JP5018891B2 - ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE - Google Patents

Description

  The present invention relates to an organic electroluminescence element material, an organic electroluminescence element, a display device, and a lighting device.

  Conventionally, there is an electroluminescence display (ELD) as a light-emitting electronic display device. Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements). Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL element has a configuration in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer to recombine excitons. It is an element that emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated. The thickness between the electrodes is only about 0.1 μm, and the light can be emitted at a relatively low voltage of several volts to several tens of volts. Therefore, it is attracting attention as a next-generation flat display and illumination from the viewpoint of space saving, portability, etc.

  In order to develop an organic EL element that emits light efficiently and with low power consumption, for example, in Japanese Patent No. 3093796, a small amount of phosphor is doped into a stilbene derivative, a distyrylarylene derivative, or a tristyrylarylene derivative. A technique for improving the luminance of light emission and extending the lifetime of the device is disclosed. Japanese Patent Application Laid-Open No. 63-264692 discloses that 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped therein. An element having an organic light emitting layer is disclosed, and Japanese Patent Application Laid-Open No. 3-255190 discloses an element having an organic light emitting layer in which 8-hydroxyquinoline aluminum complex is used as a host compound and doped with a quinacridone dye. Yes.

  However, in the technique disclosed in the above-mentioned patent document, when light emission from an excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3. Is 25% and the light extraction efficiency is about 20%, so the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, M.M. A. Baldo et al. , Nature, 395, pages 151 to 154 (1998), since Princeton University reported on organic EL devices using phosphorescent emission from excited triplets, the M.S. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) and US Pat. No. 6,097,147, research on materials that exhibit phosphorescence at room temperature has become active.

  In addition, recently discovered organic EL devices that use phosphorescence can realize a luminous efficiency that is approximately four times that of previous devices that use fluorescence. Research and development of light-emitting element layer configurations and electrodes are performed all over the world. For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), a number of compounds are studied for synthesis centering on heavy metal complexes such as iridium complexes.

  On the other hand, in terms of manufacturing cost and productivity, the structure of the organic EL element is simply a structure in which an organic layer is sandwiched between a transparent electrode and a counter electrode, and the number of parts is smaller than that of a liquid crystal display that is a typical flat display. However, the manufacturing cost should be kept low because it is overwhelmingly small. However, at present, this is not necessarily the case, and the liquid crystal display is largely drained in terms of performance and cost.

  In particular, in terms of cost, poor productivity is considered as a factor.

Most of the organic ELs currently commercialized are manufactured by a so-called vapor deposition method in which a low molecular material is deposited to form a film. In this vapor deposition method, a low-molecular compound that can be easily purified can be used as an organic EL material (a high-purity material can be easily obtained), and a laminated structure can be easily formed. Are better. On the other hand, since the deposition is performed under a high vacuum of 10 ⁻⁴ Pa or less, restrictions are imposed on the film forming apparatus, and in practice it can be applied only to a substrate with a small area. The disadvantage is low starting and low throughput. In particular, it becomes a problem when applied to lighting applications and large-area electronic displays, and organic EL elements are one of the causes that are not practically used in such applications.

  On the other hand, a coating method in which an organic compound layer is manufactured by a process such as spin coating, ink jetting, printing, or spraying can produce a thin film at normal pressure, and is suitable for producing a uniform film over a large area. However, in order to achieve high luminous efficiency and long life at the same time, it is desirable to stack a plurality of functional layers. In order to laminate a plurality of layers using the coating method, the lower layer is required not to dissolve in the upper layer coating solution. However, since it is a very thin film of the order of several tens of nm, the upper layer is formed using a hardly soluble solvent. Even if it is applied, the problem arises that the lower layer film dissolves or the interface is disturbed by the solvent. Such contamination to the upper layer of the lower layer material and disturbance of the interface cause a decrease in the light emission efficiency of the element and a deterioration in the element life, and therefore need to be improved.

  In order to solve the above problems, for example, it has been proposed to use a polymer material. However, in general, polymer materials are difficult to purify, and in particular, organic EL devices are difficult to apply because very few impurities cause the light emission life of the device to be greatly reduced.

  Further, as a method not using a polymer material, there is a technique of increasing the molecular weight after forming a constituent layer of an organic EL element using a low molecular material, and is a bifunctional having two vinyl groups in the molecule. A triphenylamine derivative is described, and after forming a film of the compound, a three-dimensionally cross-linked polymer is formed by ultraviolet irradiation (see, for example, Patent Document 1), and a plurality of materials having two or more vinyl groups are formed. A technique of adding to a layer is disclosed, and a polymerization reaction is performed by ultraviolet or heat irradiation at the time of forming an organic layer before laminating a cathode (see, for example, Patent Document 2), a vinyl group at the end of a phosphorescent dopant A manufacturing method in which AIBN (azoisobutyronitrile), which is a radical generator, is added to a mixture of vinyl group-containing comonomers as in the case of a material having a vinyl group and the polymerization reaction proceeds during film formation (for example, Patent Document 3), a manufacturing method of crosslinking by causing a Diels-Alder reaction between two molecules of the same layer (for example, see Patent Document 4), and the like.

However, as described above, ultraviolet irradiation and heat treatment at a high temperature to increase the molecular weight (resinization) of low molecular weight materials cause generation of oxides, deterioration of materials, and the like. These treatments are not preferable because they adversely affect the service life.
Japanese Patent Laid-Open No. 5-271166 JP 2001-297882 A Japanese Patent Laid-Open No. 2003-73666 JP 2003-86371 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic EL element material exhibiting high luminous efficiency and having a low driving voltage, an organic EL element using the same, an illuminating device, and a display device Is to provide.

  The above object of the present invention has been achieved by the following constitution.

  1. An organic electroluminescent element material comprising a compound represented by the following general formula (0):

(Wherein X _{11 to} X ₁₈ represent either —C (R ₀₁₁ ) _═ or —N═, and X _{21 to} X ₂₈ represent either —C (R ₀₂₁ ) _═ or —N═, X ₃₁ to X ₃₈ represents either -C _{(R 031)} = or -N = _a, X 41 _{to X 48} is -C _{(R 041)} = or -N = represents one of _{the, X 11} ~ X ₁₈ , X _{21 to} X ₂₈ , X _{31 to} X ₃₈ and X _{41 to} X ₄₈ are not all -N = R ₀₁₁ , R ₀₂₁ , R ₀₃₁ and R ₀₄₁ are a bond, a hydrogen atom or a substitution In the case where a plurality of -C (R ₀₁₁ ) =, -C (R ₀₂₁ ) =, -C (R ₀₃₁ ) = and -C (R ₀₄₁ ) = are present, R ₀₁₁ , R ₀₂₁ , R ₀₃₁ And R ₀₄₁ may be the same or different. ₁ and X ₂ each represent a divalent linking group selected from the group consisting of the following general formulas (2 ′), (3 ′), and (4 ′): m1 and m2 each represent an integer of 1 or more; If m1 and m2 is an integer of 2 or more, it may be _{X 1} and _{X 2} are a plurality of combinations of the general formula (2 ') - (4').)

