TW200948931A - Light-emitting element material and light-emitting element - Google Patents

Abstract

This invention is to provide a green light-emitting device with high light-emitting effec, long-period life, and high color purity by using a light-emitting device material containing the pyrromethene skeleton compound represented by the general formula (1), and having molecular weight of more than 450. (Each of R1 to R4 is alkyl, cycloalkyl, alkoxy, or arylether, and each of them may be the same or different. R5 and R6 are halogen, hydrogen or alkyl, and each of them may be the same or different. R7 is anyone of aryl, heteroaryl, or alkenyl, and molecular weight of more than 200. M is at least one of group selected from boron, beryllium, magnesium, aluminum, chromium, iron, cobalt, nickel, copper, zinc, and platinum, n is an integer of 0 to 4. m is an integer of 1 to 3. L bonds to M via 1 or 2 intramolecular atom, by group of valence of 1 or valence of 2 selected from halogen, hydrogen, alkyl, aryl, or heteroaryl. Each of L could be the same or different if n is 2 to 4. Each of R1 to R7 on pyrromethene skeleton could be the same or different if m is 2 or 3.

Description

200948931 * VI. Description of the Invention: [Technical Field] The present invention relates to an element for converting electrical energy into light, which can be used for display elements, flat panel displays, backlights, illumination, interiors, signs, billboards, electronic cameras, and Light-emitting elements in the field of optical signal generators and the like. [Prior Art] The organic laminated film 发光 light-emitting element which emits light when the electrons injected from the cathode and the hole injected from the anode are recombined in the organic light-emitting body sandwiched between the two electrodes is extremely popular in recent years. This light-emitting element has been attracting attention because of its high-brightness light emission at a low driving voltage and the ability to select a fluorescent material for multicolor light emission. Since the publication of the organic laminated film element which can emit high-intensity light by C. W. Tang et al. of Kodak Co., Ltd. (refer to Non-Patent Document 1), many research institutions have conducted related research. The representative structure of the organic laminated thin-film light-emitting device disclosed by Kodak's research team is based on the IT0 glass substrate, which is provided with a hole transporting diamine compound, a light-emitting layer of 8-hydroxyquinoline aluminum, and a cathode. ® Mg: Ag, with a driving voltage of about 10V, can be used for green light emission of 1,500 cd/m2. The organic laminated thin film light-emitting device of the present invention has a structure in which an electron transport layer other than the above-described component components is changed, but basically follows the structure of Kodak Co., Ltd. The organic thin film light-emitting element can obtain various light-emitting colors by using various fluorescent materials in the light-emitting layer. In particular, by combining the main material and the doping material in the light-emitting layer, a light-emitting element exhibiting high-efficiency blue, green, and red primary colors can be obtained. Although the dopant generally uses a pigment having a high luminescence quantum yield, for example, a complex having a mesopyrrole skeleton has a compound which is required to obtain a enthalpy efficiency 200948931 ', which is a high luminous efficiency, a Stokes shift, and Such a dopant having a narrow peak-to-half width of the luminescence spectrum is known to exhibit good element characteristics (refer to Patent Document 1). A well-known green compound is known as a mesopyrrole compound, and 1,3,5,7,8-pentamethyl-4,4-difluoro-4-boron-33,4&-dioxin is known. 5-5-benzodioxime, a compound having a complex indole-pyrrole skeleton in the molecule, or a compound having a condensed ring structure having a bridgehead position introduced into the methylene pyrrole skeleton (see Patent Documents 2 to 3).非 [Non-Patent Document 1] Appl. Phys. Lett. 51 (12) 21, p. 9 1 3, 1 987) [Patent Document 1] JP-A-9- 1 1 8 8 8 0 [Patent Document 2] JP-A-2002-134749 [Patent Document 3] JP-A-2004-3 1 1 030 SUMMARY OF THE INVENTION Problems to be Solved by the Invention However, 1,3,5,7,8-pentamethyl-4 , 4-difluoro-4-boron-3a, 4a-dioxa-s-benzobis', etc. There are many compounds that sublimate at low temperatures, and the control of the vaporization rate is difficult. There is a so-called agglutination due to evaporation. Or the contamination of the charge transport layer during the fabrication of the component, which reduces the problem of luminous efficiency. In addition, the compounds described in Patent Documents 2 to 3 have a high sublimation temperature, but the thermal stability is insufficient. Therefore, there are problems such as thermal decomposition during vapor deposition, shifting of the emission peak wavelength, and low color purity. The azole compound exhibits good green luminescence, but in the luminescent element, it is difficult to find luminescent properties excellent in luminous efficiency, color purity, and durability. Accordingly, the present invention has been made in view of solving the problems of the prior art, and stably proposes 200948931 for the purpose of providing a green light-emitting element having high luminous efficiency, long life, and high color purity. Means for Solving the Problem That is, the present invention is a light-emitting device material having a methylene pyrrole skeleton represented by the general formula (1) and having a molecular weight of 50,000 or more.

