organic EL device was produced in the same manner using Compound 7 instead of Compound 1. (Example 8) In Example 1, an organic EL device was produced in the same manner by using Compound 8 instead of Compound 1. (Comparative Example 1) In Example 1, an organic EL device was produced in the same manner by using the compound A having the following structure in place of the compound 1. -81 - 200920718

(A) (Comparative Example 2) The organic EL device was produced in the same manner as in Example 1 except that the compound 1 was replaced with the following structure B.

• (B) [Evaluation Method] Next, explain the evaluation method. With respect to the organic bodies of the above Examples 1 to 8 and Comparative Examples 1 to 2, the external quantum yield of the element performance at the time of driving a current density of 1 OmA/cm2 was measured. The results of these are shown in Table 1. EL element driving voltage -82- 200920718 [Table i] Electron transport material driving voltage m External quantum yield Example 1 1 4.8 4.2 Example 2 2 4.5 4.3 Example 3 3 4.0 4.4 Example 4 4 4.8 4.2 Example 5 5 4.8 4.2 Example 6 6 4.8 4.2 Example 7 7 4.8 4.2 Example 8 8 4.0 4.4 Comparative Example 1 A 6.0 3.9 Comparative Example 2 B 5.3 4.0 [Evaluation Result] As shown in Table 1, the driving voltage was confirmed. 1 to 8 are smaller than Comparative Examples 1 to 2. Further, regarding the external quantum yield, it was confirmed that Examples 1 to 8 were larger than Comparative Examples 1 to 2. In other words, when the electron transport layer having the configuration of the present invention is used, it is confirmed that when the energy gap of the short-wavelength of the blue light-emitting wavelength is used as the light-emitting layer, the light-emitting layer does not require a large voltage. An organic EL element in which electrons are injected. Further, the present invention is not limited to the above description, and modifications are intended to be included in the invention without departing from the scope of the invention. For example, the following modifications are also preferred variations of the invention. In the present invention, the light-emitting layer is preferably a charge-injecting auxiliary material. When the fluorescent light-emitting layer is formed by using the above-described material having a wide gap, the ionization potential (Ip) of the host material material and the Ip of the hole injection/transport layer become larger, and the fluorescence is emitted. The injection of the holes in the layer becomes difficult, and the driving voltage for obtaining sufficient brightness rises. In this case, since the fluorescent light-emitting layer contains a hole injection and transporting charge injection auxiliary agent, it is possible to easily inject the holes into the fluorescent light-emitting layer, and the driving voltage is lowered. As the charge injection auxiliary agent, for example, general hole injection/transport material or the like can be used. Specific examples thereof include a triazole derivative (refer to the specification of U.S. Patent No. 3,112,197, and the like), an oxadiazole derivative (refer to the specification of U.S. Patent No. 3,188,44, and the like). An imidazole derivative (refer to Japanese Patent Publication No. 3-7-6096, et al.), a polyarylalkane derivative (U.S. Patent No. 3,6,5,402, the specification of the same, No. 3,820,98, No. 3,542,544, Japanese Patent Publication No. 4-5 - 5 5 5, the same as Japanese Patent Publication No. 51-101, and Japanese Patent Publication No. 51-93224, the same as No. 55-17105, the same as No. 56-4148, and the same 5 5 - 1 0 8 6 6 7th, the same as 5 5 - 1 5 6 9 5 3, the same as S6-3 6656, etc.), a pyrazoline derivative, and a pyrazolone derivative (U.S. Patent No. 3,180, 72 No. 9 specification, the same as No. 4,278,746, Japanese Patent Laid-Open No. 5-5-8 8064, the same as 5 5-88065, the same as 4-9 - 1 0 5 5 3 7 , the same 5 5 - 5 1 0 Japanese Patent Publication No. 6-6, No. 56-80051, No. 56-88141, No. 57-45545, No. 54-112637, and No. 55-74546, etc., and a phenylene diamine derivative (US) Patent No. 3,6, 5, 404, Japanese Patent Publication No. 51-10105, Japanese Patent Publication No. 46-3712, Japanese Patent Application Publication No. -84-200920718, No. 47-25336, JP-A-54-53-43, No. 54- 1 1 05 3 No. 6 and the same as the reference of 54_n 9925, etc., arylamine derivatives (U.S. Patent No. 3,5,67,450, the same as No. 3,180,703, the same as No. 3, 240, 5 97) Instructions, the same as the 3,65 8,5 20 manual, the same as the 4,232,103 manual, the same as the 4,1 7 5,96 1 manual, the same as the 4,0 1 2,376 manual, special public Zhao 49-35702 Japanese Laid-Open Patent Publication No. 39-27577, Japanese Patent Application Laid-Open No. Hei 55-1-4250, No. 56_1-19132, Japanese Patent No. 5-6-2243, and No. 1,1 1 0, 5 1 8 (Reference), amine-substituted chalcone derivatives (refer to the specification of U.S. Patent No. 3,526,510, etc.), oxazole derivatives (expressed in the specification of U.S. Patent No. 3,257, No. 2, No. 3, etc.), styryl group Anthracene derivatives (references in JP-A-56-4, No. 6W4, etc.), anthrone derivatives (refer to Japanese Patent Laid-Open No. Hei-5 4 - 1 0 8 3 7 and the like), anthracene derivatives ( Japanese Patent No. 3,7,7,462, Japanese Patent Laid-Open No. Hei 54-59143, No. 55-52063, No. 55-52064, No. 55-46760, and No. 55-85495, the same as Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 61-210. Japanese Patent Publication No. Hei. No. 62-47646, No. 62-36674, No. 62-36674, No. 62-10652, No. 62-30255, No. 60-93455, and No. 60-94462, the same as 60 -174749, the same as the 60- 1 7 5 0 5 2 publication, etc.) 'Sand-nitrogen derivatives (US Patent No. 4, 95, 950), polydecane (Special Kaiping-85-200920718) JP-A No. 2-204996), an aniline-based copolymer (Japanese Patent Publication No. 1), and a sub-oligomer (particularly a thiophene oligomer) disclosed in JP-A No. 1-21. The material of the above-mentioned material, which is disclosed in the above-mentioned Japanese Patent Publication No. SHO-63-295695, etc., and a styrylamine compound (U.S. Patent No. Japanese Patent Publication No. 3, the same as No. 54-149, the same as No. 54-149, 634, the same as the Japanese Patent Publication No. 55-79450, the same as JP-A-55-144250, the same publication, the same as 61-295558, the same as 61-98353 No. 63-295 6 9 5, etc.), especially aromatics. Further, the J aromatic ring described in the 'US Patent No. 5,061,569 is in the molecule, and examples thereof include 4,4'-bis(N N-phenylamine)biphenyl (hereinafter abbreviated as NPD) and 4-3. The triphenylamine unit described in the publication No. 08688 is a g-type 4,4',4"-tris(N-(3-methylphenyl)-N-phenyl (hereinafter abbreviated as MTDATA). Inorganic compound hole injecting material such as P-type Si or p-type Sic, etc. B. 2-282263 Conductive high score but porphyrin compound, aromatic third 丨 4, 127, 412 5 8445, the same 5 6 - 1 1 9 1 3 2, with the third-stage amination, there are two condensations - (1-naphthyl)-opening, which is 3 star-explosive amines. Triphenylamine can also be used as -86-

