TW200922941A - Iridium complex compounds, organic electroluminescent devices and uses thereof - Google Patents

Abstract

Blue-emitting phosphorescent compounds show high solubility in solvents for coating solutions in the production of organic EL devices and have excellent thermal stability-Organic EL devices having the blue-emitting phosphorescent compounds have high luminous efficiency and long life. A blue-emitting phosphorescent compound is an iridium complex compound represented by Formula (1) below: wherein R1 is a C2-30 organic group; R2 to R4 are each independently a hydrogen atom or a C1-10 alkyl group; R5 to R8 are each independently an electron-withdrawing group selected from the group consisting of halogen atoms, C1-10 fluorine-substituted alkyl groups, C1-10 fluorine-substituted alkoxy groups, cyano group, aldehyde group, C2-10 acyl groups, C2-10 alkoxycarbonyl groups, C1-10 aminocarbonyl groups, thiocyanate group and C1-10 sulfonyl groups, a C1-10 organic group optionally having a heteroatom (except the electron-withdrawing groups) or a hydrogen atom; and at least one of R5 to R8 is the electron-withdrawing group.

Description

200922941 IX. Description of the Invention [Technical Field] The present invention relates to an illuminating metal complex compound, an organic electroluminescence device using a luminescent metal complex compound, and use thereof. [Prior Art] Since the phosphorescent compound has high luminous efficiency, the luminescent material type of the organic electroluminescent device (also referred to as an organic EL device in the present specification) has been actively developed in recent years. An organic EL element using a phosphorescent compound is expected to be expanded to various applications. However, in particular, in the development of display applications, it is necessary to develop a material having high luminous efficiency and continuous driving of the element. In the three primary colors necessary for a full-color display, an organic EL device that uses green light emission and red light emission has been found to have a phosphorescent compound having sufficiently useful characteristics such as luminous efficiency, durability, and solubility, but organic light using blue light is used. Such a phosphorescent compound is not found in EL elements. Thus, it has been desired to develop a phosphorescent blue luminescent compound having high luminous efficiency and high durability. Japanese Patent Publication No. 2003-526876 (Patent Document 1) discloses the use of an organic ruthenium complex as a phosphorescent compound, which can greatly improve the luminous efficiency of an organic EL device. The ruthenium complex is exemplified by tris(2-(2-pyridyl)phenyl)anthracene and its derivatives, and it is described that the substitution of a substituent of an aromatic structure to an alkyl group or an aryl group can change the entanglement The luminescent color of the object. In JP-A-200-247859 (Patent Document 2), each of the various groups which are substituents of tris(2-(2-pyridyl)phenyl)anthracene is exemplified. JP-A-2002-170702 (Patent Document 3) discloses a ruthenium complex having a phosphorus-based ligand as a high-efficiency light-emitting device and a novel metal complex thereof. Japanese Patent Publication No. 2004-5063 05 (Patent Document 4) discloses a metal complex compound which exhibits blue light emission, and exemplified by the fact that the metal complex compound contains ruthenium. On the other hand, a method of forming a light-emitting layer of an organic EL device generally includes a vacuum deposition method of a low molecular weight organic compound and a coating method of a high molecular weight compound solution, but the coating method is low in manufacturing cost of the device and the component is easily large. The area is favorable. However, in the past, the phosphorescent blue light-emitting compound has a lack of solubility and is difficult to apply to form a film. It is known that in order to improve the solubility of the blue light-emitting compound, it is a substituent in which a long-chain alkyl group is introduced as a ligand of an aromatic structure. For example, in Polyhedron 25 (Non-Patent Document 1), a ruthenium complex having a hexyloxy group is introduced as a substituent of a ligand of an aromatic structure (see the following formulas (4) and (5)).

200922941 [Chemical 2]

However, the compounds of the formulae (4) and (5) lack heat stability. The organic EL device using these compounds has a problem of low durability. Patent Document 1: Japanese Patent Publication No. 2 5 3 - 5 2 6 8 7 6 Patent Document 2: Japanese Patent Laid-Open No. 00 1 - 247 No. 5, No. 9 Patent Publication No. JP-A No. 2002-1 70684 Patent Document 4 :Special Table 2〇〇4-5063〇5 Bulletin Non-Patent Document 1: Inamur R.Laskar, Shih-Feng Hsu, Teng-Ming Chen, "Investigating photolurainescence and electroluminescence of iridium(III)-based blue-emitting phosphors" , Po1yhed r ο n, 2006, 25, p _ 1 1 67 - 1 1 76. [Explanation of the Invention] The present invention has an object of providing a phosphorescent blue luminescent compound having high solubility in a solvent for a coating solution at the time of production of an organic EL device and excellent thermal stability. Further, in order to solve the above problem, an organic EL device having a high luminous efficiency and a long lifetime is provided for the organic -6-200922941 EL device using the phosphorescent blue luminescent compound. As a result of the investigation, it has been found that a ruthenium complex compound having a specific structure among the phosphorescent blue luminescent compounds has high solubility in a solvent for a coating solution at the time of production of an organic EL device, and is excellent in thermal stability. In addition, when the organic EL device is produced, the coating solution in which the ruthenium complex compound is dissolved can be uniformly coated on the substrate, and the film forming property is good, and the organic EL device in which the luminescent layer contains the ruthenium complex compound is The luminous efficiency is high 'and the life is long' and the completion of the present invention is achieved. That is, the present invention can be summarized as follows. [1] A ruthenium complex compound represented by the following formula (1). [Chemical 3]

(1) (In the formula (1), R1 is an organic group having 2 to 30 carbon atoms, and R2 to R4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R5 to R8 are each independently selected from the group consisting of A halogen atom, a carbon number of 1 to 1 fluorene, a fluorine-based -7-200922941 alkyl group, a carbon number of 1 to 10, a fluorine-substituted alkoxy group, a cyano group, an aldehyde group, and a carbon number of 2 to 10 Substituent, electron-attractive substituent having a carbon number of 2 to 10, an amine carbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 10; The organic group having a hetero atom (except for the electron-attracting substituent) or the hydrogen atom may be used, and at least one of R5 to R8 is a substituent capable of attracting the electron. [2] The oxime complex compound according to [1], wherein the electron-attracting substituent is a fluorine atom, a fluorine-substituted alkyl group having a carbon number of 1 to 10, and a fluorine substitution of a carbon number of 1 to 1? Alkoxy or cyano group. [3] The ruthenium complex compound as described in [1] or [2], which is represented by the following formula (2) [Chemical 4]

(In the formula (2), R1 is an organic group having 2 to 30 carbon atoms, and R2 to R4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). The ruthenium complex compound according to any one of [1] to [3], which is represented by the following formula (3). [Chemical 5]

• (3) (In the formula (3), R1 is an organic group having 2 to 30 carbon atoms). [5] The oxime complex compound according to any one of [1] to [4] wherein R1 is an alkyl group having 2 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. [6] The oxime complex compound according to any one of [1] to [5], which is a facial body. [7] An organic electroluminescence device comprising: a substrate; and a counter electrode formed on the substrate; and an organic electroluminescence device comprising a layer of the light-emitting layer or a plurality of organic layers between the pair of electrodes, It is characterized in that the luminescent layer is a ruthenium complex compound containing any one of Π] to [6]. [8] The organic electroluminescence device according to [7], wherein the light-emitting layer is a non-conjugated polymer compound containing a charge transport property. -9- 200922941 [9] An image display device using the organic electroluminescence device according to [7] or [8]. [10] A surface-emitting light source characterized by using the electroluminescent element as described in [7] or [8]. [11] A method for producing a ruthenium complex compound, which is a method for producing a ruthenium complex compound as described in Π], characterized in that ruthenium chloride (111) trihydrate is represented by the following formula (1 · 1) The phenylpyridine derivative shown is heated in a mixed solvent of an alcohol and water to obtain a fluorene dinuclear complex represented by the following formula (1-2), and the dinuclear complex is described below. The phenylpyridine derivative represented by the formula (1-1) is heated in a solvent in the presence of a base and/or a silver salt. [Chemical 6]