(In the formula, Y represents NR, O, or S. R represents a hydrogen atom, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring. X _{51 to} X ₅₄ represent —C (R ₀₅₁ ) _═ or —N═. represents _either, X 61 _{to X 68} is -C _{(R 061)} = or -N = represents one of _{the, X 51 ~X 54, X 61} ~X 68 and _X 71 _{to X 74} are all -N R ₀₅₁ , R ₀₆₁ and R ₀₇₁ each represents a hydrogen atom or a substituent, provided that at least two of R and R ₀₆₁ are used for linking -C (R ₀₅₁ ) =, -C When there are a plurality of (R ₀₆₁ ) = and -C (R ₀₇₁ ) =, R ₀₅₁ , R ₀₆₁ and R ₀₇₁ may be the same or different.
2. _2. The organic according to 1 above, wherein A, X ₁ and X _{2 in the} general formula (0) are divalent linking groups represented by the general formula (2 ′) or (3 ′). Electroluminescence element material.

3. 3. The organic electroluminescence device material according to 1 or 2, wherein X ₆₃ and X _{66 in the} general formula (3 ′) are represented by —C (R ₀₆₁ ) =, and R ₀₆₁ is used for connection.

  4). An organic electroluminescent element material comprising a compound represented by the following general formula (1):

(In the formula, R _{11 to} R ₁₄ and R _{21 to} R ₂₄ each represent a halogen atom or a substituent. M1 and m2 each represent an integer of 1 or more, and k11 to k14 and k21 to k24 each represent 0 to 3) A, X ₁ and X ₂ each represent a divalent linking group selected from the group consisting of the following general formulas (2), (3) and (4), where m1 and m2 are integers of 2 or more. X ₁ and X ₂ may be a plurality of combinations of general formulas (2) to (4).

(Wherein R _{3 to} R ₆ each represent a halogen atom or a substituent. K 3 to k ₆ each represents an integer of 0 to 3, Y represents NR, O or S. R represents a hydrogen atom, aromatic carbonization. Represents a hydrogen ring or an aromatic heterocycle.)
5. 5. The organic electroluminescent element material according to 4, wherein A in the general formula (1) is a divalent linking group represented by the general formula (2) or (3).

6). 6. The organic electroluminescence as described in 4 or 5 above, wherein X ₁ and X _{2 in} the general formula (1) are divalent linking groups represented by the general formula (2) or (3). Element material.

  7). 7. The organic electroluminescence element material according to any one of 1 to 6, wherein m1 and m2 in the general formula (0) and the general formula (1) are 1 or 2.

8). 8. The organic electroluminescence element material according to any one of 1 to 7, wherein Y in the general formula (3 ′) and the general formula (3) is NR or O.

  9. 9. The organic electroluminescent element material as described in 8 above, wherein Y in the general formula (3) is O.

10. The substituents represented by R _{11 to} R ₁₂ , R _{21 to} R ₂₄ and R _{3 to} R ₆ in the general formulas (1) to (4) represent an aromatic hydrocarbon group or an aromatic heterocyclic group, 10. The organic electroluminescent element material according to any one of 4 to 9, wherein k11 to k14, k21 to k24, and k3 to k6 are 0 or 1.

  11. In any one of 4 to 10 above, wherein k11 to k12, k21 to k22 and k3 to k6 in the general formulas (1) to (4) are 0, and m1 and m2 are 1. The organic electroluminescent element material as described.

  12 12. An organic electroluminescence device having a plurality of organic layers including a light emitting layer sandwiched between an anode and a cathode, wherein at least one of the organic layers is the organic electroluminescence device material according to any one of 1 to 11 above. An organic electroluminescence device comprising:

  13. 13. The organic electroluminescence device as described in 12 above, wherein the light emitting layer contains the organic electroluminescence device material as described in any one of 1 to 11.

  14 14. The organic electroluminescence device as described in 12 or 13, wherein the light emitting layer contains a phosphorescent metal complex.

  15. 15. The organic electroluminescence device as described in 14 above, wherein the phosphorescent metal complex is a metal complex represented by the following general formula (5).

(In the formula, P and Q represent a carbon atom or a nitrogen atom, A1 represents an atomic group which forms an aromatic hydrocarbon ring or an aromatic heterocycle with PC, and A2 represents a coaromatic carbonization with QN. Represents a group of atoms forming a hydrogen ring or an aromatic heterocyclic ring, P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom L1 represents an atomic group that forms a bidentate ligand with P ₁ and P ₂ , j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 represents 2 or 3. M _{1 as the} central metal represents a group 8-10 metal in the periodic table.
16. 16. The organic electroluminescence device as described in 15 above, wherein A2 represented by the general formula (5) is a 5-membered heterocyclic ring.

  17. 15. The organic electroluminescence device as described in 14 above, wherein the phosphorescent metal complex is a metal complex represented by the following general formula (6).

(In the formula, Z represents a hydrocarbon ring or a heterocyclic ring. P and Q represent a carbon atom or a nitrogen atom, and A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC. .A3 is _{-C (R 01) = C (} R 02) -, - N = C (R 02) -, - C (R 01) = N- or -N = N-a _{represents, R 01} and _{R 02} Represents a hydrogen atom or a substituent, P ₁ -L ₁ -P ₂ represents a bidentate ligand, P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom or an oxygen atom, L ₁ represents P ₁ , P ₂ represents an atomic group forming a bidentate ligand, j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. A certain M ₁ represents a group 8 to 10 metal in the periodic table.)
18. 18. The organic electroluminescence device as described in 17 above, wherein Z in the general formula (6) has a substituent represented by the following general formula (7).

(In the formula, Ar ₁ represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, H ₁ represents a carrier transport unit, and n represents an integer of 0 to 10.)
19. 19. The organic electroluminescence device according to any one of 14 to 18, wherein the phosphorescent metal complex is an Ir complex.

  20. The organic electroluminescent element having a plurality of organic layers including a light emitting layer sandwiched between an anode and a cathode, wherein the layer containing the organic electroluminescent element material according to any one of 1 to 11 is a wet method. 20. The organic electroluminescent element according to any one of 12 to 19, which is formed.

  21. 21. The organic electroluminescence device according to any one of 12 to 20, which emits white light.

  22. 21. An illumination device comprising the organic electroluminescence element according to any one of 12 to 20.

  23. 21. A display device comprising the organic electroluminescence element according to any one of 12 to 20.

  According to the present invention, an organic EL element material useful for an organic EL element is obtained. By using the organic EL element material, an organic EL element exhibiting high luminous efficiency and having a low driving voltage, and the element are used. It was possible to provide a lighting device and a display device.