Claims (1)

200920718 Ο) X. Application for patent scope ~ The species of the species is represented by the following general formula: 坩1—Ch~Ar2 · · · (1) (In the general formula (1), ΓΤι 2 ^^ is not substituted or unsubstituted, and Ar is independent ' represents a substituted or unsubstituted nucleocarbon 6~ group, or a substituted or unsubstituted nucleus having 5 to 4 核, and at least one of Ar1 and Ar2 is a substituted or unsubstituted nucleon 2 40 containing a heteroaryl group). 2 ' A cave derivative characterized by the following general formula (2), the cave, the base of the arm of Ar 1 40, the number of turns 5~ (In the general formula (2), 'Ar3 and Ar4 are each independently, and represent an unsubstituted aryl group having 6 to 4 fluorene, or a substituted or unsubstituted 5 to 4 fluorene-containing group. , at least} a substituted or unsubstituted nuclear atom having a number of 5 to 40, and a heteroaryl group, ??? represents a hydrogen atom or a substituent). 3 _ A cave derivative 'The patent application scope is 1 or substituted or the nuclear atom is taken as ~R1. 2 items -87- 200920718 (2) Cave derivatives, characterized in that the heteroaryl group is a nitrogen-containing heterocyclic ring. 4. A cave derivative which is a cave derivative of claim 1 or 2, characterized in that the heteroaryl group is a nitrogen-containing 5-membered ring derivative. A cave derivative which is a cave derivative of claim 1 or 2, characterized in that the heteroaryl group is a nitrogen-containing 6-membered ring derivative. A cave derivative which is a cave derivative of claim 1 or 2, characterized in that the heteroaryl group is a structure of the following general formulas (3) to (9). • · · (4) • ·(5) -88 200920718 (3) (In the general formula (3) to (9), each of L1 to L7 represents a substituted or unsubstituted aryl group having 6 to 3 fluorene, and a to f each represents 〇~3 η <integer' R~ R16 represents a hydrogen atom or a substituent 'k is an integer of 1 to 4, and when 'k is 2 or more, R1 1 may be the same or different from each other, 1 is an integer of 1 to 3' and '1 is 2 or more' R12 They may be the same or different from each other, and m is an integer of 1 to 2'. When m is 2, R13 may be the same or different from each other, and η is an integer of 1 to 5, and when η is 2 or more, R14 may be the same as each other. Or different, Rn~R16 may be bonded to each other by a substituent adjacent to each other to form a saturated or unsaturated -89-200920718 (4) ring). An organic EL device characterized in that an organic EL element having an organic thin film layer formed of a layer or a plurality of layers of at least a light-emitting layer is sandwiched between a cathode and an anode, and at least one layer of the organic thin film layer contains a patent application. The cave derivatives of range 1 or 2 are included as separate or mixtures. 8. An organic EL device according to claim 7, wherein the organic thin film layer has an electron injecting layer or an electron transporting layer, and the electron injecting layer or the electron transporting layer contains the aforementioned cave derivative as a single or a mixture The ingredients. 9. An organic EL device according to item 7 of the patent application, characterized in that the luminescent layer contains the aforementioned cave derivative as a component of a single or a mixture. An organic EL element as claimed in claim 8 which is characterized in that the electron injecting layer or the electron transporting layer containing the above-mentioned cave derivative contains a reductive dopant. An organic EL device according to claim 10, wherein the reducing dopant is an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, Alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, rare earth metal halide, alkali metal organic complex, alkaline earth metal organic complex and rare earth metal organic One or two or more substances selected from the group formed by the complex. 1 2. An organic EL device as described in claim 7 is characterized in that the light-emitting layer is formed by the following general formula (10)-90-200920718 (5) material and dopant , • (10) (In general formula (1 〇 ), R42 to R53, except that at least one of R42 to R53 has an aryl group having a core number of 6 to 60). A hydrogen atom or a substituent, which means a substituted or unsubstituted -91 - 200920718 七无• · A single-character table is a table of the generation of the map. The table is represented by the table: N is one or two, and if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: general formula (2) R4 Ar4 (2)