(1-2) (In the formula (1-1) and the formula (Bu 2), R1 is an organic group having 2 to 30 carbon atoms, and R2 to R4 are each independently a hydrogen atom or an alkyl group having a carbon number of i 10, R 5 〜R8 are each independently selected from a halogen atom, a carbon number of 1 to 10, a fluorine-containing alkyl group of the group - 10, 2009, and a carbon number of 1 to 10, a fluorine-substituted alkoxy group having a carbon number of 1 to 10, a cyano group, an aldehyde group, and a carbon number. An electron-attractive substituent of a 2 to 10 fluorenyl group, an alkoxycarbonyl group having 2 to 1 carbon atom, an amine carbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms; The organic group having a hetero atom (except for the electron-attracting substituent) or a hydrogen atom having 1 to 10 carbon atoms, and at least one of R5 to R8 is a substituent capable of attracting electrons. (Effect of the Invention) According to the present invention, it is possible to provide a blue-emitting ruthenium complex compound which has high solubility in a solvent for a coating solution at the time of production of an organic EL device and excellent thermal stability, and further provides An organic EL device using the ruthenium complex compound is an organic EL device having high light-emitting efficiency and long life. Further, in the production of the organic EL device, the coating solution in which the ruthenium complex compound is dissolved can be uniformly applied onto the substrate, and the film formability is good. [Embodiment] Hereinafter, the present invention will be specifically described. <铱 complex compound> In the present invention, a ruthenium complex compound represented by the following formula (1) is used. -11 - 200922941 [Chem. 7]

(In the formula (1), R1 is an organic group having 2 to 30 carbon atoms, R2 to R4 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R5 to R8 are each independently selected from a halogen atom and a carbon number of 1 to a fluorine-substituted alkyl group of 10, a fluorine-substituted alkoxy group having 1 to 1 carbon atom, a cyano group, an aldehyde group, a fluorenyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and carbon An electron-attracting substituent of an amine carbonyl group, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms, and an organic group having a carbon number of 1 to 1 Å or a hetero atom (the aforementioned electrons) Except for the attractive substituent) or a hydrogen atom, at least one of R5 to R8 is the electron-attracting substituent). In the above formula (1), R1 is an organic group having 2 to 30 carbon atoms, preferably a carbon number of 2 to 30, in order to improve the solubility of the ruthenium complex compound in the solvent for the coating solution in the production of the organic EL device. The alkyl group or the aralkyl group having 7 to 30 carbon atoms is more preferably a group having 3 to 30 carbon atoms having a branched structure and/or a cyclic structure, and having an aralkyl group having a branched structure and having 8 to 30 carbon atoms. Specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 3- Methyl butyl, 1,1-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 4-methylpentyl, 2-ethylbutyl, n-heptyl, 2·heptyl, 3 -heptyl, 4-heptyl, n-octyl, 2-oct-12- 200922941, 3-octyl, 4-octyl, n-ethylhexyl, n-decyl, 2-indenyl, 3-fluorenyl , 4-indenyl, 5-indenyl, n-decyl, 3,7-dimethyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, 2-methyl-10- Hexaalkyl, n-octadecyl, n-decyl, n-docosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, diamond Alkyl, 3,5-dimethyladamantyl, benzyl, 1-phenylethyl, 2-phenylethyl, 2-(1-phenyl)propyl or 3,3-diphenylpropyl. Preferred are isopropyl, 2-butyl, isobutyl, tert-butyl, 2-pentyl, 3-pentyl, 3-methylbutyl, 1,1-dimethylpropyl, 2- Hexyl, 3-hexyl, 4-methylpentyl, 2-ethylbutyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-octyl, 3-octyl, 4-octyl, 2-ethylhexyl, 2-indenyl, 3-indenyl, 4-indenyl, 5-indenyl, 3,7-dimethyloctyl, 2-methylhexadecyl, cyclopropyl, cyclo Butyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, adamantyl, 3,5-dimethyladamantyl, 1-phenylethyl, 2-phenylethyl, 2-(1 -Phenyl)propyl or 3,3-diphenylpropyl, more preferably 2-butyl, 2-pentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclohexylmethyl or adamantyl . In order to improve the thermal stability, in the above formula (1), R2 to R4 are preferably a hydrogen atom or a hospital having a carbon number of 1 to 10. Specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-butyl group, a tert-butyl group, a 1-pentyl group, a 2-pentyl group, and a 3-pentyl group. 3-methylbutyl, hydrazine-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 4-methylpentyl, 2-ethylbutyl, n-heptyl, 2-heptyl, 3 -heptyl, 4-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, n-ethylhexyl, n-decyl, 2-indenyl, 3-indolyl, 4-anthracene Base, 5-mercapto or n-decyl-13- 200922941. Further preferred is a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom. Further, in order to obtain a blue light-emitting compound, in the above formula (丨), at least one of R5 to R8 is an electron-attracting substituent. The electron-attracting substituent is selected from the group consisting of a halogen atom, a carbon number of 1 to 1 经, a substituted group, a carbon number of 1 to 10, a fluorine-substituted alkoxy group, a cyano group, an aldehyde group, and a carbon number of 2. An electron-attractive substituent of a fluorenyl group having a fluorenyl group of 10 to 10, an alkoxycarbonyl group having 2 to 1 Å, an amine carbonyl group having a carbon number of 1 to 10, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms is preferred. . The electron-attracting substituent is more preferably a fluorine atom, a fluorine-substituted alkyl group having 1 to 1 carbon atom, a fluorine-substituted alkoxy group having 1 to 1 carbon atom or a cyanoguanidine. Specific examples thereof include fluorine. Atom, chlorine atom, bromine atom, iodine atom, trimethoxymethyl, trifluoromethoxy, cyano, aldehyde, ethyl fluorenyl, benzhydryl, methoxycarbonyl, phenoxycarbonyl, dimethylamine carbonyl, Thiocyanate group, methanesulfonyl 'benzenesulfonyl group. More preferably, it is a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a cyano group, and particularly preferably a fluorine atom. In the above formula (1), the electron-attracting substituents in R5 to R8 are an organic group having a carbon number of 1 to 10 and having a hetero atom (except for the aforementioned gastric attracting substituent) or A hydrogen atom. The oxime complex compound of the present invention is preferably a compound represented by the following formula (2) in terms of solubility in a solvent for a β coating solution at the time of production of an organic EL device, and excellent heat stability. -14- 200922941

(In the formula (2), R1 is an organic group having 2 to 30 carbon atoms. R2 to R4 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. More preferably, it is a compound represented by the following formula (3).