It is an absorption spectrum of the thin film sample 1 before and after being immersed in 1-butanol. It is the schematic of the illuminating device of this invention. It is sectional drawing which shows the one aspect | mode of the illuminating device of this invention. It is a schematic block diagram of an organic EL full-color display device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Glass substrate 102 ITO transparent electrode 103 Non-photosensitive polyimide partition 104 Hole injection layer 105B Blue light emitting layer 105G Green light emitting layer 105R Red light emitting layer 106 Al (cathode)
201 Organic EL element 202 Glass cover 205 Cathode 206 Organic EL layer 207 Glass substrate with transparent electrode 208 Nitrogen gas 209 Water catching agent

  As a result of diligent investigations on the above problems, the present inventors have found that a low molecular compound having a specific structure has a high solvent resistance to solvents such as n-butanol, acetonitrile, and fluorine without increasing the molecular weight. It was found that the upper layer can be applied using these solvents. On the other hand, the compound of the present invention is suitable for the coating method because it is highly soluble in some solvents such as toluene and has good film-forming properties. By using the material of the present invention, an organic EL element capable of simultaneously achieving high luminous efficiency and long life could be produced.

  In the organic EL element material of the present invention, the organic EL element material useful for the organic EL element has been successfully molecularly designed by the configuration defined in any one of 1 to 11 above. In addition, by using the organic EL element material, it was possible to provide an organic EL element, an illuminating device, and a display device that showed high luminous efficiency and reduced driving voltage.

  Hereinafter, details of each component according to the present invention will be sequentially described.

  The organic EL element material according to the present invention will be described.

<< Organic EL element material >>
The organic EL element material of the present invention will be described.

  The organic EL device material of the present invention contains the compound represented by the general formula (0) or the general formula (1).

  The compound according to the present invention can be prepared as a solution or a dispersion, and the film produced by coating is uniform and can be sufficiently used as an organic EL device.

  In addition, the compound according to the present invention provides an organic EL device having a sufficiently wide band gap that can be used as a host for a blue phosphorescent dopant, high external extraction quantum efficiency, and long emission lifetime. In addition, an illumination device and a display device including the organic EL element can be provided.

<< Compound Represented by Formula (0) >>
The compound represented by the general formula (0) according to the present invention will be described.

In General Formula (0), X _{11 to} X ₁₈ represent either —C (R ₀₁₁ ) _═ or —N═, and X _{21 to} X ₂₈ represent either —C (R ₀₂₁ ) _═ or —N═. X _{31 to} X ₃₈ represent either -C (R ₀₃₁ ) = or -N =, and X _{41 to} X ₄₈ represent either -C (R ₀₄₁ ) = or -N =, X _{11 to} X ₁₈ , X _{21 to} X ₂₈ , X _{31 to} X ₃₈ and X _{41 to} X ₄₈ are not all —N═. R ₀₁₁ , R ₀₂₁ , R ₀₃₁ and R ₀₄₁ represent a bond, a hydrogen atom or a substituent. When there are a plurality of -C (R ₀₁₁ ) =, -C (R ₀₂₁ ) =, -C (R ₀₃₁ ) = and -C (R ₀₄₁ ) =, R ₀₁₁ , R ₀₂₁ , R ₀₃₁ and R ₀₄₁ are Each may be the same or different. A, X ₁ and X ₂ each represent a divalent linking group selected from the group consisting of the general formulas (2 ′), (3 ′) and (4 ′). m1 and m2 each represent an integer of 1 or more, and when m1 and m2 are integers of 2 or more, X ₁ and X ₂ may be a plurality of combinations of the general formulas (2 ′) to (4 ′). .

In the general formulas (2 ′) to (4 ′), X _{51 to} X ₅₄ represent either —C (R ₀₅₁ ) = or —N =, and X _{61 to} X ₆₈ represent —C (R ₀₆₁ ) = or -N = represents one of _the, X 71 _{to X 74} is -C _{(R 071)} = or -N = represents one of _{the, X 51 ~X 54, X 61} ~X 68 and _X 71 _{to X 74} Are not all -N =. R ₀₅₁ , R ₀₆₁ and R ₀₇₁ each represents a hydrogen atom or a substituent. However, at least two of R and R ₀₆₁ are used for connection. When there are a plurality of -C (R ₀₅₁ ) =, -C (R ₀₆₁ ) = and C (R ₀₇₁ ) =, R ₀₅₁ , R ₀₆₁ and R ₀₇₁ may be the same or different. Y represents NR, O, or S. R represents a hydrogen atom, an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group. Biphenylyl group, and examples of the aromatic heterocycle include a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a quinazolinyl group, Examples thereof include a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a phthalazinyl group, and the like. R is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.

Examples of the substituent represented by R ₀₁₁ , R ₀₂₁ , R ₀₃₁ , R _{041 in} the general formula (0) and R ₀₅₁ , R ₀₆₁ , R ₀₇₁ in the general formulas (2 ′) to (4 ′) include alkyl Group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, Cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl group, 1-propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, isopropenyl group, etc.), alkynyl group ( For example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl P-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group ( For example, furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, diazacarbazolyl Any carbon atom constituting the carboline ring of the group is substituted with a nitrogen atom), a phthalazinyl group, etc.), a heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy A group (eg, methoxy) Group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy) Group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.) ), Arylthio groups (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dopamine) Decyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, Hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, Propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenyl Carbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide Groups (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group) , Phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethyl) Minocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl Group), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), sulfinyl group (For example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dode Silsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group) Group), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group) , Cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom) Etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (eg, trimethylsilyl) Group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphono group and the like.

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

A in the general formula (0) is preferably a divalent linking group represented by the general formula (2 ′) or (3 ′), and X ₁ and X _{2 in} the general formula (0) A divalent linking group represented by the general formula (2 ′) or (3 ′) is preferable.

  In the general formula (0), m1 and m2 are preferably 1 or 2.

  Y in the general formula (3 ′) is preferably NR or O, and more preferably O.

The substituent represented by R ₀₁₁ , R ₀₂₁ , R ₀₃₁ , R ₀₄₁ R ₀₅₁ , R ₀₆₁ , and R ₀₇₁ in the general formula (0) and general formulas (2 ′) to (4 ′) is an aromatic hydrocarbon group. Or it represents an aromatic heterocyclic group, and it is more preferable that m1 and m2 are 1.

<< Compound Represented by Formula (1) >>
The compound represented by the general formula (1) according to the present invention will be described.

In the general formula (1), R _{11 to} R ₁₄ and R _{21 to} R ₂₄ each represent a halogen atom or a substituent. m1 and m2 each represent an integer of 1 or more, and k11 to k14 and k21 to k24 each represent an integer of 0 to 3. A, X ₁ and X ₂ each represent a divalent linking group selected from the group consisting of the general formulas (2), (3) and (4). When m1 and m2 are integers of 2 or more, X ₁ and X ₂ may be a plurality of combinations of the general formulas (2) to (4).

In the general formulas (2) to (4), R _{3 to} R ₆ each represent a halogen atom or a substituent. k3 to k6 each represents an integer of 0 to 3, and Y represents NR, O, or S. R represents a hydrogen atom, an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group. Biphenylyl group, and examples of the aromatic heterocycle include a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a quinazolinyl group, Examples thereof include a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a phthalazinyl group, and the like. R is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.