(wherein R^R4 is alkyl, cycloalkyl, alkoxy or aryl ether, which may each be the same or different; R5 and R6 are halogen, hydrogen or alkyl, which may each be the same or different; R7 is aryl Any of a base, a heteroaryl or an alkenyl group having a molecular weight of 200 or more; the lanthanide is selected from the group consisting of boron, lanthanum, magnesium, aluminum, chromium, iron, cobalt, nickel, copper 'zinc and pin At least one of them; η is an integer of 〇~4; m is an integer of 1 to 3; and L is passed through a monovalent or valence group selected from a halogen, hydrogen, alkyl, aryl or heteroaryl group. 1 or 2 atoms in the molecule are bonded to ruthenium; in the case where η is 2 to 4, each L may be the same or different from each other; == 2 or 3, and R1 to R7 of each methylene pyrrole skeleton may be mutually Same or different). EFFECT OF THE INVENTION According to the present invention, a green light-emitting element having high luminous efficiency, long life, and high color purity can be provided. [Embodiment] The best mode for carrying out the invention 200948931 The light-emitting device material of the invention has a methylene chloride skeleton represented by the general formula (1) and a compound having a molecular weight of 450 or more.

(1) wherein 'R1 to R4 are an alkyl group, a cycloalkyl group, an alkoxy group or an aryl ether group, which may be the same or different. R5 and R6 are halogen, hydrogen or alkyl, which may be the same or different. R7 is any of an aryl group, a heteroaryl group or an alkenyl group, and has a molecular weight of 200 or more. Among these substituents, an alkyl group represents For example, a saturated aliphatic group of methyl, ethyl, n-propyl, 'isopropyl, n-butyl, t-butyl, t-butyl, etc.' may or may not have a substituent. In the case of the substitution, the substituent to be added is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heteroaryl group, and the same applies to the following description. The cycloalkyl group means a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a decyl group, an adamantyl group or the like, which may or may not have a substituent. The alkoxy group means a functional group which is bonded to an aliphatic hydrocarbon group via an ether bond such as a methoxy group, an ethoxy group, a propoxy group or the like, and the aliphatic hydrocarbon group may or may not have a substituent. The aryl ether group means a functional group which bonds an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. The dentate represents fluorine, chlorine, bromine and iodine. 200948931 'Aryl represents an aromatic hydrocarbon group such as phenyl, naphthyl, biphenyl, fluoro, phenanthryl, terphenyl, fluorenyl and fluorenyl, or such a complex bonded group' No substitution can be substituted. The substituent of such an aryl group is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl ether group, an alkylthio group, a halogen group, a cyano group, an amine group, a decyl group, a borane group or the like. The oxygen atom of the ether bond of the alkylthio alkoxy group is substituted by a sulfur atom. The alkylthio group may have a substituent or may have no substituent. The amine group means a functional group bonded to a nitrogen atom such as a benzidine group, a phenylnaphthylamino group or a dimethylamino group, and these may or may not have a substituent. The decyl group means a functional group bonded to a ruthenium atom such as a trimethyl decyl group, and these may or may not have a substituent. The borane group means, for example, a functional group having a boron atom bonded to a bis(acyl)borane group, and these may or may not have a substituent. The heteroaryl group means an aromatic cyclic structural group containing an atom other than carbon such as a furyl group, a thienyl group, a carbazolyl group, a pyridyl group, a quinolyl group or a carbazolyl group, or a complex linking group thereof, or And the like, which may be substituted with an aromatic hydrocarbon group, and may be substituted or substituted. Such a heteroaryl group may have the same substituents as the aryl group. Any part of the linking position of the heteroaryl group may be, for example, any of 2-pyridyl, 3-pyridyl or 4-pyridyl. Although the alkenyl group represents a carbon-carbon double bond-containing unsaturated aliphatic hydrocarbon group such as a vinyl group, an allyl group, and a butadienyl group, the unsaturated aliphatic hydrocarbon group and the aryl group and/or heteroaryl group are also included. And the commemoration of the link. The unsaturated aliphatic hydrocarbon group may be unsubstituted or substituted, and may have an alkyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl sulfide group, a halogen, a cyanide 200948931 • , amine, decyl and borane. In the above substituent, R1 to R4 are preferably an alkyl group from the viewpoint of color purity; and from the viewpoint of good heat stability, a methyl group or a third butyl group is preferred. Further, it is preferred to use a methyl group from the viewpoint of easiness of synthesis. From the viewpoint of thermal stability, R5 and R6 are preferably an alkyl group or hydrogen, and hydrogen is preferred from the viewpoint of easily obtaining green light having a high color purity. Further, in the compound represented by the general formula (1), the lanthanoid is at least one selected from the group consisting of boron, lanthanum, magnesium, aluminum, chromium, iron, cobalt, nickel, copper, zinc, and platinum. Preferably, it is boron, aluminum, or zinc; and from the viewpoint of imparting a steeper luminescence spectrum and obtaining higher color purity luminescence, boron is particularly preferred. L is a bond of a valence or a valence selected from a halogen, a hydrogen, an alkyl group, an aryl group or a heteroaryl group, and is bonded to the oxime through one or two atoms in the molecule. The acridine group is a type of coordination with a ruthenium through a non-shared electron pair. The so-called chelation coordination is carried out by two atoms bonded to the oxime. In the case where lanthanum is boron, fluoro is preferably a fluorine, a fluorine-containing aryl group, a fluorine-containing heteroaryl group or a fluorine-containing alkyl group, and from the viewpoint of obtaining a high fluorescence quantum yield, it is preferably a fluorine. The fluorine-containing aryl group is a fluorine-containing aryl group, and examples thereof include a fluorophenyl group, a trifluorophenyl group, and a pentafluorophenyl group. The fluorine-containing heteroaryl group is a fluorine-containing heteroaryl group, and examples thereof include a fluoroindole ratio steep group, a trifluoromethylpyridyl group, and a trifluoropyridyl group. The fluorine-containing alkyl group is a fluorine-containing hospital base, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group. Further, in the case where Μ is other than boron, LL is preferably a chelating ligand. m is an integer of 1 to 3, preferably m = l when μ is boron, m = 3 when bismuth is aluminum, and m = 2 when bismuth is zinc. n is an integer of 〇~4, preferably n = 2 when μ is boron, n = 0 when Μ is Μ, and n = 〇 when Μ is zinc. In the case where m is 2 or 3, R1 to R7 of each of the Málaga skeletons may be the same or different. Furthermore, η is 2~4. 200948931 * In the case of L, L can be the same or different. Since the molecular weight of the compound represented by the general formula (1) is 450 or more, the sublimation temperature becomes relatively high, since contamination in the chamber can be prevented, and stable high-luminance luminescence is exhibited, and high-efficiency luminescence is easily obtained. In particular, since R7 is any of an aryl group, a heteroaryl group, or an alkenyl group and has a molecular weight of 200 or more, a compound satisfying the above molecular weight can be easily obtained, and the obtained light-emitting system can achieve good color purity. . That is, a substituent such as an aryl group, a heteroaryl group or an alkenyl group is introduced into the pyrrole ring, and if a compound having a molecular weight of 450 or φ is obtained, although the color purity is low, the compound represented by the formula (1) can be obtained colorless. High luminous efficiency with low purity and long life. Further, the molecular weight of R7 is preferably 300 or more from the viewpoint of imparting a relatively high sublimation temperature and controlling the vapor deposition rate at a relatively stable level. On the other hand, the molecular weight of the compound represented by the general formula (1) is preferably 1,000 or less, and more preferably 800 or less, from the viewpoint of vapor deposition without thermal decomposition. Further, from the viewpoint of imparting a higher fluorescence quantum yield and being more difficult to thermally decompose, R7 is preferably selected from an aryl group or a heteroaryl group, and particularly preferably an aryl group. Further, R7 is preferably a bulky substituent such as a branched substituent or a 9-anthracene derivative. The term "branched structure" as used herein means a structure in which an aryl group or a heteroaryl group directly bonded to a methylene pyrrole ring further has a plurality of substituents. Because the size of R7 prevents the agglutination of molecules, it can improve luminous efficiency and life. Preferred examples of the substituent having a branched structure include the following general formula -10-(2). 200948931