(In the formula (3), R1 is an organic group having 2 to 30 carbon atoms, and when the oxime complex compound of the present invention is a facial body, it is preferable in terms of improving the luminosity of the compound. When the ruthenium complex compound of the present invention is compared with the conventional phosphorescent blue light-emitting compound, for example, a compound represented by the following formula, since it does not have a weakly bonded picidinic acid group with a ruthenium atom, Therefore, it has the characteristics of excellent thermal stability. -15- 200922941 [化10]

Lr(F2HexOppy)2(pic) <Manufacturing method of ruthenium complex compound> The method for producing the ruthenium complex compound of the present invention is not particularly limited, and for example, it can be produced by the following method. -16- 200922941 [化11]

The method for producing the ruthenium complex compound of the present invention will be described with reference to the above-described flowchart. First, the ruthenium (III) chloride trihydrate and the phenylpyridine derivative (1-1) are heated and reacted in a mixed solvent of an alcohol and water to obtain a fluorene dinuclear complex (1 - 2). This heating step can also be carried out under reflux. The alcohol in the mixed solvent may, for example, be methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 2-methoxyethanol or 2-ethoxyl. Ethanol, ethylene glycol,: 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethyl-17-200922941 diol, diethylene glycol monomethyl Ether, etc. The ratio of the alcohol to water (alcohol: water (volume ratio)) in the above mixed solvent is from 1 to 9:1. Specific examples of the mixed solvent include a mixed solvent of 2-ethoxyethanol and water (2-ethoxyethanol: water = 3:1 (volume ratio)). Further, R1 to R8 in the formulas (1-1) and (1-2) are synonymous with R1 to R8 of the formula (1), respectively. Next, the ruthenium complex compound (1) of the present invention can be obtained by heating the dinuclear complex compound and the phenylpyridine derivative (1-1) in the presence of a base and/or a silver salt in a solvent. This heating step can also be carried out under reflux. The above-mentioned base may, for example, be an inorganic base compound such as sodium carbonate or potassium carbonate, or an organic base such as tributylamine or lutidine. Further, examples of the silver salt include silver oxide (I), silver sulfide (I), silver sulfate (I), silver nitrate (I), silver (I) phosphate, silver acetate (I), and silver trifluoroacetate (I). Silver (I) p-toluenesulfonate, silver (I) methanesulfonate, silver (I) trifluoromethanesulfonate, and the like. In the second reaction step, if toluene is used as the solvent, the ruthenium compound and the meridine compound of the meridian coil are sometimes obtained in a mixture type, if a higher boiling point is used. When used as a solvent, the pharmaceutically complex ruthenium complex compound is obtained in high yield and high selectivity. <Organic EL device> The organic EL device of the present invention includes a substrate, and a pair of electrodes formed on the substrate, and an organic EL device including one layer or a plurality of organic layers between the pair of electrodes. The above-mentioned light-emitting layer is an organic EL element which is characterized by containing the compound of 铱-18-200922941 of the present invention. Further, the light-emitting layer is preferably an organic EL device characterized by a charge transporting non-conjugated polymer compound. An example of the configuration of the organic EL device of the present invention is shown in Fig. 1, but the configuration of the organic EL device of the present invention is not limited thereto. In Fig. 1, a light-emitting layer 3 is provided between the anode 2 and the cathode 4 provided on the transparent substrate 1. In the organic EL device, for example, a hole injection layer may be provided between the anode 2 and the light-emitting layer 3, and an electron injection layer may be provided between the light-emitting layer 3 and the cathode 4. In the above, the organic layer containing the ruthenium compound of the present invention and the charge transporting non-conjugated polymer compound can be used as a light-emitting layer having both hole transporting property and electron transporting property. Therefore, even if a layer composed of other organic materials is not provided, there is an advantage that it can be made into an organic EL element having high luminous efficiency. The organic layer is not particularly limited, and for example, it can be produced as follows. First, a solution obtained by dissolving the ruthenium complex compound of the present invention and a charge transporting non-conjugated polymer compound is prepared. The solvent to be used for the preparation of the above-mentioned solution is not particularly limited. For example, a chlorine-based solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran or anisole, or an aromatic hydrocarbon such as toluene or xylene may be used. Examples of the solvent, a ketone solvent such as acetone or methyl ethyl ketone, an ester solvent such as ethyl acetate, butyl acetate or ethyl cellosolve acetate. Next, the solution prepared as above is formed into a film on a substrate by an inkjet method, a spin coating method, a dip coating method, a printing method, or the like. Since the ruthenium complex compound of the present invention has high solubility in the solvent for the coating solution from -19 to 200922941, it is excellent in that the compound can be uniformly formed on the substrate when the coating solution for dissolving the compound is applied. . The concentration of the above solution depends on the compound to be used, the film formation conditions, and the like. For example, in the case of the spin coating method and the dip coating method, it is 0·1 to 1 〇 W t °/. It is better. As described above, since the ruthenium complex compound of the present invention has high solubility in a solvent, it can be easily formed into a film, and the simplification of the production process can be achieved, and the area of the element can be reduced. Further, the ruthenium complex compound of the present invention may be used alone or in combination of two or more of the light-emitting layers used in the organic EL device. The organic EL element used in the light-emitting layer of the ruthenium complex compound of the present invention has a long life and high luminous efficiency. <Other Materials> Each of the above layers may be formed by mixing a molecular material of a cartridge as a binder. Examples of the polymer material include polymethyl methacrylate, polycarbonate, polyester, polyfluorene, and polyphenylene ether. Further, the materials used in the above layers are materials in which different functions are mixed, for example, a light-emitting material 'hole transport material, an electron transport material, and the like, and each layer may be formed. In the organic layer having the ammonium complex compound of the present invention, other hole transporting materials and/or electron transporting materials may be further contained for the purpose of compensating for charge transportability. Such transport materials can be low molecular weight compounds and can also be cartridge molecular compounds. The hole transporting material forming the above-described hole transporting layer or the hole transporting material mixed in the light emitting layer may, for example, be TpD (N, N, dimethyl -20- 200922941 N, N'-(3- Tolyl-biphenyl·4,4,-diamine); α _NpD (4,4, bis[N-(l-naphthyl)-N-anilino]biphenyl); m_MTDATA(4,4,,4 , a low molecular triphenylamine derivative such as -5 (3-tolylanilino)diphenylamine); a polyethyl carbazole; a local molecule compound obtained by introducing a polymerizable substituent into the above triphenylamine derivative; For example, a polymer compound of a triphenylamine skeleton disclosed in Japanese Laid-Open Patent Publication No. Hei 8-157575, and the like. The above-mentioned hole transporting material may be used alone or in combination of two or more types, and may be laminated with different hole transporting materials. The thickness of the hole transporting layer depends on the