JP5387563B2 - ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT, LIGHTING DEVICE AND DISPLAY DEVICE - Google Patents

Description

  The present invention relates to an organic electroluminescence element material, an organic electroluminescence element, a method for producing an organic electroluminescence element, an illumination device, and a display device.

  An organic electroluminescence element (hereinafter also referred to as an organic EL element) is an all-solid-state element composed of an organic material film having a thickness of only about 0.1 μm between electrodes, and emits light of 2V to 20V. Since it can be achieved at a relatively low voltage, it is a technology expected as a next-generation flat display and illumination.

  Furthermore, the recently discovered organic EL element using phosphorescence emission can realize a light emission efficiency of about 4 times in principle compared with that using the previous fluorescence emission. Research and development of light-emitting element layer configurations and electrodes are performed all over the world.

  In addition, the structure of the organic EL element is a simple one in which an organic layer is sandwiched between a transparent electrode and a counter electrode, and the number of parts is overwhelmingly smaller than that of a liquid crystal display, which is a typical flat display. Although the cost should be kept low, this is not always the case at present, and a large amount of water is drained from the liquid crystal display in terms of performance and cost. In particular, in terms of cost, poor productivity is considered as a factor.

Most of organic EL currently commercialized are manufactured by a so-called vapor deposition method in which a low molecular material is vapor deposited to form a film. In this vapor deposition method, an organic EL material can be used as a low-molecular compound that can be easily purified (a high-purity material can be easily obtained), and a laminated structure can be easily formed. Although it is excellent, on the other hand, since vapor deposition is performed under a high vacuum condition 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, and when a plurality of layers are laminated In this case, the film formation takes time and the throughput is low.

  In particular, it becomes a problem when applied to lighting applications and large-area electronic displays, and organic EL is one cause that is not practically used in such applications.

  On the other hand, a coating method in which an organic compound layer is manufactured by processes such as spin coating, ink jet, printing, and spraying can be used to produce a thin film at normal pressure and to produce a uniform film over a large area.

  In the coating method, a necessary material (polymer material and / or low molecular weight material) is prepared as a solution or dispersion and applied in a thin film, so that a plurality of organic materials can be mixed precisely (for example, dopant for a light emitting host material, etc. For example, it is easy to make adjustments, so that even if the element is enlarged, there is a feature that unevenness in light emission is difficult to occur, which is very advantageous in terms of manufacturing cost.

  Materials used for coating methods are large and low molecular, but in general, high molecular materials are difficult to purify, especially organic electroluminescence devices, which have very small impurities that greatly reduce the light emission life of the device. This is difficult to apply.

  Conventionally known low molecular weight hole transport materials that can be used for the hole transport layer have been disclosed (for example, see Patent Document 1). When a device was formed and the device performance was evaluated, there was an increase in operating voltage compared to a device produced by vapor deposition. Furthermore, when the upper layer was formed by a coating method, the hole transport layer as the lower layer For example, a technique using a triarylamine derivative having three or more polymerizable functional groups is disclosed (for example, Patent Documents). 2 and Patent Document 3).

  However, when the present inventors examined in detail, when the number of polymerizable functional groups is large, the energy at the time of crosslinking by light or heat increases, and the polymerizable functional groups tend to remain without participating in crosslinking. And the remaining polymerizable functional group has a high activity, which contributes to deterioration of the device life.

On the other hand, when the number of polymerizable functional groups is small, the crosslink density between the compounds in the film decreases, so that there is a problem that the solvent resistance is poor and the upper layer cannot be laminated, and improvement is required.
Japanese Patent No. 2851185 JP 2005-036223 A JP 2007-094619 A

  Provided a hole transport layer that is sufficiently crosslinked at a low temperature for a shorter time than conventional organic EL element materials, has little damage due to ultraviolet light and heat, has very high solvent resistance, and high surface smoothness, and An organic EL device having high performance (high external extraction quantum efficiency and long life) using the organic EL device material of the present invention is provided.

The above object of the present invention is achieved by the following configurations 1 to 23. Specifically, according to the present invention, in the configuration 1, an organic electroluminescence element material excluding a compound represented by the following general formula (X) is provided. Provided.
[Wherein T represents a polymerizable functional group represented by formula (Y). T may be the same or different. ]
[Wherein, R ¹ represents a hydrogen atom or an alkyl group. ]

  1. An organic electroluminescent element material comprising a polymerizable compound represented by the following general formula (1) or a polymer compound having a structural unit derived from the polymerizable compound.

[Wherein, Ar ₁ and Ar ₂ each represent an unsubstituted benzene ring or an unsubstituted naphthalene ring, and X ₁ , X ₂ , X ₃ and X ₄ each represent a hydrogen atom or a general formula (a-1) A polymerizable functional group represented by any one of (a-3). However, _one of X ₁ and X ₂ and one of X ₃ and X ₄ each represents a hydrogen atom. ]

[In the formula, R represents a hydrogen atom or a methyl group, and Q represents a single bond, a linking group represented by the following general formula (b), or a divalent linking group represented by a plurality of combinations. , Q ′ represents any one of the linking groups represented by the following general formula (b) or a divalent linking group represented by a plurality of combinations. ]

[Wherein n represents an integer of 1 or more. ]
2. 2. The organic electroluminescence according to 1 above, wherein the polymerizable compound represented by the general formula (1) or a polymer compound having a structural unit derived from the polymerizable compound is a hole transport layer forming material. Element material.

  3. The polymerizable compound represented by the general formula (1) or the polymer compound having a structural unit derived from the polymerizable compound is represented by any one of the following general formulas (2) to (5). 3. The organic electroluminescent element material according to 1 or 2 above.