R9 Here, R8 and R9 may be the same or different and are selected from an aryl group or a heteroaryl group. The description of the aryl group and the heteroaryl group is the same as described above. From the viewpoint of obtaining a higher fluorescence quantum yield, an aryl group is preferably used; and from the viewpoint of thermal stability, a phenyl group and a naphthyl group are exemplified as particularly preferable examples. Further, from the viewpoint of preventing condensed molecules, at least one of R8 and R9 is preferably substituted by an alkyl group, and at least one of R8 and R9 is particularly preferably an alkyl group-substituted aryl group. Although the description of the alkyl group is the same as above, from the viewpoint of thermal stability, a methyl group and a third butyl group are particularly preferable. Further, from the viewpoint of preventing aggregation of molecules, since the substitution position of the alkyl group exerts the same effect at that position, it is not particularly limited. An example of a compound having a methylene pyrrole skeleton represented by the general formula (1) is shown below.

200948931

-12- 200948931 200948931

-14- 200948931

-15- 200948931

-16- 200948931

-17 200948931

-18- 200948931

It is produced by the method described in the publication No. 8-509471 or JP-A-2000-208262. Namely, the reaction of the methylene pyrrole compound and the metal salt in the coexistence of bases -19-200948931 is carried out to obtain the target methylene pyrrole metal complex. Further, 'for the synthesis of the methylene pyrrole-boron fluoride complex, refer to j. Org. Chem., vol. 64, No. 21, pp. 78 1 3-78 1 9 (1 999) ' Angew. Chem· , Int. Ed. Engl., vol. 36, pp. 1 33 3- 1 3 35 (1 997). The method described is manufactured. In other words, the compound represented by the general formula (3) and the compound represented by the general formula (4) are reacted in dichloromethane to form a methylene pyrrole skeleton, and then boron trifluoride etherate is added in the presence of an amine to obtain a sub- Pyrrole-boron fluoride complex. e R7—CHO ο) R5 R1