conductivity of the hole transporting layer. Depending on the determination, it is not possible to determine 'preferably 1 nm to 5 μηι, more preferably 5 nm to 1 μηη, and particularly preferably 10 nm to 500 nm. The electron transporting material of the electron transporting layer or the electron transporting material mixed in the light emitting layer may, for example, be a hydroxyquinoline derivative metal complex such as A1 q 3 (aluminum trishydroxygallinate), or an oxadiazole derivative. a low molecular compound such as a triazole derivative, an imidazole derivative, a triterpene derivative or a triarylborane derivative; or a molecular compound obtained by introducing a polymerizable substituent into the α in the above low molecular compound. For example, the above-mentioned electron transporting material may be used alone or in combination of two or more kinds, and different electron transporting materials may be laminated, for example, in the case of the poly-PBD disclosed in the above-mentioned Japanese Patent Publication No. Hei. The thickness of the electron transport layer depends on the conductivity of the electron transport layer and the like, and therefore cannot be limited, and is preferably 1 nm to 5 μm, more preferably 5 nm to Ιμηι, and particularly preferably 10 nm to 5 〇〇 nm. 'Attach to the cathode side of the light-emitting layer, suppress the hole from passing through the light-emitting layer, -21 - 200922941 and efficiently combine the holes and electrons in the light-emitting layer, and also provide a hole/barrier layer. The above-mentioned hole/barrier layer is a known material such as a triazole derivative, a thiazole derivative, or a phenanthroline derivative. It is also possible to "in order to alleviate the injection hindrance in the hole injection" between the anode and the light-emitting layer. A hole injection layer is provided. In order to form the hole injection layer, a known material such as a mixture of phthalocyanine 'polyethylenedioxythiophene (PEDOT) and polystyrene acid extension (PSS) or a fluorocarbon is used. Between the cathode and the electron transport layer 'or between the cathode and the organic layer laminated adjacent to the cathode', an insulating layer having a thickness of 0·1 to 1 Onm may be provided for the electron injection efficiency of the lift. In order to form the above insulating layer, a known material such as lithium fluoride, magnesium fluoride, magnesium oxide or oxidized metal is used. As the anode material, for example, a known transparent conductive material such as a conductive polymer such as IT 0 (indium tin oxide), tin oxide, oxidized poly, polydecene, polydole or polyamine is used. The surface resistance of the electrode formed by the transparent conductive material is preferably 1 to 50 Ω/〇 (ohm/square). The thickness of the anode is preferably 5 〇 to 3 0 0 n m. The cathode material may be, for example, a metal such as Li, Na, κ, or Cs; an alkaline earth metal such as Mg, Ca, or Ba; Al; a MgAg alloy; an alloy of Al1, AAICa, or the like, and an alkali metal or an alkaline earth metal. And other known cathode materials. The thickness of the cathode is preferably from 10 nm to 1 μm, more preferably from 5 Å to 50 Å. In the case where a metal having a high activity such as an alkali metal or an alkaline earth metal is used as a cathode, the thickness of the cathode is preferably 0.1 to 1 〇〇 nm, more preferably 〇 5 to 5 〇 nm. Further, in this case, a metal layer which is stable to the atmosphere is laminated on the cathode for the purpose of protecting the cathode metal. Examples of the metal forming the metal layer of the above -22-200922941 include A1, Ag, Au, Pt, Cu, Ni, Cr, and the like. The thickness of the metal layer is preferably i〇ntn to ΐμηι, more preferably 5 〇 to 500 nm. The substrate of the organic EL element of the present invention may be an insulating substrate transparent to the light-emitting wavelength of the luminescent material. In addition to glass, a film-forming method of the above-mentioned hole transport layer, light-emitting layer, and electron transport layer may be used, such as a transparent plastic such as PET (polyethylene terephthalate) or polycarbonate, for example, 'resistance heating can be used. A steaming method, an electron beam evaporation method, a sputtering method, an inkjet method, a spin coating method, a printing method, a spray method, a disperser method, and the like. In the case of a low molecular weight compound, it is suitable for use by an inkjet method, a spin coating method, or a printing method by using a resistance heating distillation or electron beam evaporation to suitably use a 'polymer compound'. Further, for the film forming method of the above anode material, for example, an electron beam vapor deposition method, a ruthenium plating method, a chemical reaction method, a coating method, or the like can be used, and the film forming method of the cathode material can be, for example, a resistance heating vapor deposition method. , electron beam evaporation method, sputtering method, ion plating method, and the like. <Charge-transporting non-conjugated polymer compound> The charge-transporting non-conjugated polymer compound is a group of a polymerizable compound selected from the group consisting of a hole transporting property and an electron transporting polymerizable compound. The monomer of at least one polymerizable compound is preferably a copolymerized polymer. In addition, in the present specification, a polymerizable compound having a hole transporting property and a polymerizable compound having an electron transporting property are collectively referred to as a polymerizable compound of charge transportability -23-200922941. In other words, the non-conjugated polymer compound having a charge transporting property is a structural unit derived from a polymerizable compound having one or more types of hole transporting properties, or one or more electron transporting polymerizable compounds. The derived structural unit of the polymer is preferred. If such a polymer is used, the degree of charge mobility in the light-emitting layer can be increased, and a homogeneous film can be formed by coating, and higher luminous efficiency can be obtained. In addition, the charge transporting non-conjugated polymer compound is a structural unit derived from a polymerizable compound having one or more types of hole transporting properties, and one or more kinds of electron transporting polymerizable compounds. It is more preferable that the derived structural unit polymer is composed. When such a polymer is used, since the polymer has a function of hole transporting property and electron transporting property, the hole and the electron are more efficiently combined in the vicinity of the phosphorescent compound, so that higher light is obtained. effectiveness. The above-mentioned transportable polymerizable compound and the electron transporting polymerizable compound are not particularly limited as long as they have a substituent having a polymerizable functional group, and a known charge transporting compound can be used. The polymerizable functional group may be any of a radical polymerizable property, a cationic polymerizable property, an anionic polymerizable property, an addition polymerizable property, and a condensation polymerizable functional group. Among them, a radical polymerizable functional group is preferred because it is easy to produce a polymer. The polymerizable functional group may, for example, be a urethane (meth) acrylate such as an allyl group, an alkenyl group, an acrylate group, a methacrylate group or a methacryloxyethyl urethane. Vinyl amidino groups and derivatives thereof and the like. -24- 200922941 Among them, alkenyl is preferred. More specifically, the substituent in which the polymerizable functional group is an alkenyl polymerizable functional group is the following general formula (A 1 ), and the substituent is more preferably. Among them, the following formulas (Al) and (A5) and the substituents shown above are more preferable because they are capable of a functional group of a charge transporting compound. When (A8) and (12) shown in the above -(A12) are easily introduced into the polymerization [Chemical 12] -CH 'CH: CH3 - Λ