[In the formula, Ar ₁ and Ar ₂ each represent an unsubstituted benzene ring or an unsubstituted naphthalene ring, and X ₅ represents a polymerization represented by any one of the general formulas (a-1) to (a-3) Represents a functional group. ]
4). Table with either one of _{X 1, X 2, X 3} , one and the general formula _{X 4} (2) ~ _{X 5} is the general formula (5) (a-1) of the general formula (1) The organic electroluminescent element material according to any one of the above items 1 to 3, wherein

  5. Q of said general formula (a-1) is a single bond, The organic electroluminescent element material of any one of said 1-4 characterized by the above-mentioned.

6). 6. The compound according to any one of 1 to 5 above, wherein Ar ₁ and Ar ₂ of the compound represented by any one of the general formulas (1) to (5) are each an unsubstituted benzene ring. Organic electroluminescence element material.

  7). 7. The organic electroluminescence element material according to any one of 1 to 6, wherein the polymerizable compound represented by the general formula (1) is Compound 1 or Compound 3.

  8). 8. The organic electroluminescent element material according to any one of 1 to 7 above, which is used for an organic electroluminescent element containing a phosphorescent compound as a constituent material.

9. In an organic electroluminescence device having a plurality of organic compound layers including a light emitting layer and a hole transport layer between an anode and a cathode,
At least 1 layer of this positive hole transport layer contains the organic electroluminescent element material of any one of said 1-8, The organic electroluminescent element characterized by the above-mentioned.

  10. 10. The organic electroluminescence device as described in 9 above, wherein at least one of the light emitting layers contains a phosphorescent compound.

  11. 11. The organic electroluminescence device as described in 10 above, wherein at least one of the phosphorescent compounds is a compound represented by the following general formula (6).

[In formula, P and Q represent a carbon atom or a nitrogen atom, and 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. P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2. j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M1 represents a group 8-10 metal element in the periodic table. ]
12 12. The organic electroluminescence device as described in 11 above, wherein the compound represented by the general formula (6) is a compound represented by the following general formula (7).

[Wherein, Z represents a hydrocarbon ring group, an aromatic heterocyclic group or a heterocyclic group. 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 represents -C ( _R01 ) = C ( _R02 )-, -N = C ( _R02 )-, -C ( _R01 ) = N- or -N = N-, and _R01 and _R02 represent Represents 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. L ₁ 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 is 2 or 3. M ₁ represents a group 8-10 metal element in the periodic table. ]
13. 13. The organic electroluminescence device according to any one of 9 to 12, wherein the phosphorescent compound is an iridium complex.

  14 14. The organic electroluminescent element according to any one of 9 to 13, which emits white light.

  15. The above 9 to 14, wherein the constituent layer has a hole transport layer and a light emitting layer, and the hole transport layer is produced through a process of forming and forming a film by a wet method (wet process). The organic electroluminescent element of any one of Claims.

  16. 16. The organic electroluminescence device as described in 15 above, wherein the light emitting layer is manufactured through a process in which a film is formed and formed by a wet method (wet process).

  17. The hole transport layer is formed by polymerizing the polymerizable compound represented by the general formula (1) by a wet method (wet process) and then polymerizing the polymerizable compound by applying heat or light. The organic electroluminescence device as described in 15 or 16, wherein the organic electroluminescence device is manufactured through a process.

  18. 18. When manufacturing the organic electroluminescent element of any one of said 9-17, it has a process by which a positive hole transport layer is formed into a film and formed by a wet method (wet process), The organic electroluminescent characterized by the above-mentioned. Device manufacturing method.

  19. When manufacturing the organic electroluminescent element of any one of said 9-17, it has the process in which a positive hole transport layer and a light emitting layer are formed into a film and formed by a wet method (wet process), It is characterized by the above-mentioned. Manufacturing method of organic electroluminescent element.

  20. The hole transport layer is formed by depositing the organic electroluminescent element material according to any one of 1 to 8 above by a wet method (wet process), and then applying the general formula (1) by applying heat or light. 20. The method for producing an organic electroluminescence device as described in 18 or 19 above, wherein the polymerizable compound represented by the formula is polymerized.

  21. 18. An illumination device comprising the organic electroluminescence element according to any one of 9 to 17 above.

  22. 18. A display device comprising the organic electroluminescence element according to any one of 9 to 17 above.

  23. The polymeric compound characterized by having the polymeric compound represented by General formula (1) of any one of said 1-8, or the structural unit induced | guided | derived from this polymeric compound.

  Since the organic EL device material of the present invention is sufficiently crosslinked at a low temperature for a shorter time, an organic compound layer having a very high solvent resistance with little damage caused by ultraviolet light or heat can be formed. The layer was found to have very high surface smoothness. Moreover, since it becomes possible to laminate | stack by the apply | coating method by using the organic EL element material of this invention, cost performance is high, and the organic EL element of high performance (external extraction quantum efficiency is high and long life) is obtained. Could be provided.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. 4 is a schematic diagram of a display unit A. FIG. It is a schematic diagram of a pixel. It is a schematic diagram of a passive matrix type full-color display device. It is the schematic of an illuminating device. It is a schematic diagram of an illuminating device. The schematic block diagram of an organic electroluminescent full color display apparatus is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 7 Power supply line 10 Organic EL element 11 Switching transistor 12 Drive transistor 13 Capacitor A Display part B Control part 101 Glass substrate 102 ITO transparent electrode 103 Partition 104 104 Hole injection layer 105B, 105G, 105R Luminescent layer 207 Glass substrate with transparent electrode 206 Organic EL layer 205 Cathode 202 Glass cover 208 Nitrogen gas 209 Water catching agent

  In the organic EL element material of the present invention, the organic electroluminescence element material according to any one of claims 1 to 6 is sufficiently designed to be crosslinked at a low temperature for a short time by ultraviolet light or heat. It was possible to obtain an organic EL element material capable of forming a thin film with little damage due to.

  Moreover, when the organic EL element material of the present invention was used, a method for producing an organic EL element having a high external extraction quantum efficiency and a long emission lifetime could be provided.

  In addition, it was possible to provide an organic EL element manufactured by the manufacturing method, a display device including the element, and a lighting device.