(4) Further, the compound represented by the general formula (3) is reacted with brominated benzaldehyde and a boronic acid derivative, for example, under the conditions of Suzuki coupling (Reference: Chem. Rev., vol .95 (1955)), which gives the introduction of various aryl and heteroaryl groups into R7. Next, an embodiment of the light-emitting element of the present invention will be described in detail by way of example. The light-emitting element of the present invention has an anode, a cathode, and an organic layer interposed between the anode and the cathode, the organic layer comprising at least a light-emitting layer, and the light-emitting layer emits light by electric energy. The organic layer has only one component of the light-emitting layer, and 1) a hole transport layer/light-emitting layer, 2) a hole transport layer/light-emitting layer/electron transport layer, 3) a light-emitting layer/electron transport layer, and 4) electricity Hole transport layer/light-emitting layer/hole stop layer, 5) hole transport -20- 200948931 • layer/light-emitting layer/hole stop layer/electron transport layer, 6) light-emitting layer/hole stop layer/electron transport layer, And 7) mixing any of the above combinations of the substances in one layer. That is, in the element configuration, in addition to the multi-layered structure of n to 6) above, only one layer of a luminescent material such as 7) alone or a layer containing a luminescent material and a hole transporting material or an electron transporting material may be provided. can. The layers can each be a single layer or a plurality of layers. Further, when the hole transport layer is composed of a plurality of layers, the layer connected to one side of the electrode is referred to as a hole injection layer; however, in the following description, the hole injection layer is included in the hole transport layer. On the other hand, when the electron transport layer is composed of a plurality of layers, the layer on the side of the electrode is referred to as an electron injection layer; however, in the following description, the electron injection layer is included in the electron transport layer. Further, the luminescent material in the present invention means any one suitable for self-luminescence, a substance which contributes to luminescence, a compound related to luminescence, a layer, and the like. The anode in the present invention is not particularly limited as long as it can efficiently inject the material of the hole into the organic layer, but it is preferable to use a material having a large work function. Conductive gold oxides such as tin oxide, indium oxide, indium tin oxide, and indium tin oxide (ITO) or metals such as gold, silver, and chromium, inorganic conductive materials such as copper iodide and copper sulfide, and polythiophene, The conductive polymer such as polypyrrole or polyaniline is not particularly limited. However, when light is generated from the anode side, ITO glass is preferably used. If a sufficient current can be supplied to the light emission of the element, the resistance of the anode is not particularly limited, but the power consumption of the light-emitting element is preferably low resistance. For example, an ITO substrate of 300 Ω /□ or less is a function of a component electrode, but a low resistance of 100 Ω /□ or less is preferable. The thickness of the anode can be arbitrarily selected in accordance with the resistance ,, but it is usually used between l〇〇 and 300 nm. Further, it is preferable to maintain the mechanical strength of the light-emitting element to form the anode on the substrate - 21 - 200948931. In the substrate, soda lime glass, alkali-free glass, or the like is used, and the thickness is also sufficient to maintain the mechanical strength as long as it is sufficient. Therefore, 0.5 mm or more is sufficient. Further, if the anode has a stable function, the substrate does not necessarily have to be glass. For example, the anode may be formed on the plastic substrate. The method of forming the film of the anode is not particularly limited, and is not particularly limited by the electron beam method, the sputtering method, and the chemical reaction method. If the electron can be efficiently injected into the organic layer, the cathode is not particularly limited, and generally includes uranium, gold, silver, copper, iron, tin, zinc, aluminum, antimony, chromium, lithium, sodium, potassium, calcium. , magnesium, planing, and alloys of these, etc. In order to improve the efficiency of electron injection to enhance the characteristics of the element, lithium, sodium, potassium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, these low work function metals are generally unstable in the atmosphere, and therefore, for example, high stability in which a small amount of lithium or magnesium is doped in the organic layer (the thickness of the vacuum vapor deposition is 1 nm or less) is preferably used. The method of the electrode, but an inorganic salt such as lithium fluoride may be used, but is not limited thereto. Further, as the protective electrode, a metal such as lead, gold, silver, copper, iron, tin, aluminum, or indium, or an alloy of these metals, an inorganic substance such as cerium oxide, titanium oxide, or tantalum nitride is preferably used. Organic polymer compounds such as vinyl alcohol, vinyl chloride, and hydrocarbon-based polymers. These electrodes are produced by resistance heating, electron beam, sputtering, ion plating, coating, etc., and are not particularly limited as long as they can be obtained. The hole transport layer is formed by laminating, mixing a single hole transporting substance or two or more substances, or using a mixture of a hole transporting substance and a polymer binder, and transporting holes. The substance is a triphenylamine such as N,N'-dinaphthyl-N,N'-biphenyl-4,4'-biphenyl-1, anthracene-diamine, or bis(indolyl) Oxazoles, pyrazoline derivatives, diphenyl-22-200948931 * vinyl compounds, lanthanoid compounds, anthraquinone derivatives, biological heterocyclic compounds, in the case of polymer systems on the side chain A polycarbonate or a styrene derivative, a polyvinyl carbazole, or a squad, but a compound which is required for the production of a member, and a compound capable of transporting a hole can be injected from the anode, and is not particularly limited. In the case of a hole injection layer, an inorganic salt such as iron (III) chloride may be added to the material to be transported. Further, a metal such as molybdenum oxide or vanadium oxide may be added to form a hole injection layer. Further, a compound having a strong acceptability such as an aromatic ruthenium compound or a layer injection layer is added. The luminescent layer is a single layer, any of the plurality of layers, a