Examples of the halogen atom represented by R _{11 to} R ₁₄ , R _{21 to} R _{24 in} the general formula (1) and R _{3 to} R ₆ in the general formulas (2) to (4) include a fluorine atom, a chlorine atom, A bromine atom etc. are mentioned.

Examples of the substituent represented by R _{11 to} R ₁₄ , R _{21 to} R ₂₄ in general formula (1), and R _{3 to} R ₆ in general formulas (2) to (4) include those represented by general formula (0). , R ₀₁₁ , R ₀₂₁ , R ₀₃₁ , R ₀₄₁ , R ₀₅₁ , R ₀₆₁ , R ₀₇₁ , and the like.

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

  In the general formula (1), k11 to k14 and k21 to k24 each represent an integer of 0 to 3. Of these, 0 or 1 is preferred.

A in the general formula (1) is preferably a divalent linking group represented by the general formula (2) or (3), and X ₁ and X _{2 in} the general formula (1) are the above general formulas. The divalent linking group represented by (2) or (3) is preferable.

  In formula (1), m1 and m2 are preferably 1 or 2.

  Y in the general formula (3) is preferably NR or O, and more preferably O.

The substituents represented by R _{11 to} R ₁₂ , R _{21 to} R ₂₄ and R _{3 to} R ₆ in the general formulas (1) to (4) represent an aromatic hydrocarbon group or an aromatic heterocyclic group, and k11 ˜k14, k21 to k24 and k3 to k6 are preferably 0 or 1, k11 to k12, k21 to k22 and k3 to k6 are preferably 0, and m1 and m2 are more preferably 1.

  Hereinafter, although the specific example of the compound represented by General formula (0) and General formula (1) based on this invention is shown, this invention is not limited to these.

  The compound according to the present invention can be used in any of the constituent layers of the organic EL device of the present invention, which will be described later, but the effects described in the present invention (improvement of external extraction quantum efficiency, prolongation of emission lifetime) ) Is preferably contained in the light emitting layer.

  Moreover, as a light emission dopant which concerns on this invention, the metal complex represented by the said General formula (5) is preferable, More preferably, it is a metal complex represented by the said General formula (6). These will also be described later.

  The compound according to the present invention can be synthesized with reference to conventionally known documents. Hereinafter, although an example of the synthesis | combination of the compound represented by General formula (1) based on this invention is shown, this invention is not limited to these. The compound represented by the general formula (0) according to the present invention can be synthesized in the same manner.

<< Synthesis of Exemplary Compound 1-1 >>
Add 1 ml of carbazole, 25.0 g of 3-bromoiodobenzene, 13.4 g of potassium carbonate, and 6.2 g of copper (powder) to 90 ml of N, N-dimethylacetamide (dehydrated), and heat to reflux for 7 hours under a nitrogen stream. went. The reaction mixture was cooled to room temperature, insolubles were filtered, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting mixture was purified by silica gel column chromatography to obtain 17 g of Intermediate 1. The yield was 57%. The structure of the obtained intermediate 1 was confirmed by a nuclear magnetic resonance spectrum and a mass spectrum.

Intermediate 1 20 g, bis (pinacolato) diboron 18.9 g, potassium acetate 12.2 g, PdCl ₂ (dppf) · CH ₂ Cl ₂ ([1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride To 1.0 g of dichloromethane complex), 300 ml of dimethyl sulfoxide was added and stirred with heating at 100 ° C. for 16 hours under a nitrogen stream. The reaction mixture was cooled to room temperature, insolubles were filtered, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting mixture was purified by silica gel column chromatography to obtain 20.6 g of intermediate 2. The yield was 90%. The structure of the obtained intermediate 2 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

Intermediate 2 24.6 g, Intermediate 3 13.7 g, Potassium carbonate 23.1 g, Pd (dba) ₂ (Bis (dibenzylideneacetone) palladium) 0.64 g, dppf (diphenylphosphinoferrocene) 0.62 g 550 ml of 1,2-dimethoxyethane and 70 ml of water were added, and the mixture was heated to reflux for 5 hours. The reaction mixture was cooled to room temperature, insolubles were filtered, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting mixture was purified by silica gel column chromatography to obtain 16.5 g of intermediate 2. The yield was 72%. The structure of the obtained intermediate 4 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

  To 0.29 g of palladium acetate, 2.1 g of a 50 mass% toluene solution of ter-butylphosphine and 10 ml of xylene (dehydrated) were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen stream. Subsequently, 7.5 g of Intermediate 4, 2.9 g of 1,3-diiodobenzene, 2.1 g of sodium t-butoxide, and 120 ml of xylene (dehydrated) were added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After cooling the reaction solution to room temperature, insolubles were filtered, water was added, and the mixture was extracted with toluene. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting mixture was purified by silica gel column chromatography and recrystallized from toluene to obtain 5.7 g of Exemplified Compound 1-1. The yield was 73%. The obtained exemplary compound 1-1 was confirmed in structure by nuclear magnetic resonance spectrum and mass spectrum.

  Other compounds can be synthesized in the same manner.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode In the organic EL device of the present invention, the blue light emitting layer preferably has a light emission maximum wavelength of 430 to 480 nm, and the green light emitting layer has a light emission maximum wavelength of 510 to 550 nm, The red light emitting layer is preferably a monochromatic light emitting layer having a light emission maximum wavelength in the range of 600 to 640 nm, and is preferably a display device using these. Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.

  Each layer which comprises the organic EL element of this invention is demonstrated.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 10 to 80 nm.

  For the production of the light emitting layer, a light emitting dopant and a host compound described later are applied by, for example, a coating method such as a spin coating method or a die coating method, a wet method such as an ink jet method, a screen printing method, a casting method or an LB method, a vacuum. The film can be formed by a known thinning method such as a vapor deposition method. When using the compound of this invention for a light emitting layer, forming by a wet method is preferable.

  The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant) or fluorescent dopant). .

(Host compound (also called luminescent host))
The host compound used in the present invention will be described.

  In the present invention, the host compound has a mass ratio of 20% or more in the compound contained in the light emitting layer, and a phosphorescence quantum yield of phosphorescence emission is 0 at room temperature (25 ° C.). Defined as less than 1 compound. The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer. Moreover, when it has a several light emitting layer, it is preferable that mass ratio 20% or more of the host compound of each of these layers is the same compound, since it is easy to obtain a uniform film property over the whole organic layer.

  As a host compound used for this invention, it is preferable to contain the compound represented by the said General formula (0) and General formula (1). In the present invention, a known host compound may be used in combination.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.

  The host compound used in the present invention preferably has a Tg of 100 ° C. or higher. If the Tg is lower than 100 ° C., the deterioration of the device over time (decrease in luminance, deterioration in film properties) is large, and the production process is not preferable because of restrictions in terms of the drying step and the like. That is, in order to satisfy brightness, durability, and productivity, Tg is preferably 100 ° C. or higher. Tg is more preferably 130 ° C. or higher.

  As the known host compound that may be used in combination, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable.