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

<< Polymerizable compound represented by general formula (1), polymer compound derived from the compound >>
The polymerizable compound represented by the general formula (1) relating to the organic EL device material of the present invention or a polymer compound derived from the compound will be described. In addition, the polymeric compound guide | induced from the said polymeric compound can be produced | generated by applying a heat | fever or an ultraviolet-ray etc. to the polymeric compound represented by General formula (1) of this invention.

In the general formula (1), Ar ₁ and Ar ₂ each represent an unsubstituted benzene ring or an unsubstituted naphthalene ring, and X ₁ , X ₂ , X ₃ , and X ₄ each represent a hydrogen atom or the general formula (a -1) It represents a polymerizable functional group represented by any one of (a-3). However, _one of X ₁ and X ₂ and one of X ₃ and X ₄ each represents a hydrogen atom.

  In the polymerizable functional group represented by any one of the general formulas (a-1) to (a-3) in the general formula (1), R represents a hydrogen atom or a methyl group, and Q represents a single bond or Any one of the linking groups represented by the general formula (b) or a divalent linking group represented by a plurality of combinations, Q ′ is any of the linking groups represented by the following general formula (b), Alternatively, it represents a divalent linking group represented by a plurality of combinations.

  Furthermore, in the linking group represented by the general formula (b) according to the general formula (1), n represents an integer of 1 or more.

  The polymerizable compound represented by the general formula (1) or the polymer compound having a structural unit derived from the compound according to the organic EL element material of the present invention is a constituent layer or an organic compound layer of the organic EL element of the present invention. However, it is particularly preferable as a material for forming a hole transport layer.

  The constituent layers and organic compound layers of the organic EL device of the present invention will be described in detail later.

<< Polymerizable compound represented by any one of formulas (2) to (5) >>
Among the polymerizable compound represented by the general formula (1) or the polymer compound derived from the compound, a polymer represented by any one of the general formulas (2) to (5) is preferably used. Or a high molecular compound derived from the compound.

In each polymerizable compound represented by any one of the general formulas (2) to (5) or a polymer compound derived from the polymerizable compound, the general formulas (a-1) to (a) represented by X ₅ -3) is the same as the polymerizable functional group represented by any one of the general formulas (a-1) to (a-3) in the general formula (1). .

Further, the polymerizable compound represented by any of formulas (1) to (5), the polymerizable functional group represented by X _5, polymerizable functional represented by the general formula (a-1) In the polymerizable functional group represented by formula (a-1), Q is preferably a single bond. Furthermore, in the polymerizable compound represented by any one of the general formulas (1) to (5), Ar ₁ and Ar ₂ are each preferably an unsubstituted benzene ring.

  Among the polymerizable compounds represented by any one of the general formulas (1) to (5) according to the present invention, the following Compound Example 1 and Compound Example 2 are particularly preferably used. In addition, about the compound example 1 and the compound example 2, it describes in the place of the specific example of a polymeric compound mentioned later.

  Hereinafter, although the specific example of the polymeric compound represented by either of General formula (1)-(5) is shown, this invention is not limited to these.

<< Constitutional layer of organic EL element, organic compound layer >>
The constituent layers and organic compound layers of the organic EL device of the present invention will be described. Although the preferable specific example of the layer structure of the organic EL element of this invention is shown below, this invention is not limited to these.

(I) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iii) Anode / hole transport layer / Light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (iv) anode / anode buffer layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode << Organic compound layer (also called organic layer) >>
The organic compound layer according to the present invention will be described.

  The organic EL device of the present invention preferably has a plurality of organic compound layers as a constituent layer, and examples of the organic compound layer include a hole transport layer, a light emitting layer, and a hole blocking layer in the above-described layer configuration. As the organic compound layer according to the present invention, an organic compound contained in a constituent layer of the organic EL element, such as a hole injection layer or an electron injection layer, is included. Defined.

  Further, when an organic compound is used for the anode buffer layer, the cathode buffer layer, and the like, the anode buffer layer, the cathode buffer layer, and the like each form an organic compound layer.

  The organic compound layer includes a layer containing “organic EL element material that can be used for a constituent layer of an organic EL element” or the like.

  In the organic EL device of the present invention, the light emitting maximum wavelength of the blue light emitting layer is preferably 430 nm to 480 nm, the green light emitting layer has a light emitting maximum wavelength of 510 nm to 550 nm, and the red light emitting layer has a light emitting maximum wavelength of 600 nm to 640 nm. A monochromatic light emitting layer in the range is preferable, and a display device using these is preferable.

  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 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 a 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 nm to 200 nm, and particularly preferably in the range of 10 nm to 20 nm.

  For the production of the light-emitting layer, a light-emitting dopant or a host compound, which will be described later, is formed by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink-jet method. it can.

  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.

  Here, in the present invention, the host compound means a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. A rate is defined as a compound of less than 0.1. 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.

  In the present invention, the compound having the carbazole ring as a partial structure, the compound having a polymerizable group and having the carbazole ring as a partial structure, and a polymer of the compound are particularly preferably used as the host compound.

  In addition, as a host compound, a well-known host compound may be used together, and may be used in combination of multiple types. 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. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  A conventionally known host compound that may be used in combination is preferably 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). .

  Specific examples of conventionally known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(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 having higher luminous efficiency, the above-mentioned host compound may be used as the luminescent dopant (simply referred to as a luminescent material) used in the light emitting layer or the light emitting unit of the organic EL device of the present invention. It is preferable to contain a phosphorescent dopant at the same time as containing.

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

  The phosphorescent compound 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 compound 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 compounds. In principle, the recombination of carriers occurs on the host compound to which carriers are transported, and an excited state of the host compound is generated. This energy is phosphorescent. An energy transfer type that obtains light emission from the phosphorescent compound by transferring to the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, and recombination of carriers on the phosphorescent compound is performed. And a carrier trap type in which light emission from the phosphorescent compound is obtained.