mixture of the material and the doping material, a separate main material, and the β main material and the doping material may each be one type or may be combined. The doping material may be contained in all of the main materials and may be contained. Either the doping material is laminated with the main material, and any of the materials can be used. Since the amount of the dopant material is too large, the phenomenon is preferably 'being more preferably 2% by weight or less based on the total of the main material and the dopant material. The doping method may be formed by co-evaporation with a main material, or may be carried out after pre-mixing the main material. Although the light-emitting element material of the present invention can also be used as a doping material from a high fluorescence quantum yield and a small half-width of the luminescence spectrum. In the case of using the light-emitting element material of the present invention, strong light emission is exhibited in the green range. From the sub-representation of porphyrin, it is preferable to have the monomer, etc., into the hole, and to implant the oxide in the hole of the above-mentioned hole, and the cyano group may also form electricity, which may be the main one. For the part of the plural group, any one of the main materials from the main material concentration extinction by 10% by weight of the doping material doping material, from the point of view, as a doped pyrrole-doped -23- 200948931 * From the viewpoint that the dopant can emit light even in a very small amount, a trace amount of the compound can be sandwiched in the main material in a sandwich form. In this case, it is possible to laminate layers or layers of two or more main materials. In addition, the doping material added in the 'light-emitting layer is not necessarily limited to one type of the above-mentioned methylene-pluton-based dopant, and a mixed plural number of methylene sulphate-based dopants or a mixture of known doping materials is used. A pyrrole-based dopant can also be used. In this case, a desired light emission such as white light emission can be obtained by a dopant which combines light emission of different wavelength ranges. Specifically, it is known from the conventional knowledge that a rare earth such as a naphthaleneimine derivative such as bis(diisopropylphenyl)-flowered tetramine acid imide, a purple ring ketone derivative or an Eu complex can be obtained. Complex, 4-(monomethylidene)-2-methyl-6-(p-monomethylaminophenyrene) _4Η-Πϋ: a metal such as sulphur or its analog, magnesium phthalocyanine Anthraquinone derivatives, deazaflavin derivatives, Hui, blue, fused tetraphenyl, children, benzene, condensed polycyclic aromatic hydrocarbons such as ruthenium and osmium, or derivatives thereof , furan, pyrrole, thiophene, benzothiophene, benzofuran, anthracene, dibenzothiophene, dibenzofuran, imidazolium, pyridinium and sulfonium III, etc. An amine styrene derivative such as a stilbene benzene derivative or a 4,4'-bis(2 _(4-benzidinephenyl)vinyl)diphenyl group, or a 2-oxo oxypyrrole [3,4-c Pyrrole derivatives, 2,3,5,6-lH, 4H-tetrahydro-9-(2'-benzothiazole) quinone and [9,9a, Ι-gh] coumarin Derivatives, and N,N'-biphenyl-N,N'-bis(3-tolyl The aromatic amine derivative represented by the-4,4'-biphenyl-M'-diamine or the like coexists, but is not particularly limited thereto. The main material is not particularly limited, but a metal chelate derived from a derivative having a condensed aromatic group such as ruthenium or osmium or the like as a basic skeleton, and ginseng (8-salotidate) aluminum (III) may be used. Synthetic Oxygen Type-24- 200948931 • (〇xin〇id) compound, bisstyrene hydrazine derivative or stilbene benzene derivative, such as bis-benzene derivative, quinone derivative, quinone derivative As the styrene-pyridyl derivative, the azole derivative, and the polymer, a polyphenylacetylene derivative, a polyparaphenylene derivative, a polyfluorene derivative, a polyvinylcarbazole derivative, a polythiophene derivative, or the like can be used. When a derivative having a condensed aromatic group such as ruthenium or osmium as a basic skeleton is used as a main material, it is preferable since the compound having the methylene pyrrole skeleton of the present invention has a high luminous efficiency effect. Specifically, when a compound selected from the group consisting of an anthracene compound, an anthracene compound, and a stilbene arylene derivative is used as a main material, it is more preferable. Further, from the viewpoint of high heat resistance and carrier transport ability, when a ruthenium compound or a ruthenium compound is used as a main material, a light-emitting element having high efficiency and long life can be obtained, which is preferable. The electron transporting layer is necessary for efficiently transporting electrons from the cathode between the electrodes having the electric field, and is desirably formed by an electron transporting material which is highly efficient in electron injection and efficiently transports the injected electrons. Since this requires a large electron affinity, and the electron mobility is large, and the stability is excellent, it is difficult to generate a substance which forms impurities of the well at the time of manufacture and use. Examples of the substance satisfying such a condition include a quinolol derivative metal complex represented by aluminum quinolate, a hydroxyazole complex such as a hydroxyphenyl carbazole complex, a phenanthrene derivative, and a purple ketone. a derivative, a compound having a condensed aromatic ring such as naphthalene or anthracene or a derivative thereof, an anthraquinone derivative, a bisstyrene derivative, a phenanthroline derivative, a phosphorus oxide derivative, a benzimidazole derivative, or a silole ) derivatives, three-ploughed derivatives, and the like. The compound having the methylene pyrrole skeleton of the present invention has a strong acceptability of -25 to 200948931*, and is combined with an electron transport layer having excellent electron transporting ability to obtain high-efficiency and long-life light-emitting. The electron transporting material is preferably formed by using an element selected from the group consisting of carbon, hydrogen, nitrogen, oxygen, helium and phosphorus to preferably use a compound having a heteroaryl ring structure containing electron-accepting nitrogen. The electron accepting nitrogen system represents a nitrogen atom which forms a complex bond with an adjacent atom. Since the nitrogen atom is highly anisotropic, the complex has the property of accepting electrons. The electron transporting ability is excellent, and the use in the electron transporting layer can lower the driving voltage of the light emitting element. Therefore, the heteroaryl ring containing