H3C CH3 h2c —c. ch5 ch2 (A1) ch2 (A2) (A3) (A4) CHa

H2C

-25- 200922941

CH W

(A12) CH2 The above-mentioned polymerizable compound having a hole transport property is specifically a compound represented by the following general formulas (E1) to (E6), and the charge mobility in the non-conjugated polymer compound is preferable. From the viewpoint, a compound represented by the following formulas (E1) to (E3) is more preferable. [Chem. 13]

-26- 200922941

Specifically, the electron transporting polymerizable compound is preferably a compound represented by the following general formulas (E7) to (E15), and from the viewpoint of charge mobility in the non-conjugated polymer compound. The compounds represented by the following formulas (E7) and (E12) to (E14) are more preferred. [Chem. 14]

(E7)

m

-27- 200922941

(E13)

<E15) Further, in the above formulae (El) to (E15), the substituent represented by the above formula (A1) is replaced by a substituent represented by the above general formula (A2) to (A12). It is particularly preferable to use a compound having a substituent represented by the above (A1) or (A5) in order to allow a functional group to be easily introduced into a polymerizable compound. In addition, the compound represented by any one of the above formulas (E1) to (E3) which is the above-mentioned electron transporting polymerizable compound and the above (E7) and (E) which are the electron transporting polymerizable compounds are used. 12) A compound in which the compound represented by any of (E 14) is copolymerized is more preferable. When such a non-conjugated polymer compound is used, it is possible to further combine the holes and electrons on the phosphorescent compound to obtain higher luminous efficiency. Further, an organic layer having a uniform distribution can be formed simultaneously with the phosphorescent compound, and an organic EL element excellent in durability can be obtained. In the organic layer (light-emitting layer) containing the ruthenium complex compound and the non-conjugated polymer compound used in the organic EL device of the present invention, the ruthenium complex compound is used for the non-conjugated polymer compound. The formed matrix is contained in a dispersed state. Therefore, it is possible to obtain light emission which is generally difficult to use, that is, light emission by a triplet excitation state of a phosphorescent compound. Therefore, high luminous efficiency can be obtained by using the above organic layer. Further, the charge transporting non-conjugated polymer compound ' may further contain a structural unit derived from another polymerizable compound, without departing from the object of the present invention. The polymerizable compound may, for example, be a compound having no charge transporting property such as alkyl (meth)acrylate such as methyl acrylate or methyl methacrylate, or styrene or a derivative thereof, but is not limited thereto. Further, the charge transporting non-conjugated polymer compound preferably has a weight average molecular weight of 1,000 to 2,000,000, more preferably 5,000 to 1,000,000. The molecular weight in the present specification means a molecular weight in terms of polystyrene measured by a GPC (gel permeation chromatography) method. If the above molecular weight is in this range, the polymer is soluble in an organic solvent to obtain a uniform film. Therefore, the charge transporting non-conjugated polymer compound may be a random copolymer, a segmented copolymer, and an interactive copolymer. Any of the things. The method for polymerizing the charge transporting non-conjugated polymer compound may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred. <Application> The organic EL device of the present invention is suitably used in a video display device in a pixel form of a matrix method or a segment method by a known method. Further, the organic EL device does not form a pixel, and is also suitably used as a surface light source. -29- 200922941 The organic EL device of the present invention is specifically suitable for use in a display device such as a computer, a television, a portable terminal, a mobile phone, a car navigation device, a video camera, a backlight, an electronic photo, an illumination source, Record light source, exposure light source, reading light source, sign, kanban, interior decoration, optical communication, etc. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. <Measurement device, etc.>

1)! NMR NMR apparatus: JNMEX270 manufactured by Sakamoto Electronics (JEOL) 270MHz dissolved in: ^: Heavy chloroform [Synthesis Example 1] (Synthesis of ruthenium compound (4a)) -30- 200922941

(HO

RK

MiPP^NtjCO»

[化15]

