JPWO2008029729A1 - Organic electroluminescence element, lighting device and display device - Google Patents

Abstract

The present invention provides an organic electroluminescence element having a high external extraction quantum efficiency and a long light emission lifetime, and further provides an illumination device and a display device including the organic electroluminescence element. The organic electroluminescence device has at least an anode and a cathode on a support substrate, and has at least one light emitting layer between the anode and the cathode, and a partial structure and reaction represented by the following general formula (a) It contains a compound A having a functional group as at least a part, and a polymer obtained by polymerizing the compound A through the reactive group. [Wherein X represents O, S, CR′R ″ or SiR′R ″. R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring.]

Description

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

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

  On the other hand, an organic EL element has a configuration in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer to recombine excitons. This is an element that emits light by utilizing the emission of light (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability.

  As the development of organic EL elements for practical use in the future, there is a demand for organic EL elements that emit light efficiently and with high luminance with lower power consumption. For example, in Japanese Patent No. 3093796, JP-A 63-264692 discloses a technique for doping a stilbene derivative, distyrylarylene derivative or tristyrylarylene derivative with a small amount of phosphor to improve emission luminance and extend the lifetime of the device. And 8-hydroxyquinoline aluminum complex as a host compound, and a device having an organic light emitting layer doped with a small amount of phosphor is disclosed. Japanese Unexamined Patent Publication No. 3-255190 discloses an 8-hydroxyquinoline aluminum complex. As a host compound, an element having an organic light emitting layer doped with a quinacridone dye is known.

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

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

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

  In addition, the organic EL element is an all-solid element composed of an organic material film having a thickness of only about 0.1 μm between the electrodes, and the light emission can be achieved with a relatively low voltage of about 2V to 20V. Therefore, it is a technology that is expected as a next-generation flat display and illumination.

  However, since the organic EL element is based on a light emission phenomenon utilizing deactivation from an excited state of an organic material to a ground state, an organic EL element has a short wavelength region such as blue or blue-green. In order to emit light, it is necessary to increase the band gap, and thus a high voltage is required to excite the large gap.

  Further, since the excited state itself is located at a high level, the damage upon returning to the ground state is large, and the lifetime tends to be shorter than that of green or red light emission. In particular, phosphorous that uses light emission from the triplet excited state is used. The tendency becomes remarkable in light emission.

  There are various techniques for solving the above-mentioned problems. For example, there is a technique of increasing the molecular weight after forming a constituent layer of an organic electroluminescence element. A bifunctional triphenylamine derivative having two is described. After the compound is formed into a film, a three-dimensionally crosslinked polymer is formed by ultraviolet irradiation (see, for example, Patent Document 1). A technique for adding a material having a vinyl group to a plurality of layers is disclosed, and a polymerization reaction is performed by irradiation with ultraviolet rays or heat at the time of forming an organic layer before laminating the cathode (for example, see Patent Document 2). AIBN (azoisobutyronitrile) as a radical generator is added to a mixture of comonomers having a vinyl group in the same manner as a material having a vinyl group at the end of a phosphorescent dopant. A production method in which a polymerization reaction proceeds during film formation (for example, see Patent Document 3), a production method in which a Diels-Alder reaction occurs between two molecules in the same layer (for example, see Patent Document 4), and the like. Can be mentioned.

As described above, phosphorescent dopants, particularly phosphorescent dopants applicable to blue, have a very large band gap and can be used as a host for such dopants, achieving high luminous efficiency and long life simultaneously, There is no known material applicable to the coating method (also called wet method).
Japanese Patent Laid-Open No. 5-271166 JP 2001-297882 A Japanese Patent Laid-Open No. 2003-73666 JP 2003-86371 A

  An object of the present invention is to provide an organic electroluminescence element having a high external extraction quantum efficiency and a long light emission lifetime, and further providing an illumination device and a display device including the organic electroluminescence element.

  The above object of the present invention has been achieved by the following configurations 1 to 22.

1. In an organic electroluminescence device having at least an anode and a cathode on a support substrate, and having at least one light emitting layer between the anode and the cathode,
Containing at least a part of the compound A having a partial structure and a reactive group represented by the following general formula (a), and containing a polymer obtained by polymerizing the compound A via the reactive group An organic electroluminescence device characterized by the above.