electron-accepting nitrogen has high electron 〇 affinity. Examples of the heteroaryl ring containing an electron-accepting nitrogen include a pyridine ring, a pyridene ring, a pyrimidine ring, a sinyl ring, a quinoxaline ring, a naphthyridine ring, a pyrimidopyrimidine ring, a benzoquinoline ring, and a phenanthroline ring. , imidazole ring, carbazole ring, oxadiazole ring, triazole ring, thiazole ring, thiadiazole ring, benzofluorene ring, benzothiazole ring, benzimidazole ring and phenymidazole ring. As a compound having such a heteroaromatic ring structure, preferred examples of the compound include a benzimidazole derivative, a benzoxazole derivative, a benzothiazole derivative, an oxadiazole derivative, a thiadiazole derivative, and a triazole derivative. , pyridine derivative, phenanthroline derivative, quinoxaline derivative, quinoline derivative, benzoquinoline derivative, oligopyridine derivative such as dipyridine or tripyridine, quinoxaline derivative and naphthyridine Derivatives, etc. Among them, from the viewpoint of electron transporting ability, it is preferred to use a hydrazine derivative such as ginseng (N-phenylbenzimidazole-2-yl)benzene or 1,3-bis[(4-tert-butylbenzene). a oxadiazole derivative such as 1,3,4-oxadiazole] benzene, a triazole derivative such as N-naphthalene-2,5-biphenyl-1,3,4-triazole, ι, a phenanthroline derivative of 3-bis(1,10-morpholin-9-yl)benzene, 2,2,-bis(benzo[H]quinolin-2-yl)-9,9'-spiro Benzoquinoline derivative of hydrazine, etc., 2,5-bis(6'-(2,2"-dipyridyl)-1,1-dimethyl-3,4-diphenylpyrrole, etc. Dipyridine derivative; i,3,-26-200948931 'Tripyridine derivative of bis (4'-(2,2':6'2"-tripyridine))benzene, bis(1-naphthalene)- A naphthyridine derivative such as 4-(1,8-naphthyridin-2-yl)phenylphosphine oxide. The electron transporting material may be used alone, or may be laminated or mixed with different electron transporting materials, or may be used in combination with one or more other electron transporting materials. Further, it may be used in combination with a metal such as an alkali metal or an alkaline earth metal or a metal complex or the like. Although the free potential of the electron transport layer is not particularly limited, it is preferably 5.8 eV or more and 8. OeV or less, more preferably 6.0 eV or more and 7.5 eV or less. © The hole blocking layer is a layer that prevents the holes from the anode and the electrons from the cathode from moving back in the electrode between the electric field, and the layer is made by inserting the layer according to the material constituting the material of each layer. The probability of recombination of holes and electrons increases, and there is a case where the illuminance rate is increased. Therefore, the hole-blocking material is expected to reduce the highest occupied molecular orbital energy level by the hole transporting material, making it difficult to form an excitation complex with the material constituting the adjacent layer. Specifically, a phenanthroline derivative or a triazole derivative may be mentioned, but it is not particularly limited as long as it forms a film required for the production of the element and can effectively prevent the compound from moving from the hole of the anode. The above hole transport layer, the light emitting layer, the electron transport layer, and the hole blocking layer may be laminated, mixed with two or more materials alone, or may be a polymer binder, polycarbonate, polystyrene, poly (N- It is used by dispersing a vinyl carbazole, polymethyl methacrylate, and the like. The formation method of the above layers for forming the light-emitting layer is resistance heating, steam evaporation, electron beam evaporation, sputtering, molecular layering, coating, inkjet, printing, laser-induced thermal transfer, etc., and there is no particular In general, resistance heating evaporation or electron beam evaporation is preferred in terms of characteristics. The thickness of the layer is -27- 200948931. • It is determined by the resistance of the substance that controls the light, but it cannot be limited, but it can be selected between 1 and 100om. The light-emitting element of the present invention has a function of converting electrical energy into light. Here, DC current is mainly used as electric energy, but pulse current or alternating current can also be used. The current 値 and voltage 値 are not particularly limited, but in consideration of the power consumption or life of the element, it is preferable to obtain the maximum brightness with the lowest possible energy. The light-emitting element of the present invention can be applied, for example, as a display which is displayed in a matrix and/or a segment. In the matrix mode of the present invention, the pixels for display are arranged in a lattice shape, and characters or images are displayed in a set of pixels. The segment method of the present invention forms a pattern in such a manner as to display predetermined information, and causes the determined range to emit light. Further, the matrix display and the segment display may coexist in the same panel. EXAMPLES The invention is illustrated by the following examples, but the invention is not limited by the examples. © j-NMR system, using superconducting FT-NMR EX-270 (manufactured by JEOL Ltd.), and measuring in a heavy chloroform solution. Synthesis method of the compound [1] of Synthesis Example 1 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), hydrazine (triphenylphosphine) palladium (0) (0.4 g), and potassium carbonate (2, Og) were placed in a flask and replaced with nitrogen. Degassed toluene (30 ml) and degassed water (10 ml) were added and refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate, and the filtered solvent was evaporated. The reaction product obtained was purified by hydrazine gel chromatography to give 3,5-bis (p- -28-200948931 * tributylphenyl) benzaldehyde (3.5 g) as a white solid. Add 3,5-bis(4-t-butylphenyl)benzaldehyde (1.52) and 2,4-dimethylpyrrole (0.7 g) to the reaction solution, dehydrated dichloromethane (200 ml), trifluoro Acetic acid (1 drop) was added and stirred for 4 hours. A solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (〇.85 g) in dehydrated dichloromethane was added and stirred for 1 hour. After the completion of the reaction, boron trifluoride diethyl ether complex (7.0 ml) and diisopropylethylamine (7.0 ml) were added and stirred for 4 hours, and water (100 ml) was added to the mixture, and the organic layer was separated. The organic layer was dried over magnesium sulfate, and the filtered solvent was evaporated. The reaction product obtained was purified by hydrazine gel chromatography to give 0.4 g (yield: 18%) of the compound (1) shown below. Ή-ΝΜΚ(αΧ:13,ρριη): 7.95(s,lH), 7.63-7.48(m,10H), 6.00(s,2H), 2.58(s,6H), 1.50(s,6H), 1.37( s, 18H).