  Specific examples of known host compounds include JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002. No. 8860, No. 2002-334787, No. 2002-15871, No. 2002-334788, No. 2002-43056, No. 2002-334789, No. 2002-75645, No. 2002-338579, No. 2002-105445 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453, 2003-3165, 2002-234888 2003-27048, 2002-255934, 2002-260861, 2002-280183, 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002 And compounds described in publications such as -308837.

(Luminescent dopant)
The light emitting dopant according to the present invention will be described.

  As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used. From the viewpoint of obtaining an organic EL device with higher luminous efficiency, the light emitting dopant used in the light emitting layer or light emitting unit of the organic EL device of the present invention (sometimes simply referred to as a light emitting material) is phosphorescent. It is preferable to contain a dopant. Further, a phosphorescent dopant and a fluorescent dopant may be used in combination.

(Phosphorescent dopant)
The phosphorescent dopant according to the present invention will be described.

  The phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield. The phosphorescence quantum yield is preferably 0.1 or more, although it is defined as a compound of 0.01 or more at 25 ° C.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence emitting dopant according to the present invention achieves the above phosphorescence quantum yield (0.01 or more) in any solvent. It only has to be done.

  There are two types of light emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound. The energy transfer type is to obtain light emission from the phosphorescent dopant by transferring to the phosphorescent dopant, and the other is that the phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent dopant to cause phosphorescence. There is a carrier trap type in which light emission from a photoluminescent dopant can be obtained.

  In any of the above cases, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device.

  The phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table, more preferably an iridium compound (Ir complex), an osmium compound, or a platinum compound ( Platinum complex compounds) and rare earth complexes, most preferably iridium compounds (Ir complexes).

  The compound used as the phosphorescent dopant according to the present invention is, for example, Inorg. Chem. 40, 1704 to 1711, and the like.

  In the present invention, the phosphorescent maximum wavelength of the phosphorescent dopant is not particularly limited, and in principle can be obtained by selecting a central metal, a ligand, a ligand substituent, and the like. The emitted light wavelength can be changed.

(Metal complex represented by the general formula (5))
Moreover, as a preferable phosphorescence-emitting dopant in this invention, the metal complex represented by the said General formula (5) is preferable. Here, the metal complex represented by the general formula (5) will be described.

In General formula (5), P and Q represent a carbon atom or a nitrogen atom, A1 represents the atomic group which forms an aromatic-hydrocarbon ring or an aromatic heterocyclic ring with PC. A2 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with QN. P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. L1 represents an atomic group forming a bidentate ligand with P ₁ and P ₂ . j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M ₁ which is the central metal represents a group 8 to 10 metal in the periodic table.

Specific examples of the aromatic hydrocarbon ring represented by A1 include a benzene ring, chlorobenzene ring, mesitylene ring, toluene ring, xylene ring, naphthalene ring, anthracene ring, azulene ring, acenaphthene ring, fluorene ring, phenanthrene ring, Indene ring, pyrene ring, biphenyl ring, terphenyl ring, perylene ring and the like can be mentioned. Further, the hydrocarbon ring group may be substituted with, for example, a substituent described in R ₀₁ and R ₀₂ described later, and further a condensed ring (for example, a quinolyl group quinoline obtained by condensing a heterocyclic ring to a phenyl group benzene ring) Ring) or the like.

Specific examples of the aromatic heterocycle represented by A1 or A2 include oxazole ring, oxadiazole ring, oxatriazole ring, isoxazole ring, tetrazole ring, thiadiazole ring, thiatriazole ring, isothiazole ring, thiophene. Examples include a ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a diazine ring, and a triazine ring. Further, the heterocyclic ring may be substituted with the substituent described for R ₁₁ , for example, and may further form a condensed ring.

In the general formula (5), specific examples of the bidentate ligand represented by P ₁ -L ₁ -P ₂ include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, Examples include pyraza ball, acetylacetone, and picolinic acid.

  j1 represents an integer of 1, 2 or 3, j2 represents an integer of 0, 1 or 2, and j1 + j2 is 2 or 3. Among these, j2 is preferably 0.

In the general formula (5), M ₁ which is the central metal is a transition metal element of Group 8 to 10 (also referred to simply as a transition metal) in the periodic table, and among them, iridium and platinum are preferable, and iridium is particularly preferable.

  A2 represented by the general formula (5) is preferably a 5-membered aromatic heterocyclic ring. The 5-membered aromatic heterocycle includes oxazole ring, oxadiazole ring, oxatriazole ring, isoxazole ring, tetrazole ring, thiadiazole ring, thiatriazole ring, isothiazole ring, thiophene ring, furan ring, pyrrole ring, imidazole A ring, a pyrazole ring, a triazole ring, etc. are mentioned.

  A2 represented by the general formula (5) is preferably an imidazole ring, a pyrazole ring, a pyridine ring, or an isoquinoline ring.

(Metal complex represented by the general formula (6))
As a preferable phosphorescent dopant in the present invention, a metal complex represented by the general formula (6) is preferable.

In General formula (6), Z represents a hydrocarbon ring or a heterocyclic ring. P and Q represent a carbon atom or a nitrogen atom, and A1 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocycle together with PC. A3 is an atomic group that forms an aromatic heterocycle with NQN, and is —C (R ₀₁ ) ═C (R ₀₂ ) —, _—N═C (R ₀₂ ) —, —C (R ₀₁ ) = N— or —N═N—, and R ₀₁ and R ₀₂ represent a hydrogen atom or a substituent. P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. L1 represents an atomic group forming a bidentate ligand with P ₁ and P ₂ . j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M1 which is a central metal represents a group 8 to 10 metal in the periodic table.

  The aromatic hydrocarbon ring and aromatic heterocycle represented by A1 have the same meaning as the aromatic hydrocarbon ring or aromatic heterocycle represented by A1 in the general formula (5).

  The nitrogen-containing aromatic heterocycle formed together with A3 and NQN is synonymous with the aromatic heterocycle represented by A1 in the general formula (5), and preferably an imidazole ring, triazole ring, tetrazole A ring etc. are mentioned. Particularly preferred is an imidazole ring.

In the general formula (6), P ₁ Specific examples of the bidentate ligand represented by -L1-P _2, the general formula P ₁ -L1-P ₂ represented bidentate is of (5) Synonymous with ligand.

  j1 represents an integer of 1, 2 or 3, j2 represents an integer of 0, 1 or 2, and j1 + j2 is 2 or 3. Among these, j2 is preferably 0.

In the general formula (6), the central metal M ₁ is a group 8-10 transition metal element (also simply referred to as a transition metal) in the periodic table of the elements. Among them, iridium and platinum are preferable, and iridium is particularly preferable.

  In General formula (6), Z represents a hydrocarbon ring or a heterocyclic ring. Although the preferable example of Z is given to the following, Z may have a substituent other than the following illustrations. It is not limited to these examples. Note that * represents a bonding position.