NM〇2 HO tVa ——-tya, Liu·t Guang _

(1«): R-n-X# (lb) : R-2-T# (lc) : R«2-ethylhexyl

\α,,Κ {2e): R_n-butyl (2b): R-2-TS (2e): R-2-ethylhexyl

(3a): R = η-butyl (3b): R = 2-TS of 3c$: R * 2-ethylhexyl

(4e): R = n butyl (4b): R = 2-T* (4ci: R«2·ethylhexyl is described with reference to the above scheme. <Synthesis of 2-chloro-4-hydroxypyridine> 40% sulfuric acid (50 g) and 4-amino-2-chloropyridine (3.0 g, 23.3 mmol) were added to the eggplant flask and dissolved. The sodium nitrite was added while stirring at 〇 ° C ( 1.9 3 g '2 8.0 mmoles, and stirred at room temperature for 24 hours. After the reaction, the reaction solution was neutralized by adding aqueous sodium hydroxide solution and aqueous sodium hydrogencarbonate solution, and the organic layer was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and evaporated to dryness, and then evaporated to dryness to give 2-2-31 - 200922941 chloro-4-hydroxypyridine (thick brown solid). Yield 2.78 g, yield 9 2 1H-NMR (270MHz, DMSO-d6) ppm: ll_20(s, 1H, - OH), 8.09 (d, 1H 'J = 5_4Hz, ArH), 6.81 (s, 1H, ArH), 6.77 (d, 1 H, J = 2.2 Hz, ArH) <Synthesis of Compound (1 a)> In the two-necked flask equipped with a Dimroth cooling tube and a three-way stopcock, the above-mentioned synthesized 2-chloro- 4-hydroxypyridine (2.6 g, 20 mmol) Ear), potassium carbonate (5.5 g, 40 mmol), and nitrogen exchange. Also, add dehydrated DMF (80 ml), 1-bromobutane (4.1 g, 30 mmol), and at 1 〇 The mixture was stirred for 3 hours. After the reaction, toluene was added, and the mixture was washed twice with pure water, and the organic layer was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, evaporated and evaporated. The compound (1 a) (colorless liquid) was obtained by the following drying. The yield was 3.6 g, and the yield was 97%. <Synthesis of Compound (2a)> In a three-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock, Compound (la) (3.6 g, 19.4 mmol), 2,4-difluorophenylboronic acid (3.7 g, 23.3 mmol), potassium carbonate (5.5 g '40 mmol), 1,2-two Methoxyethane (50 ml), pure water (20 ml), and blown with nitrogen for 5 minutes. Further, 'add [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (II) The dichloromethane complex (3 26 mg, 0.4 mmol) was refluxed while stirring for 3 hours. After the reaction, it was cooled to room temperature, added with pure water, and extracted with ethyl acetate. Machine layer -32- 200922941. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated. The residue was purified by column chromatography (solvent: chloroform), and the solvent was evaporated and evaporated under reduced pressure. Drying gives compound (2 a) (colorless liquid). The yield was 4.57 g and the yield was 90%. <Synthesis of Compound (3 a)> In a two-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock, Compound (2a) (2.0 g '7.6 mAh), ruthenium chloride (in) trihydrate was added. (1.07 g of '3.04 mmol), 2-ethoxyethanol (36 ml), and pure water (12 ml) were placed and nitrogen was blown, and the mixture was refluxed while stirring for 2 hours. After the reaction, 'cooled to room temperature', pure water was added to precipitate the product. The precipitate was collected by filtration, washed with methanol and dried under reduced pressure to give compound (3a) (yellow powder). The yield was 1.88 g and the yield was 82%. <Synthesis of Compound (4a)> In a two-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock, a compound (3a) (400 mg, 0.27 mmol) and potassium carbonate (187 mg, 1 to 35 mmol) were added. Ear), compound (2a) (280 mg, 1.06 mmol) and nitrogen exchange. Further, (6 ml) and silver trifluoromethanesulfonate (1) (171 mg '0.67 mmol) were added, and the mixture was refluxed while stirring for 4 hours. After the reaction, the mixture was cooled to room temperature, and chloroform was added thereto, followed by filtration using Celite® to remove insolubles. The solvent of the filtrate was distilled off, and the residue was purified by silica gel chromatography (solvent: chloroform/hexane = 1/1), and then recrystallized from methanol/dichloromethane and dried in vacuo to give compound (4a) crystallization). The yield was 400 mg, and the yield was -33-200922941, 76%. When analyzed by 1H-NMR, no peak corresponding to a meridional body was observed, and it was found that all of the obtained compounds were facial bodies. 1 Η - NMR (2 7 0 Μ Η z > CDCl3) ppm : 7.78 (m ' 3H * ArH) > 7.28 (d ' 3H, J = 6.2 Hz, ArH), 6.49 (dd, 3H, J = 6.5 , 2.4 Hz > ArH), 6.3 6 (m, 3 H, Ar H), 6.2 6 (dd, 3 H, J = 9 · 2 ' 2.7 Hz, ArH), 3 _ 9 3 (d, 6 H, J = 5.7 H z, CH 2 0), 1 _ 7 4 (m , 1H, CH), 1.51 - l_31 (m, 24H, CH 2 ), 0.96 - 0.87 (m, 18H, CH3). [Synthesis Example 2] (Synthesis of ruthenium complex compound (4b)) 2-chloro-4-hydroxypyridine synthesized in Synthesis Example 1 (1.30 g) was placed in a two-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock. , 10 millimoles), potassium carbonate (2.76 grams, 20 millimoles), and subjected to nitrogen replacement. Further, dehydrated DMF (20 ml), 2-bromobutane (2.06 g, 15 mmol) were added, and stirred at 80 ° C for 14 hours. After the reaction, chloroform was added, and the mixture was washed twice with pure water, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated. The residue was purified by medium pressure tannin column chromatography (solvent: chloroform / hexane = 1 / 1 to chloroform), and the solvent was evaporated and dried under reduced pressure to give compound ( lb) (colorless liquid). The yield is 1.8 5 grams' yield is 100%. 1 Η - NMR (2 7 0 ΜΗ z 1 CDCl3) ppm : 8.16 (d >1H; J = 5.9 Hz > ArH), 6.8 0 (d, 1 H, J = 2 · 4 Hz 'ArH), 6 · 7 1 ( dd, -34- 200922941 1H, J = 5.8, 2. 0Ηζ, ArH), 4.38 (m, 1H, CH), 1.71 (m, 2H, CH2), 1.33 (d, 3H, J = 6.5 Hz, CH3), 0.97 (t, 3H, J = 7.4 Hz, CH3). <Synthesis of Compound (2b)> In a three-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock, Compound (113) (1.85 g, 10 mmol) and 2,4-difluorophenylboronic acid ( 1.90 g, 12 mmol, sodium carbonate (2.12 g, 20 mmol), 1,2-dimethoxyethane (30 ml), pure water (10 ml), and nitrogen was blown for 5 min. A [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (163 mg, 0.2 mmol) was added, and the mixture was refluxed for 3 hours while stirring. After the reaction, it was cooled to room temperature, pure water was added, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated. The residue was purified by medium pressure tannin column chromatography (solvent: chloroform / hexane = 1 / 1 to chloroform - ethyl acetate / chloroform = 2.5 / 97.5 gradient), and the solvent was evaporated, and dried under reduced pressure to give compound (2b) (colorless liquid). The yield was 2.10 g and the yield was 80%. 