Example 1 A light-emitting device using the compound [1] was produced in the following manner. The ITO transparent conductive film was deposited into a 150 nm glass substrate (made by Asahi Glass Co., Ltd., 15 Ω /□, electron beam vapor-deposited material), and cut into 30×40 mm, and etched. The obtained substrate was washed with acetone, SEMIKOKURIN (registered trademark) 56" (manufactured by Furuchi Chemical Co.) for 15 minutes, and then washed with ultrapure water. Then, it was washed with isopropyl alcohol for 15 minutes, and then washed with isopropyl alcohol for 15 minutes. After immersing in hot methanol for 15 minutes, it is dried. The substrate is treated with UV-ozone before the component is fabricated. 1 -29- 200948931 • The hour is set in the vacuum evaporation device, and the vacuum is discharged to the device within 5 χ 10_5 Pa. The resistance heating method first vaporizes copper anthraquinone l〇nm into a hole injecting material, and then vapor-deposits 4,4'-bis(Ν·(1-naphthalene)-N-aniline)biphenyl 50 nm as a hole transporting material. Secondly, with ginseng (8-quinolinate) aluminum (Alq3) as the main material, and compound [1] as the dopant material, the doping concentration was 1% by weight and evaporated to 40 nm thickness as the luminescent material. Secondly, the layer was laminated. 1,3-bis(1,10-morpholin-2-yl)benzene to a thickness of 25 nm as an electron transporting material. Next, after doping lithium with a thickness of 0.5 nm on the organic layer, aluminum is vapor-deposited as a cathode to prepare G. 5x5mm square element. The so-called film thickness is the display of the crystal oscillation film thickness meter. The component can obtain CIE chromaticity coordinates (0.24, 0.67), high efficiency of luminous efficiency of 10 cd/A, high color purity green light emission (ELpeak wavelength 524 nm). When the light-emitting element is continuously driven by direct current of 5 mA/cm 2 , the luminance is halved. 3700 hours. Example 2 A light-emitting element was produced as in Example 1 except that the compound shown below was used as the main material. From this light-emitting element, CIE chromaticity coordinates (〇·22, 0_72) were obtained, and the luminous efficiency was 12 cd/A. High-efficiency green light emission (ELpeak wavelength 524 nm). When the light-emitting element was continuously driven with a direct current of 5 mA/cm 2 , the luminance halving time was 3,900 hours.