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

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

  The phosphorescent compound 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, with iridium compounds (Ir complexes) being most preferred among them.

<< Phosphorescent Compound Represented by General Formula (6) >>
As the phosphorescent compound according to the present invention, a compound represented by the general formula (6) is preferably used.

  In the general formula (6), the aromatic hydrocarbon ring represented by A1 includes a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, Examples include a pyranthrene ring and anthraanthrene ring. These rings may further have a substituent described later.

  In the general formula (6), examples of the aromatic heterocycle represented by A1 include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a benzimidazole. Ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indazole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, isoquinoline Ring, phthalazine ring, naphthyridine ring, carbazole ring, carboline ring, diazacarbazole ring (showing a ring in which one of the carbon atoms constituting the carboline ring is further substituted with a nitrogen atom) and the like.

  These rings may further have a substituent described later.

<< Substituent >>
Examples of the substituent that the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A1 may have an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group). 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, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, 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, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group) Groups (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, Flazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (carbon constituting the carboline ring of the carbolinyl group) One of the atoms is a nitrogen atom Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy 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, cyclyl). Rohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.) An aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), a sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexyl) Aminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylamino Sulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group) , Pyridylcarbonyl group etc.), acyloxy group (eg acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group etc.), amide group (eg methylcarbonyl) Amino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethyl Xylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group) Pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, , Methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenyl Ureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthyl) Sulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or hetero An arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethyl Amino 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.

  In addition, 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 (6), the aromatic hydrocarbon ring and aromatic heterocycle represented by A2 are respectively synonymous with the aromatic hydrocarbon ring and aromatic heterocycle represented by A1 in the general formula (6). is there.

  In the general formula (6), examples of the bidentate ligand represented by P1-L1-P2 include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone. And picolinic acid.

  In the general formula (6), M1 is a transition metal element of group 8 to 10 in the periodic table of elements (also simply referred to as a transition metal), among which iridium and platinum are preferable, and iridium is particularly preferable.

<< Phosphorescent Compound Represented by General Formula (7) >>
Among the phosphorescent compounds represented by the general formula (6) according to the present invention, the phosphorescent compounds represented by the general formula (7) are preferably used.

  In the general formula (7), examples of the hydrocarbon ring group represented by Z include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or may have a substituent which the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A1 may have.

  Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) include, for example, 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 the like. These groups may be unsubstituted or may have a substituent which the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A1 may have.

  In the general formula (7), the aromatic hydrocarbon ring represented by A1 has the same meaning as the aromatic hydrocarbon ring represented by A1 in the general formula (6).

  In the general formula (7), the aromatic heterocycle represented by A1 has the same meaning as the aromatic heterocycle represented by A1 in the general formula (6).

In A3 of the general formula (7), each of the substituents represented by R ₀₁ and R ₀₂ has the aromatic hydrocarbon ring or the aromatic heterocycle represented by A1 in the general formula (6). Is synonymous with a good substituent.

  In the general formula (7), the bidentate ligand represented by P1-L1-P2 has the same meaning as the bidentate ligand represented by P1-L1-P2 in the general formula (6). .

In the general formula (7), 8-10 metal elements in the periodic table represented by _{M 1} are the compounds of formula (6), a transition metal of Group 8 to Group 10 in the periodic table represented by _{M 1} Synonymous with element (also referred to simply as transition metal).

  Specific examples of the compound used as the phosphorescent compound are shown below, but the present invention is not limited thereto. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like.

  Hereinafter, although the specific example of the phosphorescence-emitting dopant 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 a constituent layer 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.

  The injection layer refers to a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the light emission luminance. “The organic EL element and the forefront of its industrialization (issued by NTT Corporation on November 30, 1998) 2 of 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.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (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.

<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 nm to 100 nm, and more preferably 5 nm 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, and also 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-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 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, since a higher performance light emitting device can be obtained, the present invention contains a polymerizable compound represented by the general formula (1) or a polymer compound having a structural unit derived from the polymerizable compound. The organic EL element material is preferably used as a hole transport material, and the above materials may be used in combination.

  The hole transport layer can be 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. However, in the present invention, it is preferably produced by a coating method (wet process). 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 nm-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 the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and 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 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 nm-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 materials 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. 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 nm to 1000 nm, preferably 10 nm 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, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. 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 a 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 nm 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 by the film thickness of 1 nm-20 nm to a cathode, the 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, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ ml / (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. However, 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. Furthermore, the polymer film has a oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · MPa) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 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, but it is lightweight and thin. It is preferable to use a polymer film.

《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. It 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 taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. 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 element of the present invention is processed to provide, for example, a microlens array-like structure on the light extraction side of the substrate, or in combination with a so-called condensing sheet, so that the organic EL element is in front of the element light emitting surface. By condensing in the 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 μm 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 / hole blocking layer / electron transport layer / electron injection layer / cathode Will be explained.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm, to form an anode.

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

  As a method for forming each of these layers, 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 uniform 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.

  In particular, the layer containing a compound having a carbazole ring as a partial structure according to the present invention, the compound having a polymerizable group, and a polymer of the compound is preferably formed by the above-described coating method. Is preferably a light emitting layer.

  Further, when the total number of layers (the constituent layers of the organic EL element) existing between the anode and the cathode is 100%, 50% or more of the total number of layers is preferably formed by a coating method. .

  For example, in the anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode mentioned as an example of the organic EL element, the hole injection layer In the case where the total number of layers / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer is 6, it is preferable that at least three layers are formed by a coating method.

  When the constituent layers of the organic EL device of the present invention are formed by coating, examples of the liquid medium for dissolving or dispersing various organic EL materials used for coating include ketones such as methyl ethyl ketone and cyclohexanone, and fatty acid esters such as ethyl acetate. , Halogenated hydrocarbons such as dichlorobenzene, aromatic hydrocarbons such as toluene, xylene, mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO be able to.