[Wherein, X represents O, S, CR′R ″ or SiR′R ″. R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring.]
2. 2. The organic electroluminescence device according to 1 above, wherein X represents O or S.

  3. 2. The organic electroluminescence device according to 1 above, wherein X represents O.

  4). 4. The organic electroluminescence device according to any one of 1 to 3 above, which is the Ar, carbazole ring, carboline ring or benzene ring.

  5. 5. The organic electroluminescence device according to any one of 1 to 4, wherein Ar is a benzene ring having a substituent.

  6). 6. The organic electroluminescence device according to any one of 1 to 5, wherein Ar is a benzene ring having a carbazolyl group.

  7). 7. The organic electroluminescence device according to any one of 1 to 6, wherein the general formula (a) is represented by the following general formula (a ′).

[Wherein, X represents O, S, CR′R ″ or SiR′R ″. R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring.]
8). 8. The organic electroluminescence device according to any one of 1 to 7, wherein the reactive group is represented by any one of the following general formulas (2) to (5).

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents one selected from a divalent linking group group consisting of the following general formulas (c), (d) and (e), or the divalent A group represented by a plurality of combinations of linking groups is represented. ]

[Wherein, R ₁ and R ₂ each represent a hydrogen atom or a methyl group, and Cy represents a 3-membered or 4-membered cyclic ether. n represents an integer of 1 or more. ]
9. 9. The organic electroluminescence device according to any one of 1 to 8, wherein the compound A or a polymer of the compound A is contained in a light emitting layer.

  10. 10. The organic electroluminescent element according to any one of 1 to 9, wherein the light emitting layer contains the polymer and a phosphorescent dopant.

  11. 11. The organic electroluminescence device according to any one of 1 to 10, wherein the polymer is a copolymer of the compound A and a phosphorescent dopant.

  12 12. The organic electroluminescence device according to 10 or 11, wherein the phosphorescent dopant is an Ir complex.

  13. The organic electroluminescence device according to any one of 10 to 12, wherein a 0-0 transition band of a phosphorescence wavelength of the phosphorescent dopant is 485 nm or less.

  14 14. The organic electroluminescence device as described in 13, wherein the phosphorescent dopant is a metal complex represented by the following general formula (1).

[In the formula, Z represents a hydrocarbon ring or a heterocyclic ring in which a substituent having a steric parameter value (Es value) of −0.5 or less is bonded to at least one of the third atoms counted from the nitrogen atom to be bonded. Represents. X and Y represent a carbon atom or a nitrogen atom, and A represents an atomic group necessary for forming a 5- or 6-membered hydrocarbon ring or heterocyclic ring together with X-C. B 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. X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ 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 X ₁ and X ₂ . m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3. M ₁ which is the central metal represents a group 8 to 10 metal in the periodic table. ]
15. 15. The organic electroluminescence device according to any one of 1 to 14, wherein the compound A or a polymer of the compound A has a 0-0 transition band of phosphorescence wavelength of 460 nm or less.

  16. 16. The organic electroluminescence device according to any one of 1 to 15, wherein the layer containing the compound A or the polymer of the compound A is formed by a wet method.

  17. The organic electroluminescence device according to any one of 1 to 16, wherein the compound A is polymerized after being applied.

  18. 18. The organic electroluminescent element according to any one of 1 to 17, wherein the constituent layer includes a plurality of organic compound layers.

  19. It has at least one anode buffer layer between the anode and the light emitting layer or at least one cathode buffer layer between the cathode and the light emitting layer, and at least one layer of the light emitting layer is 19. The organic electroluminescence device as described in any one of 1 to 18 above, which comprises a compound or a polymer of the compound, and the light emitting layer is formed by a wet method.

  20. 20. The organic electroluminescence device according to any one of 1 to 19, which emits white light.

  21. 21. A display device comprising the organic electroluminescence element according to any one of 1 to 20 above.

  22. 21. An illuminating device comprising the organic electroluminescent element according to any one of 1 to 20 above.