Comparative Example 1 A light-emitting device was produced as in Example -30-200948931 except that the compound [2] shown below was used as a dopant. Although the CIE chromaticity coordinates (0.24, 0.68) of the high color purity recording light can be obtained from the light-emitting element, the luminous efficiency is reduced to 36 (1/eight (ELpeak wavelength 520 nm)» This light-emitting element is continuously continuous with 5 mA/cm 2 of direct current. When driving, the brightness is halved for 300 hours.

Comparative Example 2 A light-emitting device was produced as in Example 1 except that the compound [3] shown below was used as a dopant. This light-emitting element has high color purity green light emission of C.I.E chromaticity coordinates (0.25, 0.67), but low light emission efficiency of 4 cd/A (ELpeak wavelength of 5 23 nm). When the light-emitting element was continuously driven by a direct current of 5 mA/cm2, the luminance was halved for 3 30 hours.

Examples 3 to 6 A light-emitting device was produced as in Example 1 except that the compound shown below was used as a main material. The C.I.E chromaticity coordinates, the light-emitting efficiency, and the luminance halving time when the light-emitting elements were continuously driven by the direct current of 5 mA/cm2 were shown in Table 1. -31- 200948931 Table 1

Main material CIE Chromaticity coordinate efficiency (cd/A) Half-life life (hr) Example 3 Η-3 (0.22, 0.72) 12 3500 Example 4 Η-4 (0.22, 0.72) 15 3900 Example 5 Η-5 (0.22, 0.72) 15 4000 Example β Η-6 (0.22, 0.72) 18 4000

Examples 7 to 1 1 A light-emitting device was produced as in Example 1 except that ruthenium-6 was used as a main material, and the compound shown below or Alq3 was used as the electron transport layer. The C.I.E chromaticity coordinates obtained by the light-emitting elements, the luminous efficiency, and the luminance halving time when the direct current is continuously driven at 5 mA/cm2 are shown in Table 2. -32- 200948931 Table 2 Electron transport layer CIE Chromaticity coordinate efficiency (cd/A) Half-life life (hr) Example 7 E-2 (0.22, 0.72) 15 4000 Example 8 E-3 (0.22, 0.72) 14 4100 Example 9 E-4 (0.22, 0.72) 14 3500 Example 10 E-5 (0.22, 0.72) 18 4500 Example 11 Alq3 (0.24, 0.70) 12 3000

Example 1 2 to 18. Comparative Example 3 A light-emitting device was produced as in Example 1 except that H-5 was used as a main material and a compound shown below was used as a dopant material. The C.I.E chromaticity coordinates obtained by the light-emitting elements, the luminous efficiency, and the luminance halving time when the direct current is continuously supplied at 5 mA/cm2 are shown in Table 3. -33- 200948931

Table 3 Dopant CIE Chromaticity Coordinate Efficiency (cd/A) Half-life (hr) Example 12 D-4 (0.22, 0.72) 10 3000 Example 13 D-5 (0.22, 0.72) 12 3200 Example 14 D-6 (0.22, 0.72) 16 3900 Example 15 D-7 (0.22, 0.72) 15 3200 Example 16 D-8 (0.22, 0.72) 15 3500 Example 17 D-9 (0.22, 0.72) 16 3600 Implementation Example 18 D-10 (0.22, 0.72) 11 3000 Comparative Example 3 D-11 (0.22, 0.72) 7 2000

• 34- 200948931

INDUSTRIAL APPLICABILITY The light-emitting element material of the present invention can provide a light-emitting element material which can be used for a light-emitting element -35-200948931 or the like and which is excellent in film stability. The illuminating element of the present invention can be utilized in the fields of display elements, flat panel displays, backlights, illumination, interiors, signs, kanbans, electronic cameras, and optical signal generators. [Simple description of the diagram] None. [Main component symbol description] None.

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Claims (1)

200948931 VII. Patent application scope: 1. A light-emitting device material having a molecular weight of 450 or more, which is represented by the general formula (1), methylene pyrrole # $ ' & Μ—(L)n (1) (wherein R l K is an alkyl group, a cycloalkyl group, an alkoxy group or an aryl ether group, which may be the same or different; R 5 and R 6 are halogen, hydrogen or alkyl, Each of which may be the same or different; r7 is any of an aryl group, a heteroaryl group or an alkenyl group, and has a molecular weight of 200 or more; the lanthanoid series is selected from the group consisting of boron, lanthanum, magnesium, aluminum, chromium, iron, austen, nickel, and copper. And at least one of the group formed by zinc and platinum; η is an integer of 〇~4; m is an integer of ^; and L is selected from the group consisting of halogen, hydrogen alkyl, aryl or heteroaryl. The base of zero valence, in the case where 1 $ 2 atoms in the molecule are bonded to M, and '11 is 2 to 4, each l can be asked or different from each other; in the case where m is 2 or 3, each sub- The Rj~R7 of the shame skeleton may be the same or different from each other). 2. The light-emitting element material of claim i, wherein the general formula (1) is boron, L is fluorine, and η is 2. 3. A light-emitting device material according to claim 2, wherein R7 of the general formula (1) is an aryl group or a heteroaryl group. 4. The light-emitting element material according to item 2 of the patent application, wherein R7 of the general formula (1) is represented by the following general formula (2), -37- 200948931 (wherein R8 and R9 may be the same or different. 5. The light-emitting element material of claim 4, wherein r8 and r9 are aryl groups. 〇❿ 6. The light-emitting element material of claim 5, wherein And the ruler 9 is at least one of which is an aryl group substituted with an alkyl group. 7. The light-emitting device material according to claim 5 or 6 wherein the molecular weight of the structure represented by the general formula (2) is 3 Å or more. 8. A light-emitting element characterized in that a light-emitting substance exists between an anode and a cathode, and an element that emits light by electric energy, the element contains a light-emitting element according to any one of claims 1 to 7. 9. The light-emitting element of the patent application scope is as follows: wherein the light-emitting layer has a main material: a material and a doping material, and the compound represented by the general formula (1) is a doping material-38-200948931. a) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: No. ❹ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. (LJn