  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 1 μm or less, preferably by a method such as vapor deposition or sputtering so that the film thickness is in the range of 50 nm to 200 nm. By providing, a desired organic EL element can be obtained.

  Further, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the hole blocking 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 V to 40 V with the anode as + and the cathode as-. 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 device may be patterned. 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.

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 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

<Display device>
The display device of the present invention will be described. The display device of the present invention comprises the organic EL element of the present invention.

  Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.

  In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.

  The configuration of the organic EL element provided in the display device is selected from the above-described configuration examples of the organic EL element as necessary.

  Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect | mode of manufacture of the organic EL element of said invention.

  In the case of applying a DC voltage to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. The present invention is not limited to these examples.

  Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below.

  In the figure, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)

  When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.

  Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 3 is a schematic diagram of a pixel.

  The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

  That is, the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels, and light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good. The potential of the capacitor 13 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 4 is a schematic view of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.

  In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

《Lighting device》
The lighting device of the present invention having the organic EL element will be described.

  The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

  The organic EL material of the present invention can be applied as an illumination device to an organic EL element that emits substantially white light. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.

  It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved.

  According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

<< One Embodiment of Lighting Device of the Present Invention >>
One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.

  The non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material. LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and an illumination device as shown in FIGS. Can be formed.

  FIG. 5 shows a schematic diagram of a lighting device, and the organic EL element 201 of the present invention is covered with a glass cover 202 (in addition, the sealing operation with the glass cover is to bring the organic EL element 201 into contact with the atmosphere. And a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more).

  6 shows a cross-sectional view of the lighting device. In FIG. 6, 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.

  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. The structures of the compounds used in the examples are shown below.

Example 1
<< Preparation of Organic EL Material Thin Film 1-1 >>: The present invention A quartz substrate of 30 mm × 30 mm × 1.1 mm is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. A thin film was obtained by attaching a solution obtained by dissolving Compound Example 1 (100 mg) in 10 ml of toluene to a commercially available spin coater by spin coating at 1500 rpm for 30 seconds and further vacuum drying at 25 ° C. for 1 hour. It was.

  The obtained thin film was irradiated with ultraviolet light for 60 seconds to prepare a polymer compound thin film (organic EL material thin film 1-1) having the structural unit of Compound Example 1.

  About the obtained organic EL material thin film 1-1, the absorption spectrum was measured with the spectrophotometer U-3300 (made by Hitachi).

<< Preparation of Organic EL Material Thin Films 1-2 to 1-4 >>: Present Invention Same as the preparation of the organic EL material thin film 1-1 except that Compound Examples 18, 19, and 22 were used instead of Compound Example 1, respectively. Thus, organic EL material thin films 1-2 to 1-4 were respectively prepared.

<< Preparation of Organic EL Material Thin Film 1-5 >>: Comparative Example Organic EL material thin film 1-5 was prepared in the same manner as in the preparation of organic EL material thin film 1-1 except that Comparative Compound 1 was used instead of Compound Example 1. (Comparative example) was produced.

<< Solvent Resistance Evaluation of Organic EL Material Thin Film >>: Curability of Organic EL Element Material In evaluating the curability of the organic EL element material, each of the obtained organic EL material thin films 1-1 to 1-5 is described below. Thus, the solvent resistance of the thin film was evaluated.

  Each of the obtained organic EL material thin films 1-1 to 1-5 was immersed vertically in toluene at 20 ° C., held for 3 seconds with the entire substrate immersed, pulled up, and vacuum dried at 25 ° C. for 1 hour. did.

  For each of the organic EL material thin films 1-1 to 1-5 after the immersion, the absorption spectrum is measured in the same manner as before the immersion, and the absorbance at the maximum wavelength of 200 nm to 250 nm is compared before and after the immersion. Evaluation was performed.

A: (absorbance after immersion / absorbance before immersion) exceeds 0.98 O: (absorbance after immersion / absorbance before immersion) exceeds 0.95 to 0.98
Δ: (absorbance after immersion ÷ absorbance before immersion) is 0.90 to 0.95
X: The value of (absorbance after immersion ÷ absorbance before immersion) is less than 0.90. The results obtained are shown below.

Organic EL material thin film No. Organic EL material Solvent resistance Remarks Organic EL material thin film 1-1 Compound example 1 ◎ The present invention Organic EL material thin film 1-2 Compound example 18 △ The present invention Organic EL material thin film 1-3 Compound example 19 △ The present invention Organic EL material thin film 1-4 Compound Example 22 ○ Present Organic EL Material Thin Film 1-5 Comparative Compound 1 × Comparative Example From the above, organic EL material thin films 1-1 to 1-4 produced using the organic EL element material of the present invention. Shows higher solvent resistance than the comparative organic EL material thin film 1-5, the organic EL element material of the present invention has practically sufficient crosslinkability (also referred to as curability) and is solvent resistant. It can be seen that a highly thin film is formed.
Example 2
<< Preparation of Organic EL Material Thin Film 2-1 >>: The present invention A quartz substrate of 30 mm × 30 mm × 1.1 mm was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. A solution obtained by dissolving Compound Example 3 (60 mg) in 10 ml of toluene was formed by spin coating at 1000 rpm for 30 seconds, and further vacuum dried at 25 ° C. for 1 hour to obtain a film thickness. A thin film of about 25 nm was obtained.

  The resulting thin film was irradiated with ultraviolet light for 90 seconds to prepare a polymer compound thin film (organic EL material thin film 2-1) having the structural unit of Compound Example 3.

<< Preparation of Organic EL Material Thin Films 2-2 to 2-4 >>: Present Invention The same as in the preparation of the organic EL material thin film 2-1, except that instead of Compound Example 3, each of Compound Examples 10, 14, and 21 was changed. Thus, organic EL material thin films 2-2 to 2-4 were produced.

<< Preparation of Organic EL Material Thin Film 2-5 >>: Comparative Example In the preparation of the organic EL material thin film 2-1, the organic EL material thin film 2-5 was prepared in the same manner except that Comparative Compound 1 was used instead of Compound 3. Produced.