'H-NMRClTOMHz, CDCl3) ppm: 8.48 (d , 1 Η , J = 5.7 Hz, ArH), 7.97 (m, 1H, ArH), 7.24 (m, 1H, ArH), 6.99 (m, 1H, ArH), 6.90 (m, 1H, ArH), 6.75 (dd, 1H, J = 5.8, 2_6Hz, ArH), 4.45 (m, 1H, CH), 1.74 (m, 1H, CH2), 1.35 (d, 3H, J = 5.9 Hz, CH3), 0.99 (t, 3H, 1 = 7.21^, CH3) ° <Synthesis of Compound (3b)> 35- 200922941 In a two-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock , compound (2b) (885 mg, 3.4 mmol), cerium (III) chloride trihydrate (494 mg, 1.4 mmol), 2-ethoxyethanol (21 ml), pure water (7) ML), and after blowing nitrogen gas, it was refluxed while stirring for 69 hours. After the reaction, it was cooled to room temperature, and pure water was added to precipitate the product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure to give Compound (3b) (yellow powder). The yield was 73 3 mg and the yield was 70%. <Synthesis of Compound (4b)> In a two-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock, Compound (3b) (301 mg, 0.2 mmol) and potassium carbonate (138 mg, 1.0 mmol) were added. Ear), compound (2b) (132 mg, 0.5 mmol) and nitrogen exchange. Further, after adding (4 ml) and silver trifluoromethanesulfonate (1) (123 mg, 0.48 mmol), the mixture was refluxed for 4 hours while stirring. After the reaction, the mixture was cooled to room temperature, and chloroform was added thereto, and the mixture was filtered through Celite to remove insoluble materials. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (solvent: chloroform/hexane = 1/3 to chloroform), and then recrystallized from methanol/dichloromethane. ) (yellow crystals of yellow). The yield was 332 mg and the yield was 85 %. When analyzed by 1 Η - N M R , the peak corresponding to the meridional body was not observed, and it was found that all of the obtained compounds were facial bodies. 1H-NMR (270MHz > CD C13 ) ppm : 7 · 7 6 (m, 3 Η, A r Η), 7.27 (d ' 3H, J = 6.8HZ, ArH), 6.46 (dd, 3H, J = 6.3 , 2 _ 3 H z ' A r H) ' 6 · 3 6 (m,3 H,A r H),6.2 6 ( m,3 H ' A r H) ' -36- 200922941 4.41(m,3H, CH) ' 1.72(m ' 3H,CH2), 1.34(d,9H, J = 5.7Hz, CH3) ' 0.98(t,9H,J = 7.〇Hz, CH3). [Synthesis Example 3] <Synthesis of Compound (Ic)> 2-N-chloro-4-hydroxypyridine synthesized in Synthesis Example 1 was added to a two-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock (2.34 g, 18.1). Millol), potassium carbonate (5.00 g '36.2 mmol) and subjected to nitrogen replacement. Further, dehydrated DMF (72 ml), 2-ethylhexyl bromide (5·24 g, 27.15 mmol) was added, and stirred at 80 ° C for 5 hours. After the reaction, toluene was added, and the mixture was washed twice with pure water, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, filtered, and evaporated. The residue was purified by column chromatography on EtOAc (EtOAc: EtOAc (EtOAc:EtOAc) The yield was 2.12 grams and the yield was 48%. !Η-ΝΜΚ(270ΜΗζ, CDCl3)ppm : 8.17(d, 1Η , J = 5.9Hz, ArH), 6.8 3 ( d,1 H,J = 2 · 2 H z,A r H),6 · 7 4 (dd, 1H, J = 5.9, 2.4 Hz, ArH), 3.89 (d, 2H, J = 5.7 Hz, CH20), 1.74 (m, lH, CH), 1.54-1.31 (m, 8H, CH2), 0.96 -0.8 8 (m, 6 H, CH 3). <Synthesis of Compound (2c)> A compound (1 〇 (2.12 g, 8.77 mmol), 2,4-difluorophenylboronic acid was added to a three-necked flask equipped with a Dim Roche cooling tube and a three-way stopcock. 37- 200922941 (1.66 g, 10.52 mmol), sodium carbonate (1.86 g '17.54 mmol), 1,2-dimethoxyethane (27 ml), pure water (9 ml)' and blowing Nitrogen gas was introduced for 5 minutes, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (Π) dichloromethane complex (163 mg, 0.2 mmol) was added while stirring for 2 hours. After the reaction, the mixture was cooled to room temperature, pure water was added, and the organic layer was extracted with ethyl acetate. The organic layer obtained was dried over magnesium sulfate, filtered, and evaporated to remove solvent. : ethyl acetate / hexane = 5/95 to 3 0/7 0 gradient) After purification, the solvent was evaporated, and dried under reduced pressure to give compound (2c) (colorless liquid). Yield: 2.17 g, yield 78 1H-NMR (270MHz, CDCl3) ppm: 8.50 (d , 1 Η , J = 5.9 Hz, ArH), 7.97 (m, 1 Η, ArH), 7.25 (d, 1 Η, ArH) ' 6.98 (m, 1H, ArH), 6_90 (m, 1H, ArH), 6.79 (dd, 1H, J = 5.7, 2.4 Hz, ArH), 3.9 4 (d, 2 H, J = 5 _ 9 H z, C Η 2 O), 1.77 (m , lH, CH), 1.5 5 - 1.3 2 (m, 8H, CH2), 0_97-0.88 (m, 6H, CH3). <Synthesis of Compound (3c)> With Dim Roche Cooling Tube and Three-way Stopcock In a two-necked flask, compound (2c) (767 mg, 2.4 mmol), ruthenium (III) chloride trihydrate (3 5 3 mg, 1. 〇 millimol), 2-ethoxyethanol were added. (15 ml), pure water (5 ml), and nitrogen gas, and refluxed while stirring for 23 hours. After the reaction, the mixture was cooled to room temperature, and pure water was added to precipitate the product. The precipitate was collected by filtration and washed with methanol. Thereafter, the compound (3c) (yellow powder) was obtained by drying under reduced pressure. Yield: 736 g, yield: 85%. -38 - 200922941 <Synthesis of Compound (4c)> with Dim Roche Cooling Tube Add compound (3 〇 (3 46 mg, 0.2 mmol), potassium carbonate (138 mg, 1.0 mmol), compound (2c) (160 mg, 0.5 mmol) in a two-necked flask with a three-way stopcock. And carry out nitrogen replacement. After addition to (4 ml), silver trifluoromethanesulfonate (1) (123 mg, square. 48 mmol), refluxed for three hours under stirring. After the reaction, the mixture was cooled to room temperature, and chloroform was added thereto, and the mixture was filtered through Celite to remove insoluble materials. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (solvent: chloroform/hexane = 5/95 to 20/8 0), and then recrystallized from methanol/dichloromethane. (4c) (yellow crystals of yellow). The yield was 394 mg and the yield was 86%. When analyzed by 1H-NMR, the peak corresponding to the meridional body was not observed, and it was found that all of the obtained compounds were facial bodies. 1 H-NMR (2 7 0 MHz > CDCl 3 ) ppm : 7.78 (m 5 3H 5 ArH) » 7.28 (d, 3H, J = 6.2 Hz, ArH), 6.49 (dd, 3H, J = 6.5, 24 Hz > Ar6) '6_36(m,3H,ArH) ' 6.2 6 (dd,3 H,J = 9 · 2 , 2.7 Hz, ArH), 3.93 (d, 6H, J = 5.7 Hz, CH20), 1.74 (m , :1H 'CH), 1.51-1.31 (m, 24H, CH2), 0.96-0_87 (m, 1 8H, CH3). <Solubility Test> [Example 1] Compound (4a) was mixed with chloroform or toluene at a specified concentration, and -39-200922941 was visually confirmed to be stirred at room temperature for 1 hour. All dissolved or dissolved remaining. The test results are shown in Table 1. [Example 2] The compound (4b) was mixed with chloroform or toluene at a predetermined concentration, and it was visually confirmed that the compound (4b) was stirred at room temperature for 1 hour, and all of the apricots were dissolved or dissolved. The test results are shown in Table 1. [Example 3] The compound (4c) was mixed with chloroform or toluene at a specified concentration, and it was visually confirmed whether or not the compound (4c) which was stirred at room temperature for 1 hour was completely dissolved or dissolved. The test results are shown in Table 1. [Comparative Example 1] Ir(F2MeOppy) 3 (a facial body, see the following figure) was mixed with chloroform or toluene at a predetermined concentration, and it was visually confirmed that Ir(F2MeOppy) 3 was stirred at room temperature for 1 hour. Whether it is completely dissolved or dissolved remains. The test results are shown in Table 1. [Comparative Example 2] Ir(F2HexOppy) 2 (PiC) (refer to the following figure) was mixed with chloroform or toluene at a specified concentration, and it was visually confirmed whether Ir(F2HexOppy) 2 (pic) was stirred at room temperature for 1 hour. All dissolved or dissolved remaining. The test results are shown in Table 1. -40 * 200922941 [Comparative Example 3] Ir(PPy) 3 (surface type, see the following figure) was mixed with 5 fingers or toluene, and it was visually confirmed whether all of the room temperature Ir (ppy) 3 was dissolved or dissolved. The rest. The results of the test g were stirred for 1 hour with chlorine, and the results are shown in Table 1. [Chemistry 16]