Z represented by the general formula (6) is preferably represented by the general formula (7). Ar ₁ represented by the general formula (7) represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, H ₁ represents a carrier transport unit, and n represents an integer of 0 to 10.

The aromatic hydrocarbon ring and aromatic heterocycle represented by Ar ₁ have the same meaning as the aromatic hydrocarbon ring or aromatic heterocycle represented by A1 in the general formula (5).

The carrier transport unit represented by H ₁ is a unit that transports carriers with a compound composed of an aromatic hydrocarbon ring or an aromatic heterocycle. It refers to a general organic EL electron transport material, hole transport material, and host material, preferably a carbazole derivative.

  Hereinafter, although the specific example of the phosphorescence-emitting metal complex which concerns on this invention is shown, this invention is not limited to these.

(Fluorescent dopant (also called fluorescent compound))
Fluorescent dopants (fluorescent compounds) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Next, an injection layer, a blocking layer, an electron transport layer and the like used as the constituent layers of the organic EL element of the present invention will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  Details of the cathode buffer layer (electron injection layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like.

  Cathode buffer materials used include alkali metal compounds (alkali metals and their salts, oxides, complexes, etc.) and alkaline earth metal compounds (alkaline earth metals, their salts, oxides, complexes, etc., including magnesium) And metals represented by strontium, aluminum and the like, salts thereof, oxides, complexes and the like. You may use these in combination of multiple types.

  The cathode buffer layer (electron injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm, although it depends on the material. Further, the material used for the cathode buffer layer is not only used alone as the cathode buffer layer, but may be mixed in the electron transport layer.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  The hole blocking layer preferably contains the azacarbazole derivative mentioned as the host compound.

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.

  (1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can do. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. Any material may be used as long as it has a function of transferring electrons to the light-emitting layer, and any material can be selected from conventionally known compounds.

  Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.

  Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum. Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be manufactured.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.

Specific examples of such electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

  The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal with a film thickness of 1-20 nm on a cathode, a transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less of a barrier film, and oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ cm ³ / (m ² · 24 h · MPa) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.

  Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned. Further, the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ cm ³ / (m ² · 24 h · MPa) or less, and conforms to JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the method is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less. .

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15 to 20% of the light generated in the light emitting layer. Is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be extracted outside the device, This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

  In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

  The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

  At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

  The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, thereby producing an anode.

  Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are organic EL element materials, is formed thereon.

  As the method for forming each layer, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a homogeneous film and a pinhole is generated. In view of difficulty, etc., film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.

  Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm. By providing, a desired organic EL element can be obtained.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

Further, when the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 Cd / m ² is X when the 2-degree viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example 1 << Solvent Resistance >>
A quartz substrate of 30 mm × 30 mm × 1.1 mm was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, then attached to a commercially available spin coater, and Example Compound 1-1 (50 mg) Was dissolved in 10 ml of toluene by spin coating at 1500 rpm for 30 seconds, and further vacuum dried at 25 ° C. for 1 hour to prepare Sample 1 (thin film) having a film thickness of about 25 nm. About the obtained sample 1, the absorption spectrum was measured with the spectrophotometer U-3300 (made by Hitachi).

  Next, the sample 1 was immersed vertically in 1-butanol at 20 ° C. (manufactured by Wako Pure Chemical Industries, Ltd., for spectroscopic analysis), left still for 3 seconds with the entire substrate immersed, and then pulled up to 25 ° C. For 1 hour. About the sample 1 after immersion, the absorption spectrum was measured similarly to before immersion. FIG. 1 shows absorption spectra of Sample 1 before and after immersion.

  When the absorbance at 341 nm before and after the immersion was compared, it was 0.158 before the immersion and 0.152 after the immersion, and the difference was 4%. The thin film containing the compound of the present invention was compared with 1-butanol. It was found to have high solvent resistance.

  Samples 2 to 8 were prepared in the same manner except that Comparative Compounds 1 to 3, Example Compounds 1-2, 1-5, 1-16, and 1-24 were used instead of the Example Compound 1-1.

  For Samples 2 to 8, the solvent resistance was measured in the same manner as Sample 1, and the difference (%) in absorbance before and after immersion in 1-butanol was determined. The results are shown in Table 1.

  From the table, it was found that the compound of the present invention has high application suitability and high solvent resistance against 1-butanol.

Example 2
<< Production of Organic EL Element 1-1 >>
After patterning on a substrate (NH-Techno Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. Then, the film was formed by spin coating and then dried at 200 ° C. for 1 hour to provide a 20 nm-thick hole transport layer.

  This substrate was transferred to a nitrogen atmosphere, and a solution in which 50 mg of the hole transport material 1 was dissolved in 10 ml of toluene was formed on the hole transport layer by spin coating at 1500 rpm for 30 seconds. In a nitrogen atmosphere, ultraviolet light was irradiated for 180 seconds to perform photopolymerization / crosslinking to form a second hole transport layer having a thickness of about 20 nm.

  On this second hole transport layer, a solution prepared by dissolving 100 mg of Comparative Compound 2 and 10 mg of Ir-15 in 10 ml of toluene was formed by spin coating under conditions of 1000 rpm and 30 seconds. It vacuum-dried at 120 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 50 nm.

  Next, a solution obtained by dissolving 50 mg of the electron transport material 1 in 10 ml of 1-butanol was formed on this light emitting layer by spin coating under the condition of 5000 rpm for 30 seconds. It vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 15 nm.

Subsequently, this substrate is fixed to a substrate holder of a vacuum deposition apparatus, the vacuum chamber is decompressed to 4 × 10 ⁻⁴ Pa, lithium fluoride 1.0 nm is deposited as a cathode buffer layer, and aluminum 110 nm is deposited as a cathode to form a cathode. Then, an organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-7 >>
Organic EL elements 1-2 to 1-7 were prepared in the same manner as the organic EL element 1-1 except that the comparative compound 1 was replaced with the compounds shown in Table 2 in the preparation of the organic EL element 1-1.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 1-1 to 1-7, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material, and this is overlaid on the cathode and brought into close contact with the transparent support substrate. Then, it was cured and sealed, and an illumination device as shown in FIGS. 2 and 3 was formed and evaluated.

  FIG. 2 is a schematic diagram of the lighting device, and the organic EL element 201 is covered with a glass cover 202. In addition, the sealing operation with the glass cover was performed in a glove box under a nitrogen atmosphere without bringing the organic EL element 201 into contact with the atmosphere (in a high-purity nitrogen gas atmosphere with a purity of 99.999% or more).

  FIG. 3 is a cross-sectional view illustrating one embodiment of the lighting device of the present invention. In FIG. 3, reference numeral 205 denotes a cathode, 206 denotes an organic EL layer, and 207 denotes a glass substrate with a transparent electrode. The glass cover 202 is filled with nitrogen gas 208 and a water catching agent 209 is provided.

  Next, the external extraction quantum efficiency and emission lifetime were measured as follows.

(External extraction quantum efficiency)
About the produced organic EL element, the external extraction quantum efficiency (%) when a ^2.5 mA / cm ² constant current was applied in a dry nitrogen gas atmosphere at 23 ° C. was measured.