<< Smoothness evaluation of organic EL material thin film >>: Smoothness evaluation before solvent immersion and after solvent immersion For each of the obtained organic EL material thin films 2-1 to 2-5, the central part of the thin film before and after ultraviolet light irradiation The average surface roughness (Ra) of 50 μm square was measured using an atomic force microscope (AFM). The average surface roughness according to the present invention represents the surface roughness defined in JIS-B 0601-1994.

  Next, each of the organic EL material thin films 2-1 to 2-5 was immersed vertically in toluene at 20 ° C., rested for 3 seconds in a state where the entire substrate was immersed, then pulled up and vacuum dried at 25 ° C. for 1 hour.

  About each thin film after immersion, average surface roughness (Ra) was measured similarly to before immersion, and rank evaluation was performed as shown below.

A: Less than 0.44 nm B: 0.44 nm to 0.49 nm
Δ: More than 0.49 nm to 0.54 nm
X: exceeding 0.54 nm The obtained results are shown below.
Organic EL material thin film No. Compound Average surface roughness Average surface roughness Remarks
(Before dipping) (After dipping)
Organic EL Material Thin Film 2-1 Compound Example 3 ◎ ◎ Organic EL Material Thin Film 2-2 Compound Example 10 ◎ ○ Organic EL Material Thin Film 2-3 Compound Example 14 ○ △ Organic EL Material Thin Film 2-4 Compound of the Present Invention Example 21 △ △ Organic EL Material Thin Film of the Present Invention 2-5 Comparative Compound Example 1 XX Comparative Example From the above, the organic EL material thin film of the present invention is in any thin film before or after the solvent immersion. It is apparent that a film having a high surface smoothness is given and that the film has a high smoothness even after being exposed to a solvent.
Example 3
<< Manufacture of Organic EL Element 3-1 >>: Comparative Example A substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode. After patterning, the transparent support substrate provided with the ITO transparent electrode 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. After forming the film by spin coating, the film was dried at 200 ° C. for 1 hour to provide a 20 nm-thick hole transport layer.

  The substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of Comparative Compound 2 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 carry out photopolymerization and crosslinking to form a second hole transport layer having a thickness of about 20 nm.

  On this second hole transport layer, a solution of 100 mg of the host material 1 and 10 mg of Ir-15 dissolved 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 a 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 3-1 was produced.

<< Production of Organic EL Elements 3-2 to 3-6 >>
Organic EL elements 3-2 to 3-6 were respectively prepared in the same manner except that Comparative Compound 2 was replaced with the compound shown below in preparation of the organic EL element 3-1.

<< Evaluation of Organic EL Elements 3-1 to 3-6 >>
When evaluating the obtained organic EL elements 3-1 to 3-6, 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 in the periphery, and this is placed on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 5 and 6 was formed and evaluated.

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

(External extraction quantum efficiency)
The organic EL devices fabricated, 23 ° C., 2.5 mA under a dry nitrogen atmosphere / cm ² external extraction quantum efficiency upon application of a constant current (%) was measured.

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

  Moreover, the measurement result of the external extraction quantum efficiency was expressed as a relative value when the measurement value of the organic EL element 3-1 was 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 Sensing) was used.

  Moreover, the measurement result of the lifetime was expressed as a relative value when the organic EL element 3-1 was 100.

  The results obtained are shown below.

Organic EL element Compound External extraction Life Remarks
Quantum Efficiency 3-1 Comparative Compound 2 100 100 Comparative Example 3-2 Compound Example 3 360 300 Present Invention 3-3 Compound Example 12 370 290 Present Invention 3-4 Compound Example 13 400 240 Present Invention 3-5 Compound Example 15 420 230 Invention 3-6 Compound Example 19 330 270 Invention Example 4
<< Preparation of Organic EL Element 4-1: Preparation of Full Color Display Device >>
FIG. 7 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.) formed by forming a 100 nm ITO transparent electrode (102) 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 was ejected and injected between polyimide partition walls on the ITO electrode using an inkjet head (manufactured by Epson Corporation; MJ800C), irradiated with ultraviolet light for 120 seconds, 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 layers (105B, 105G, 105R), and an organic EL element 4-1 as a full-color display device was produced.

  It was found that the produced organic EL element 4-1 emitted blue, green, and red light by applying a voltage to each electrode, and could be used as a full-color display device.

(Hole injection layer composition)
Compound Example 6 20 parts by mass of cyclohexylbenzene 50 parts by mass of isopropyl biphenyl 50 parts by mass (blue light emitting layer composition)
Host compound 2 0.7 parts by mass D-3 0.04 parts by mass cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass (green light emitting layer composition)
Host compound 2 0.7 parts by mass Ir-1 0.04 parts by mass cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass (red light emitting layer composition)
Host compound 2 0.7 parts by mass Ir-14 0.04 parts by mass cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 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 In addition to D-3, Ir-1, and Ir-14, compounds Ir-2 to Ir-27, Pt-1 to Pt-3 , A-1, d-1 to 6, Pd-1 to 3, Rh-1 to 3, (1) to (187), and organic EL devices fabricated using D-1 to 27 are similarly full-color display. It was found that it can be used as a device.
Example 5
<< Preparation of White Light-Emitting Organic EL Element 5-1 >>
A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water on the transparent electrode substrate of Example 3 is 3000 rpm. After forming the film by spin coating in 30 seconds, the film was 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 of 50 mg of Compound Example 1 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 carry out photopolymerization and crosslinking to form a second hole transport layer having a thickness of about 20 nm. Further, as a light-emitting layer, a solution prepared by dissolving 100 mg of the host compound 2, 10 mg of Ir-15, and 0.1 mg of Ir-9 in 10 ml of toluene was formed 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 3, an electron transport layer, a lithium fluoride layer, and an aluminum cathode were formed to produce a white light-emitting organic EL element 5-1, and sealed in the same manner as in Example 3.