  According to the present invention, an organic electroluminescence element having a high external extraction quantum efficiency and a long emission lifetime can be provided, and a lighting device and a display device including the organic electroluminescence element can be provided.

The schematic block diagram of an organic electroluminescent full color display apparatus is shown. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Glass substrate 102 ITO transparent electrode 103 Partition 104 Hole injection layer 105B, 105G, 105R Light emitting layer 207 Glass substrate with a transparent electrode 206 Organic EL layer 205 Cathode 202 Glass cover 208 Nitrogen gas 209 Water capturing agent

  In the organic electroluminescent element (also referred to as an organic EL element) of the present invention, by having the configuration according to any one of claims 1 to 20, the external extraction quantum efficiency is high and the emission lifetime is long. An organic electroluminescence device was obtained.

  Moreover, it succeeded also in obtaining the high-intensity display apparatus and illuminating device which comprised the said organic electroluminescent element.

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

<< Compound A, polymer of the compound >>
The compound A according to the present invention and the polymer of the compound A will be described.

  In the present invention, the polymer obtained by polymerizing compound A only needs to contain compound A in part of the polymer, and compound A is polymerized via a reactive group (or polymerizable group). It is what you are doing.

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

  In addition, the compound A or the polymer of the compound A has a sufficiently wide band gap that can be used as a host for a blue phosphorescent dopant, has a high external extraction quantum efficiency, and has a long emission lifetime. A luminescence element can be provided, and further, an illumination device and a display device including the organic electroluminescence element can be provided.

  In the organic EL device of the present invention, it may be incorporated into the device in the state of Compound A, that is, the state before polymerization (also referred to as a monomer or a monomer), and prepared in advance as a polymer of Compound A. , And may be incorporated in a component layer of the element.

  In particular, when a component layer of an element is formed by a wet method such as coating, for example, when the compound A is incorporated as a monomer at the time of forming a light emitting layer, photopolymerization such as ultraviolet irradiation or heat generated by heating. It is preferable to provide an electron transport layer or the like on a light emitting layer obtained by forming a polymer through a step of performing polymerization or the like.

  On the other hand, it is also possible to incorporate the compound A according to the present invention into the constituent layer of the organic EL element of the present invention by vapor deposition or the like while maintaining the monomer (state before polymerization).

  In that case, after the organic EL element is formed, the compound A is polymerized by a polymerization reaction by active species generated by energization.

  It is also preferable to put a drying process before polymerization after preparing the coating film of Compound A and before polymerization, for example, heating at a temperature slightly higher than the boiling point of the coating solvent. Moreover, after polymerizing the coating film, it is also preferable to add a process such as rinsing the polymer film with an appropriate solvent (which does not dissolve the polymer film) to remove insoluble materials, and further laminating and coating the upper layer.

  By using the element in this way, when the polymerization reaction proceeds, it is possible to obtain an effect of improving the characteristics of the element, ie, extending the light emission lifetime.

  In the compound A having the partial structure and the reactive group represented by the general formula (a), examples of the reactive group include the following substituent groups, but are not limited thereto. Among them, preferable reactive substituents include substituents containing a carbon-carbon double bond, and more preferably vinyl groups. In addition, the compound A preferably has two or more reactive substituents.

  In addition, when the compound A has two or more reactive groups, the reactive groups may be the same or different.

  Compound A has a partial structure and a reactive group represented by the general formula (a), and X represents O, S, CR′R ″ or SiR′R ″, and more preferably O or S, particularly preferably X is O.

  In X of the general formula (a), as substituents represented by R ′ and R ″, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, Hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl group, 1-propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, isopropenyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic carbocyclic group, aryl group) 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, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group) , Triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one carbon atom constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) 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, hexyl) Oxy group, octyl Xyl group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group) Propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (Eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxy Carbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecyl) Aminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group ( For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonyl) Amino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group ( For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, Hexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethyl) Ureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido 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, naphthylsulfinyl group, 2-pyridyl Sulfinyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group etc.), arylsulfonyl group or heteroarylsulfonyl group (eg Phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, Anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, penta) Fluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphono group, etc. Is mentioned.