Lr(ppy)3 -41 - 200922941 [Table i] Table 1

Material Solvent • Concentration 0.1 wt% 0.5 wt% 1 wt% Compound (4a) Chloroform oxime toluene XX Compound (4b) Chloroform oxime toluene X Compound (4c) Chloroform oxime toluene Ir F2MeOppy) 3 surface chloroform 〇 XX toluene XXX Ir (F2HexOppy) 2 (pic) chloroform 〇〇〇 toluene XX Ir (ppy) a surface chloroform 〇 XX toluene 〇 〇 全部: all dissolved X: dissolved by As can be seen from Table 1, the blue luminosity of the present invention is compared with the Ir(F2MeOppy)3 of the blue luminescent ruthenium complex compound and the erbium complex Ir(ppy)3 of the green luminescent composition. The compounds (4a), (4b) and (4c) of the ruthenium complex compound have high solubility in an organic solvent. Further, it was found that Ir(F2Hex〇ppy) 2 (pic) of the previously known blue luminescent ruthenium complex compound has high solubility in an organic solvent. [Embodiment 4] <Production of Organic EL Element> -42- 200922941

The substrate of the glass substrate of 25 mm square is used as a substrate with two holes of 4 mm wide as an anode to form a stripe-shaped substrate with τ 〇 (indium tin oxide) (Nippo Electric, Nippo Electric Co., LTD) , making organic EL components. First, 'poly(3,4-ethylenedioxythiophene)·polystyrenesulfonic acid (manufactured by Bayer Co., Ltd., trade name "Bitron P") was used on the IT crucible (anode) on which the ITO substrate was attached. The spin coating method was applied under the conditions of a number of revolutions of 35 rpm and a coating time of 40 seconds, and then dried in a vacuum dryer at 60 ° C for 2 hours under reduced pressure to form an anode buffer layer. The resulting anode buffer layer had a thickness of about 50 nm. Next, a coating solution for forming a light-emitting layer is prepared. In other words, 15 mg of the compound (4a) synthesized in Synthesis Example 1 and 35 mg of poly(N-vinylcarbazole) were dissolved in chloroform (manufactured by Wako Pure Chemical Industries, Ltd., special grade), 980 mg, and the resulting solution was obtained. The coating solution was prepared by filtration through a sieve having a pore size of 0.2 μm. Next, on the anode buffer layer, the prepared coating solution was applied by spin coating at a number of revolutions of 3000 rpm and a coating time of 30 seconds, and dried at room temperature (25 ° C) for 30 minutes to form a light. Floor. The resulting light-emitting layer had a film thickness of 10 Onm. Next, the substrate ′ which forms the light-emitting layer was placed in the vapor deposition apparatus, and the thickness of 5 ntn was vapor-deposited at a deposition rate of 〇1 nm/S, and then aluminum as a cathode was vapor-deposited at a deposition rate of 1 nm/s at 150 nm. The organic EL element 1 was produced in thickness. Further, the layer of tantalum and aluminum was formed in a stripe shape having two widths of 3 mm perpendicularly to the extending direction of the anode, and four organic light-emitting elements of 4 mm in length and 3 mm in width were produced for each glass substrate. -43-200922941 <Evaluation of EL light-emitting characteristics> Using a programmable DC voltage/current source TR6143 manufactured by Ad vante St, a voltage was applied to the organic EL element to emit light, and a brightness meter BM-made by Topcon was used. 8 Determine the luminance of the light. As a result, the obtained luminescent color, uniformity of luminescence, external quantum efficiency at the time of lighting of l〇〇cd/m2, and luminance half-life of the case when the constant current was driven by the initial luminance l〇〇cd/m2 are shown in Table 2 ( The external quantum efficiency and the luminance half-life time 値 are the average 値 of the four elements formed by one substrate). In addition, the measurement result of the luminance half-life time of Table 2 is a relative 値 when the measurement of the organic EL element 4 described later is regarded as 100 Å. [Example 5] An organic EL device 2 was produced and treated in the same manner as in Example 4 except that the compound (4a) was changed to the compound (4b). The evaluation results are shown in Table 2. [Example 6] An organic EL device 3 was produced and treated in the same manner as in Example 4 except that the compound (4a) was changed to the compound (4c). The evaluation results are shown in Table 2. [Comparative Example 4] The organic EL device 4 was produced and treated in the same manner as in Example 4 except that the compound (4a) was changed to Ir(F2MeOppy)3. The evaluation results are shown in Table 2-44 - 200922941. [Comparative Example 5] The organic EL device 5 was produced and treated in the same manner as in Example 4 except that the compound (4a) was changed to Ir(F2HexOppy) 2 (pic). The evaluation results are shown in Table 2. [Reference Example 1] An organic EL device 6 was produced and treated in the same manner as in Example 4 except that the compound (4a) was changed to Ir(PPy)3. The evaluation results are shown in Table 2. Element No. Luminescent material Luminescence color Luminescence uniformity External quantum efficiency r%i Luminance half-life time 1 (Example 4) Compound (4a) Blue uniform 5.3 147 2 (Example 5) Compound (4b) Blue uniform 7.9 198 3 (Example 6) Compound (4c) Blue uniform 7.8 202 4 (Comparative Example 4) Ir(F2MeOppy) 3 Blue unevenness 2.2 100 5 (Comparative Example 5) Ir(F2HexOppy) 2 (pic) Blue uniform 5.7 104 6 (Reference Example 1) 'Mppy) 3 Green uniformity 5.5 144 It can be seen from Table 2 that the previously known blue luminescent ruthenium complex compound (Ir(F2MeOppy) 3) is used for the organic EL element of the light-emitting layer (Comparative In Example 4), the chelating complex compound of the luminescent material is agglomerated, and uniform luminescence cannot be obtained. In contrast, the erbium complex compound of the present invention is used for the organic EL element of the luminescent layer of -45-200922941. (Examples 4 to 6), a light-emitting layer of a uniform sentence can be obtained. Further, it was found that the previously known blue luminescent ruthenium complex compound (Ir(F2Hex〇ppy) 2 (pic)) was used in the organic EL device (Comparative Example 5) of the light-emitting layer, because the compound itself was easily decomposed. In the organic EL device (Examples 4 to 6) in which the ruthenium complex compound of the present invention is used in the light-emitting layer, the characteristics of the external quantum efficiency and the luminance half-life time are also improved. The organic EL device (Reference Example 1) using the previously known green luminescent ruthenium complex is equivalent or more. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of an organic EL element of the present invention. [Description of main component symbols] 1 : Glass substrate 2 : Anode 3 · · Light-emitting layer 4 : Cathode 46-

Claims (1)

200922941 X. Patent application scope 1. A ruthenium complex compound represented by the following formula (1), [Chemical 1] (In the formula (1), R1 is an organic group having 2 to 30 carbon atoms, and R2 to R4 are each independently a hydrogen atom or an alkyl group having 1 to 1 carbon number, and R5 to R8 are each independently selected from a halogen atom and a carbon number. Fluorine-substituted alkyl group of 1 to 1 fluorene, fluorine-substituted alkoxy group having 1 to 10 carbon atoms, cyano group, aldehyde group, fluorenyl group having 2 to 1 carbon number, and alkyl group having 2 to 10 carbon atoms An electron-attractive substituent of an oxycarbonyl group, an amine carbonyl group having 1 to 1 carbon atom, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms, or an organic group having a carbon number of 1 to 10 or a hetero atom The group (except for the electron-attracting substituent) or the hydrogen atom, and at least one of R5 to R8 is the electron-attracting substituent). 2. The compound of the above formula, wherein the electron-attracting substituent is a fluorine atom, a fluorine-substituted alkyl group having a carbon number of 1 to 1 fluorene, and a fluorine having a carbon number of 1 to 10; Substituted alkoxy or cyano. 3 _If the compound of the bismuth compound of item 1 or item 2 of the patent application is not the following formula (2), -47- 200922941 (In the formula (2), R1 is an organic group having 2 to 30 carbon atoms, and R2 to R4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). 4. The compound of the ruthenium complex according to any one of the first to third aspects of the patent application, which is represented by the following formula (3), [Chemical 3] (In the formula (3), R1 is an organic group having 2 to 30 carbon atoms). The compound of the ruthenium complex according to any one of claims 1 to 4, wherein R1 is an alkyl group having 2 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. 6. The ruthenium complex compound according to any one of claims 1 to 5, which is a facial body. An organic electroluminescence device comprising a substrate, a counter electrode formed on the substrate-48-200922941, and an organic layer containing one or several organic layers of the light-emitting layer between the pair of electrodes A light-emitting element characterized in that the light-emitting layer is a ruthenium complex compound containing any one of items 1 to 6 of the patent application. 8. The organic electroluminescence device according to claim 7, wherein the light-emitting layer is a non-conjugated polymer compound containing a charge transporting property. An image display device characterized by using an organic electroluminescence device according to claim 7 or 8. 10. A surface-emitting light source characterized by using an organic electroluminescent element according to claim 7 or 8. 1 1 A method for producing a ruthenium complex compound, which is a method for producing a ruthenium complex compound according to the first aspect of the patent application, which is characterized in that ruthenium (III) chloride trihydrate has the following formula ( The phenylpyridine derivative shown in 1-1) is heated and reacted in a mixed solvent of an alcohol and water to obtain a dinuclear complex of the oxime represented by the following formula (1-2), and the dinuclear complex is obtained. The phenylpyridine derivative represented by the following formula (1-1) is heated in a solvent in the presence of a base and/or a silver salt, -49- 200922941 (In the formula (1-2), R1 is an organic group having 2 to 30 carbon atoms, and R2 to R4 are each independently a hydrogen atom or an alkyl group having 10 carbon atoms, and R5 to R8 are each independently It is a fluorine-substituted courtyard group selected from a halogen atom, a carbon number of 1 to 1 fluorene, a fluorine-substituted alkoxy group having a carbon number of 1 to 10, a cyano group, a ketone group, a carbon number of 2 to 10, and a carbon group. An electron-attracting substituent of an alkoxycarbonyl group having 2 to 1 fluorene, an amine carbonyl group having 1 to 1 carbon atom, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms, and a carbon number of 1 to 10 An organic group having a hetero atom (except for the electron-attracting substituent) or a hydrogen atom, and at least one of R5 to R8 is a substituent capable of attracting the electron.) -50-