When the obtained 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 6
<< Preparation of Organic EL Material Thin Film 6-1 >>: The present invention A quartz substrate of 30 mm × 30 mm × 1.1 mm was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. A solution obtained by dissolving Compound Example 1 (100 mg) in 10 ml of toluene was formed into a film by spin coating at 1000 rpm for 30 seconds, and further vacuum dried at 25 ° C. for 1 hour to obtain a film thickness. A thin film of about 50 nm was obtained.

  The obtained thin film was irradiated with ultraviolet light for 30 seconds in a nitrogen atmosphere, and then the irradiation was stopped for 30 seconds. The polymer having the structural unit of Compound Example 1 was subjected to photopolymerization and crosslinking by repeating 5 sets. A compound thin film (organic EL material thin film 6-1) was prepared.

<< Preparation of Organic EL Material Thin Films 6-2 to 6-3 >>: Present Invention In the preparation of the organic EL material thin film 6-1 in the same manner except that Compound Examples 7 and 16 are used instead of Compound Example 1, respectively. Organic EL material thin films 6-2 to 6-3 were prepared.

<< Preparation of Organic EL Material Thin Film 6-4 >>: Comparative Example In the preparation of organic EL material thin film 6-1, organic EL material thin film 6-4 was prepared in the same manner except that compound 1 was used instead of compound 1. Produced.

<< Smoothness evaluation of organic EL material thin film >>
For each of the obtained organic EL material thin films 6-1 to 6-4, the average surface roughness (Ra) of the central 50 μm square was measured using an atomic force microscope (AFM) for the thin films before and after ultraviolet light irradiation. did. The average surface roughness according to the present invention represents the surface roughness defined in JIS-B 0601-1994.

  Rank evaluation as shown below was performed about the average surface roughness (Ra) of the obtained thin film.

A: Less than 0.44 nm B: 0.44 nm to 0.49 nm
Δ: More than 0.49 nm to 0.54 nm
X: exceeding 0.54 nm Table 6 shows the obtained results.

<< Analysis of concentration of polymerizable functional group in organic EL material thin film >>
The obtained organic EL material thin films 6-1 to 6-4 were analyzed by IR analysis using FT-IR Magna 860-NIC plan IR-Microscope manufactured by Nicorey Co., Ltd. Double bond) was measured. The peak intensity of the vinyl group double bond site before irradiating each organic EL material thin film with ultraviolet light was set to 100, the peak intensities after ultraviolet light irradiation were compared, and the following rank evaluation was performed. Peak intensity after light irradiation ○: Less than 0.1 Δ: 0.1 to 0.3
X: More than 0.3 Table 6 shows the obtained results.
Organic EL material Compound Average surface roughness After UV irradiation Remarks Thin film no. Peak intensity
6-1 Compound Example 1 ◎ ○ Invention 6-2 Compound Example 7 ◎ ○ Reference Example 6-3 Compound Example 16 ○ △ Invention 6-4 Comparative Compound Example 3 × × Comparative Example From the above, Comparative Compound Example 3 was used. Since the organic EL material thin film had a large number of polymerizable functional groups, shrinkage occurred during crosslinking, the smoothness of the film was disturbed, and the polymerizable functional groups tended to remain even when irradiated with the same amount of ultraviolet light. On the other hand, it is clear that the organic EL material thin film of the present invention gives a film having high surface smoothness, and there is almost no polymerizable functional group remaining after irradiation with ultraviolet light.
Example 7
<< Manufacture of Organic EL Element 7-1 >> Comparative Example On a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode. After patterning, the transparent support substrate provided with the ITO transparent electrode 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. After forming the film by spin coating, the film was 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 of 30 mg of Comparative Compound 3 dissolved in 10 ml of chloroform was formed on the hole transport layer by spin coating at 1000 rpm for 30 seconds.

  Under a nitrogen atmosphere, irradiation with ultraviolet light for 30 seconds was followed by stopping the irradiation for 30 seconds as one set, and photopolymerization / crosslinking was performed by repeating 5 sets to form a second hole transport layer.

  On this second hole transport layer, a solution prepared by dissolving 100 mg of the host material 3 and 15 mg of Ir-12 in 10 ml of toluene was formed by spin coating at 1000 rpm for 30 seconds. It vacuum-dried at 60 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 50 nm.

Then, the substrate was fixed to a substrate holder of a vacuum deposition apparatus, after the pressure in the vacuum tank was reduced to 4 × 10 -4 ^Pa, thereby forming an electron transport layer BAlq ₃ to 30nm deposited on the light-emitting layer.

  Subsequently, 0.4 nm of sodium fluoride was deposited as a cathode buffer layer, and 110 nm of aluminum was deposited as a cathode to form a cathode, thereby fabricating an organic EL element 7-1.

<< Production of Organic EL Elements 7-2 to 7-6 >>
In the production of the organic EL element 7-1, organic EL elements 7-2 to 7-6 were produced in the same manner as the organic EL element 7-1 except that the comparative compound 3 was replaced with the following compound.

<< Evaluation of Organic EL Elements 7-1 to 7-6 >>
When evaluating the obtained organic EL elements 7-1 to 7-6, 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 in the periphery, and this is placed on the cathode to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 5 and 6 was formed and evaluated.

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

(External extraction quantum efficiency)
The organic EL devices fabricated, 23 ° C., 2.5 mA under a dry nitrogen atmosphere / cm ² external extraction quantum efficiency upon application of a constant current (%) was measured.

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

  Moreover, the measurement result of the external extraction quantum efficiency was expressed as a relative value when the measurement value of the organic EL element 7-1 was 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 Sensing) was used.

  The lifetime was expressed as a relative value when the organic EL element 3-1 was set to 100.