  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 (a), examples of the aromatic ring represented by Ar include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic ring may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent as described later.

  In the general formula (a), examples of the aromatic hydrocarbon ring represented by Ar include 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.

  In the general formula (a), examples of the aromatic heterocycle represented by Ar include a furan ring, a dibenzofuran ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. , Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole 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 of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), etc. Can be mentioned. These rings may further have a substituent.

  Among the above, in the general formula (a), the aromatic ring represented by Ar is preferably a carbazole ring, a carboline ring, a dibenzofuran ring, or a benzene ring, and particularly preferably used is a carbazole ring, A carboline ring or a benzene ring.

  Among the above, a benzene ring having a substituent is preferable, and a benzene ring having a carbazolyl machine is particularly preferable.

  Further, in the general formula (a), the aromatic ring represented by Ar is preferably a condensed ring having 3 or more rings, as shown below, and is an aromatic hydrocarbon condensed in which 3 or more rings are condensed. Specific examples of the ring include naphthacene ring, anthracene ring, tetracene ring, pentacene ring, hexacene ring, phenanthrene ring, pyrene ring, benzopyrene ring, benzoazulene ring, chrysene ring, benzochrysene ring, acenaphthene ring, acenaphthylene ring, triphenylene Ring, coronene ring, benzocoronene ring, hexabenzocoronene ring, fluorene ring, benzofluorene ring, fluoranthene ring, perylene ring, naphthoperylene ring, pentabenzoperylene ring, benzoperylene ring, pentaphen ring, picene ring, pyranthrene ring, coronene ring, Naphthocoronene ring, Ovalene ring, Ansula Ntoren ring and the like.

  In addition, these rings may further have a substituent.

  Specific examples of the aromatic heterocycle condensed with three or more rings include an acridine ring, a benzoquinoline ring, a carbazole ring, a carboline ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a carboline ring, a cyclazine ring, Kindin ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (any one of the carbon atoms constituting the carboline ring is a nitrogen atom Phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, benzodifuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, A Tiger thiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring, such as thio fan Tren ring (naphthaldehyde thiophene ring), and the like. In addition, these rings may further have a substituent.

  Here, in the general formula (a), the aromatic group represented by Ar may have a substituent represented by R ′ and R ″ in X of the general formula (1), respectively. It is synonymous.

  Moreover, it is preferable that the reactive group of the compound A which concerns on this invention is represented by either of the said General formula (2)-(5) as a preferable aspect. In addition, * shows the coupling | bonding position of a reactive group here.

In each of the general formulas (2) to (5), Q is one selected from the divalent linking group group consisting of the above general formulas (c), (d), and (e) or the divalent linking group. R, R ₁ and R ₂ each represent a hydrogen atom or a methyl group, and Cy represents a 3-membered or 4-membered cyclic ether. The 3-membered or 4-membered cyclic ether may have a substituent represented by R ′ and R ″ in X in the general formula (1).

<< Molecular Weight and Molecular Weight Distribution of Compound A Polymer (Mw / Mn) >>
The molecular weight (weight average molecular weight Mw) of the polymer of the compound A according to the present invention is preferably 1000000 or less, more preferably 10000 to 200000. Further, the ratio (molecular weight distribution) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) according to the present invention is preferably 3 or less.

  The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer of the compound A according to the present invention are measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a column solvent. It can be carried out.

  Moreover, about the molecular weight of the polymer obtained by compound A being incorporated in the light emitting layer of the organic EL element in the state before polymerization, and then energizing the organic EL element, and polymerization proceeding in the light emitting layer. In addition, a layer containing only Compound A is separately prepared in advance, and a plurality of samples (for example, about 10 samples) after photopolymerization in which the ultraviolet irradiation time is adjusted are prepared. The ultraviolet irradiation time and the molecular weight of the polymer (weight average) A calibration curve (number average molecular weight, etc.) is prepared in advance, and the molecular weight (weight average molecular weight, number average molecular weight or molecular weight distribution) can be determined from the ultraviolet irradiation time.

  On the other hand, the molecular weight of the polymer itself can be measured by a conventionally known method.