  For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used in the same manner.

  The measurement results of the external extraction quantum efficiency in Table 1 are expressed as relative values when the measured value of the organic EL element 1-1 is 100.

(lifespan)
When driving at a constant current of ^2.5 mA / cm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured, and this was calculated as the half-life time (τ 0.5). As an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used. The lifetime was expressed as a relative value when the organic EL element 1-1 was taken as 100.

  The obtained results are shown in Table 2.

  From the table, it is clear that the organic EL device of the present invention exhibits a high external extraction quantum efficiency, a low driving voltage, and a long emission lifetime as compared with the organic EL device of the comparative example.

Example 3
<< Production of organic EL full-color display device >>
FIG. 4 shows a schematic configuration diagram of an organic EL full-color display device. After patterning at a pitch of 100 μm on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) having a 100 nm thick ITO transparent electrode (102) formed on a glass substrate 101 as an anode, non-between the ITO transparent electrodes on this glass substrate. A photosensitive polyimide partition 103 (width 20 μm, thickness 2.0 μm) was formed by photolithography.

  A hole injection layer composition having the following composition is ejected and injected between polyimide partition walls on the ITO electrode using an inkjet head (manufactured by Epson; MJ800C), irradiated with ultraviolet light for 2 minutes, and dried at 60 ° C. for 10 minutes. A hole injection layer 104 having a thickness of 40 nm was produced by the treatment.

  On the hole injection layer, the following blue light-emitting layer composition, green light-emitting layer composition, and red light-emitting layer composition were similarly discharged and injected using an inkjet head, and dried at 60 ° C. for 10 minutes. Each light emitting layer (105B, 105G, 105R) was formed. Finally, Al (106) was vacuum-deposited as a cathode so as to cover the light emitting layer 105, and an organic EL element was produced.

(Hole injection layer composition)
Hole transport material 1 20 parts by mass Cyclohexylbenzene 50 parts by mass Isopropyl biphenyl 50 parts by mass (Blue light emitting layer composition)
Exemplified Compound 1-1 0.7 parts by mass D-3 (dopant) 0.04 parts by mass Cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass (green light emitting layer composition)
Illustrative compound 1-1 0.7 parts by mass Ir-1 (dopant) 0.04 parts by mass Cyclohexylbenzene 50 parts by mass Isopropyl biphenyl 50 parts by mass (red light emitting layer composition)
Illustrative compound 1-1 0.7 parts by mass Ir-14 (dopant) 0.04 parts by mass Cyclohexylbenzene 50 parts by mass Isopropyl biphenyl 50 parts by mass (electron transport layer composition)
Electron transport material 1 20 parts by mass 1-butanol 50 parts by mass Isopropyl biphenyl 50 parts by mass The produced organic EL device exhibits light emission of blue, green, and red, respectively, by applying voltage to each electrode. It turns out that it can be used.

  Further, instead of D-3, Ir-1, and Ir-14, compounds Ir-2 to Ir-27, Pt-1 to Pt-3, A-1, DD-1 to 6, Pd-1 to 3, Rh -1 to 3 and (1) to (187) and D-1 to 27 are also used as full-color display devices in the same manner in organic EL devices prepared by using compounds 1-2 to 59 instead of compound 1-1. I understood that I could do it.

Example 4
<< Production of White Organic EL Element 3-1 >>
On the transparent electrode substrate of Example 2, a hole transport layer / second hole transport layer was formed by spin coating as in Example 2, and 100 mg of Exemplified Compound 1-1, 10 mg as a light emitting layer. A solution of Ir-26 and 0.1 mg Ir-9 dissolved in 10 ml of toluene was deposited by spin coating at 1000 rpm for 30 seconds. It vacuum-dried at 120 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 50 nm.

  Next, in the same manner as in Example 2, an electron transport layer, a lithium fluoride layer, and an aluminum cathode were formed to produce a white light-emitting organic EL element 3-1. The obtained organic EL element 3-1 was sealed in the same manner as in Example 2.

  When this organic EL element 3-1 was energized, almost white light was obtained, and it was found that it could be used as a lighting device. In addition, it turned out that white light emission is obtained similarly even if it replaces a host compound with the other compound which concerns on this invention.

Example 5
<< Production of Organic EL Element 5-1 >>
After patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under conditions of 30 seconds and then dried at 200 ° C. for 1 hour to provide a 20 nm-thick hole transport layer.

  This substrate was transferred to a nitrogen atmosphere, and a mixed solution prepared by dissolving 5 mg of the hole transport material 2 and 45 mg of the hole transport material 3 in 10 ml of toluene on the hole transport layer was used at 1000 rpm for 30 seconds. A thin film was formed by spin coating on the hole transport layer. Further, ultraviolet light was irradiated for 180 seconds to perform photopolymerization / crosslinking, thereby forming a second hole transport layer having a film thickness of about 25 nm.

  A film obtained by dissolving 100 mg of the host compound 1 and 10 mg of D-23 in 10 ml of toluene was formed on the second hole transport layer by spin coating under conditions of 1500 rpm and 30 seconds. Furthermore, ultraviolet light was irradiated for 180 seconds, photopolymerization and crosslinking were performed, and a light emitting layer having a film thickness of about 50 nm was obtained.

  Next, a thin film was formed on the light emitting layer by spin coating using a solution of 50 mg of Comparative Compound 4 dissolved in 10 ml of toluene at 2500 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the 1st electron carrying layer.

A thin film was formed on the first electron transport layer by a spin coating method at 1000 rpm for 30 seconds using a solution of 50 mg of electron transport material 2 dissolved in 10 ml of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the 2nd electron carrying layer with a film thickness of about 30 nm.
Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, lithium fluoride was deposited at 0.4 nm as a cathode buffer layer, and aluminum was deposited at 110 nm as a cathode. Then, a cathode was formed, and an organic EL element 5-1 was produced.

<< Production of Organic EL Element 5-2 >>
In the production of the organic EL element 5-1, an organic EL element 5-2 was produced in the same manner as the organic EL element 5-1, except that the comparative compound 4 was replaced with 1-40.

<< Evaluation of Organic EL Elements 5-1, 5-2 >>
When evaluating the obtained organic EL elements 5-1, 5-2, the external extraction quantum efficiency and lifetime were evaluated in the same manner as the organic EL element 2-1.

  The obtained results are shown in Table 3.

  From the table, it is clear that the organic EL device of the present invention exhibits a high external extraction quantum efficiency, a low driving voltage, and a long emission lifetime as compared with the organic EL device of the comparative example.