The results obtained are shown below.
Organic EL Element Hole Transport Compound Dopant External Extraction Life Remarks Quantum Efficiency 7-1 Comparative Compound 3 Ir-12 100 100 Comparative Example 7-2 Compound Example 16 Ir-12 360 270 Invention 7-3 Compound Example 16 Ir-16 370 1200 Invention 7-4 Compound Example 7 Ir-16 370 1300 Reference Example 7-5 Compound Example 7 140 390 2000 Reference Example 7-6 Compound Example 1 140 400 2100 Invention

Claims (22)

It contains a polymerizable compound represented by the following general formula (1) or a polymer compound having a structural unit derived from the polymerizable compound (excluding a compound represented by the following general formula (X)). Organic electroluminescence element material characterized by the above.
[Wherein, Ar ₁ and Ar ₂ each represent an unsubstituted benzene ring or an unsubstituted naphthalene ring, and X ₁ , X ₂ , X ₃ and X ₄ each represent a hydrogen atom or a general formula (a-1) A polymerizable functional group represented by any one of (a-3). However, _one of X ₁ and X ₂ and one of X ₃ and X ₄ each represents a hydrogen atom. ]
[In the formula, R represents a hydrogen atom or a methyl group, and Q represents a single bond, a linking group represented by the following general formula (b), or a divalent linking group represented by a plurality of combinations. , Q ′ represents any one of the linking groups represented by the following general formula (b) or a divalent linking group represented by a plurality of combinations. ]
[Wherein n represents an integer of 1 or more. ]
[Wherein T represents a polymerizable functional group represented by formula (Y). T may be the same or different. ]
[Wherein, R ¹ represents a hydrogen atom or an alkyl group. ] The polymerizable compound represented by the general formula (1) or the polymer compound having a structural unit derived from the polymerizable compound is represented by any one of the following general formulas (2) to (4). the organic electroluminescence device material according to claim 1, wherein the.
[In the formula, Ar ₁ and Ar ₂ each represent an unsubstituted benzene ring or an unsubstituted naphthalene ring, and X ₅ represents a polymerization represented by any one of the general formulas (a-1) to (a-3) Represents a functional group. ] Table with either one of _{X 1, X 2, X 3} , one and the general formula _{X 4} (2) ~ _{X 5} is the general formula (4) (a-1) of the general formula (1) The organic electroluminescent device material according to claim 1 or claim 2, wherein the material is an organic electroluminescent device material. The organic electroluminescent element material according to any one of claims 1 to 3, wherein Q in the general formula (a-1) is a single bond. Formula (1) ~ (4) Ar 1, Ar range of ₂ are each claim 1, wherein which is a unsubstituted benzene ring-claims fourth compound represented by any one of The organic electroluminescent element material of any one of claim | items. The organic compound according to any one of claims 1 to 5, wherein the polymerizable compound represented by the general formula (1) is a compound 1 or a compound 3. Luminescence element material.
The organic electroluminescent element material according to any one of claims 1 to 6 , wherein the organic electroluminescent element material is used for an organic electroluminescent element containing a phosphorescent compound as a constituent material. In an organic electroluminescence device having a plurality of organic compound layers including a light emitting layer and a hole transport layer between an anode and a cathode,
The hole at least one layer of the transport layer, the organic electroluminescent device characterized by containing the organic electroluminescence device material according to any one of claims first through Section claims paragraph 7. 9. The organic electroluminescence device according to claim 8, wherein at least one of the light emitting layers contains a phosphorescent compound. The organic electroluminescence device according to claim 9, wherein at least one of the phosphorescent compounds is a compound represented by the following general formula (6).
[In formula, P and Q represent a carbon atom or a nitrogen atom, and 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. P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2. 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 represents a group 8-10 metal element in the periodic table. ] The organic electroluminescent device according to claim 10, wherein the compound represented by the general formula (6) is a compound represented by the following general formula (7).
[Wherein, Z represents a hydrocarbon ring group, an aromatic heterocyclic group or a heterocyclic group. 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 represents -C ( _R01 ) = C ( _R02 )-, -N = C ( _R02 )-, -C ( _R01 ) = N- or -N = N-, and _R01 and _R02 represent Represents a hydrogen atom or a substituent. P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2. 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 represents a group 8-10 metal element in the periodic table. ] The organic electroluminescence device according to any one of claims 8 to 11, wherein the phosphorescent compound is an iridium complex. The organic electroluminescence element according to any one of claims 8 to 12, which emits white light. As a layer having a hole transport layer and light emitting layer, the claims, characterized in that the hole transport layer is prepared by the steps of film formation, it is formed by a wet method (wet process) 8 The organic electroluminescent device according to any one of claims 13 to 14 . 15. The organic electroluminescence device according to claim 14, wherein the light emitting layer is manufactured through a process in which a film is formed and formed by a wet method. The hole transport layer is formed by polymerizing the polymerizable compound represented by the general formula (1) by a wet method (wet process) and then polymerizing the polymerizable compound by applying heat or light. 16. The organic electroluminescence device according to claim 14 , wherein the organic electroluminescence device is manufactured through a process. In manufacturing the organic electroluminescence device according to any one of claims 8 to 16 , a step in which the hole transport layer is formed and formed by a wet method (wet process) is performed. A method for producing an organic electroluminescence element, comprising: In manufacturing the organic electroluminescent device according to any one of claims 8 to 16 , the hole transport layer and the light emitting layer are formed and formed by a wet method. A process for producing an organic electroluminescence element, comprising the steps of: The hole transport layer is formed by depositing the organic electroluminescent element material according to any one of claims 1 to 7 by a wet method, and then heat or light. The production of an organic electroluminescence device according to claim 17 or claim 18, wherein the polymerizable compound represented by the general formula (1) is polymerized by application of Method. An illuminating device comprising the organic electroluminescence element according to any one of claims 8 to 16 . A display device comprising the organic electroluminescence element according to any one of claims 8 to 16 . A polymerizable compound represented by the general formula (1) according to any one of claims 1 to 7 or a structural unit derived from the polymerizable compound. High molecular compound.