Claims (23)

An organic electroluminescent element material comprising a compound represented by the following general formula (0):
(Wherein X _{11 to} X ₁₈ represent either —C (R ₀₁₁ ) _═ or —N═, and X _{21 to} X ₂₈ represent either —C (R ₀₂₁ ) _═ or —N═, X ₃₁ to X ₃₈ represents either -C _{(R 031)} = or -N = _a, X 41 _{to X 48} is -C _{(R 041)} = or -N = represents one of _{the, X 11} ~ X ₁₈ , X _{21 to} X ₂₈ , X _{31 to} X ₃₈ and X _{41 to} X ₄₈ are not all -N = R ₀₁₁ , R ₀₂₁ , R ₀₃₁ and R ₀₄₁ are a bond, a hydrogen atom or a substitution In the case where a plurality of -C (R ₀₁₁ ) =, -C (R ₀₂₁ ) =, -C (R ₀₃₁ ) = and -C (R ₀₄₁ ) = are present, R ₀₁₁ , R ₀₂₁ , R ₀₃₁ And R ₀₄₁ may be the same or different. ₁ and X ₂ each represent a divalent linking group selected from the group consisting of the following general formulas (2 ′), (3 ′), and (4 ′): m1 and m2 each represent an integer of 1 or more; If m1 and m2 is an integer of 2 or more, it may be _{X 1} and _{X 2} are a plurality of combinations of the general formula (2 ') - (4').)
(In the formula, Y represents NR, O, or S. R represents a hydrogen atom, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring. X _{51 to} X ₅₄ represent —C (R ₀₅₁ ) _═ or —N═. represents _either, X 61 _{to X 68} is -C _{(R 061)} = or -N = represents one of _{the, X 51 ~X 54, X 61} ~X 68 and _X 71 _{to X 74} are all -N R ₀₅₁ , R ₀₆₁ and R ₀₇₁ each represents a hydrogen atom or a substituent, provided that at least two of R and R ₀₆₁ are used for linking -C (R ₀₅₁ ) =, -C When there are a plurality of (R ₀₆₁ ) = and -C (R ₀₇₁ ) =, R ₀₅₁ , R ₀₆₁ and R ₀₇₁ may be the same or different. _2. The first aspect of the invention is characterized in that A, X ₁ and X _{2 in the} general formula (0) are divalent linking groups represented by the general formula (2 ′) or (3 ′). The organic electroluminescent element material described in 1. The X ₆₃ and X _{66 in the} general formula (3 ′) are represented by —C (R ₀₆₁ ) =, and R ₀₆₁ is used for connection. Organic electroluminescence element material. An organic electroluminescent element material comprising a compound represented by the following general formula (1):
(In the formula, R _{11 to} R ₁₄ and R _{21 to} R ₂₄ each represent a halogen atom or a substituent. M1 and m2 each represent an integer of 1 or more, and k11 to k14 and k21 to k24 each represent 0 to 3) A, X ₁ and X ₂ each represent a divalent linking group selected from the group consisting of the following general formulas (2), (3) and (4), where m1 and m2 are integers of 2 or more. X ₁ and X ₂ may be a plurality of combinations of general formulas (2) to (4).
(Wherein R _{3 to} R ₆ each represent a halogen atom or a substituent. K 3 to k ₆ each represents an integer of 0 to 3, Y represents NR, O or S. R represents a hydrogen atom, aromatic carbonization. Represents a hydrogen ring or an aromatic heterocycle.) The organic electroluminescence device material according to claim 4, wherein A in the general formula (1) is a divalent linking group represented by the general formula (2) or (3). . The X ₁ and X _{2 in} the general formula (1) are divalent linking groups represented by the general formula (2) or (3). The organic electroluminescent element material described in 1. The organic electroluminescence device according to any one of claims 1 to 6, wherein m1 and m2 in the general formula (0) and the general formula (1) are 1 or 2. material. The organic electroluminescent element material according to any one of claims 1 to 7, wherein Y in the general formula (3 ') and the general formula (3) is NR or O. . The organic electroluminescent element material according to claim 8, wherein Y in the general formula (3) is O. The substituents represented by R _{11 to} R ₁₂ , R _{21 to} R ₂₄ and R _{3 to} R ₆ in the general formulas (1) to (4) represent an aromatic hydrocarbon group or an aromatic heterocyclic group, The organic electroluminescent element material according to any one of claims 4 to 9, wherein k11 to k14, k21 to k24, and k3 to k6 are 0 or 1. In the general formulas (1) to (4), k11 to k12, k21 to k22, and k3 to k6 are 0, and m1 and m2 are 1. Organic electroluminescent element material of any one of these. The organic electroluminescence device having a plurality of organic layers including a light emitting layer sandwiched between an anode and a cathode, wherein at least one of the organic layers is according to any one of claims 1 to 11. An organic electroluminescence device comprising the organic electroluminescence device material. The organic light-emitting device according to claim 12, wherein the light-emitting layer contains the organic electroluminescence device material according to any one of claims 1 to 11. The organic light-emitting element according to claim 12 or 13, wherein the light-emitting layer contains a phosphorescent metal complex. The organic electroluminescent device according to claim 14, wherein the phosphorescent metal complex is a metal complex represented by the following general formula (5).
(In the formula, P and Q represent a carbon atom or a nitrogen atom, A1 represents an atomic group which forms an aromatic hydrocarbon ring or an aromatic heterocycle with PC, and A2 represents a coaromatic carbonization with QN. Represents a group of atoms forming a hydrogen ring or an aromatic heterocyclic ring, P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom L1 represents an atomic group that forms a bidentate ligand with P ₁ and P ₂ , j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 represents 2 or 3. M _{1 as the} central metal represents a group 8-10 metal in the periodic table. The organic electroluminescent device according to claim 15, wherein A2 represented by the general formula (5) is a 5-membered heterocyclic ring. The organic electroluminescence device according to claim 14, wherein the phosphorescent metal complex is a metal complex represented by the following general formula (6).
(In the formula, Z represents a hydrocarbon ring or a heterocyclic ring. P and Q represent a carbon atom or a nitrogen atom, and A1 represents an atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC. .A3 is _{-C (R 01) = C (} R 02) -, - N = C (R 02) -, - C (R 01) = N- or -N = N-a _{represents, R 01} and _{R 02} Represents a hydrogen atom or a substituent, P ₁ -L ₁ -P ₂ represents a bidentate ligand, P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom or an oxygen atom, L ₁ represents P ₁ , P ₂ represents an atomic group forming a bidentate ligand, j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. A certain M ₁ represents a group 8 to 10 metal in the periodic table.) The organic electroluminescence device according to claim 17, wherein Z in the general formula (6) has a substituent represented by the following general formula (7).
(In the formula, Ar ₁ represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, H ₁ represents a carrier transport unit, and n represents an integer of 0 to 10.) The organic electroluminescence device according to any one of claims 14 to 18, wherein the phosphorescent metal complex is an Ir complex. An organic electroluminescent element having a plurality of organic layers including a light emitting layer sandwiched between an anode and a cathode, comprising the organic electroluminescent element material according to any one of claims 1 to 11. The organic electroluminescence device according to any one of claims 12 to 19, wherein the layer is formed by a wet method. 21. The organic electroluminescent element according to claim 12, which emits white light. An illuminating device comprising the organic electroluminescent element according to any one of claims 12 to 20. A display device comprising the organic electroluminescence element according to any one of claims 12 to 20.