  Specifically, 1 ml of THF (using a degassed sample) is added to 1 mg of a measurement sample, and the sample is stirred using a magnetic stirrer at room temperature to be sufficiently dissolved. Subsequently, after processing with a membrane filter having a pore size of 0.45 μm to 0.50 μm, it is injected into a GPC (gel permeation chromatograph) apparatus.

  GPC measurement conditions are measured by stabilizing the column at 40 ° C., flowing THF (tetrahydrofuran) at a flow rate of 1 ml / min, and injecting about 100 μl of a sample having a concentration of 1 mg / ml.

  As the column, it is preferable to use a combination of commercially available polystyrene gel columns. For example, Shodex GPC KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko KK, TSKgel G1000H, G2000H, G3000H, G4000H, G5000H, G6000H, G7000H, TSK guard, etc. manufactured by Tosoh Corporation A combination of these is preferred.

  As the detector, a refractive index detector (RI detector) or a UV detector is preferably used. In the measurement of the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points are preferably used as polystyrene for preparing a calibration curve.

  In the present invention, the molecular weight was measured under the following measurement conditions.

(Measurement condition)
Equipment: Tosoh High Speed GPC Equipment HLC-8220GPC
Column: TOSOH TSKgel Super HM-M
Detector: RI and / or UV
Eluent flow rate: 0.6 ml / min Sample concentration: 0.1% by mass
Sample volume: 100 μl
Calibration curve: prepared with standard polystyrene: standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 100000 to 500-500 calibration curves (also referred to as calibration curves) were used to calculate the molecular weight. . It is preferable that the 13 samples are substantially equally spaced.

<< 0-0 Transition Band of Compound A or Polymer of Compound A >>
The compound A or the polymer of the compound A according to the present invention can be used in any of the constituent layers of the organic EL device of the present invention described later, but the effects described in the present invention (external extraction quantum efficiency From the viewpoint of improvement and longer life of the light emission), it is preferably contained in the light emitting layer.

  Moreover, the compound whose phosphorescence 0-0 transition band of the compound A concerning this invention or the polymer of this compound A is 460 nm or less is mentioned as a preferable compound.

  The method for measuring the 0-0 transition band will be described in detail in the light emitting dopant described later.

  Moreover, as such a luminescent dopant, the metal complex represented by the said General formula (1) is preferable. This will also be described later.

  Hereinafter, although the specific example of the compound A concerning this invention or the polymer of this compound A is shown, this invention is not limited to these.

  In addition, the compound A according to the present invention and the polymer of the compound A are synthesized by referring to the conventionally known documents described in New Polymer Experimental 2 Polymer Synthesis / Reaction (Kyoritsu Publishing Co., Ltd.), etc. I can do it.

<< 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. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode << organic compound layer (also referred to as 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 film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 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. 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.

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

  The light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). Light emitting host).

  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 2001-257076 A, JP 2002-308855 A, JP 2001-313179 A, 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 dopant)
The phosphorescent dopant according to the present invention will be described.

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

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

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

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

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

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

  Although the specific example of the compound used as a phosphorescent dopant below is shown, this invention is not limited to these. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like.

<< 0-0 transition band >>
In the phosphorescent dopant according to the present invention, the 0-0 transition band of the phosphorescent wavelength is preferably 485 nm or less, and the ionization potential of the phosphorescent dopant is preferably 5.5 eV or less.

(Measurement method of 0-0 transition band)
A method for measuring the 0-0 transition band of phosphorescence of the phosphorescent dopant according to the present invention will be described.

  First, a method for measuring a phosphorescence spectrum will be described.

  The compound to be measured (both phosphorescent dopant and host compound can be measured in the same manner) is dissolved in a well-deoxygenated mixed solvent of ethanol / methanol = 4/1 (vol / vol), and phosphorescence measurement is performed. After being put in the cell, excitation light is irradiated at a liquid nitrogen temperature of 77 ° K, and an emission spectrum at 100 ms is measured after the excitation light irradiation. Since phosphorescence has a longer emission lifetime than fluorescence, it can be considered that light remaining after 100 ms is almost phosphorescence.

  For compounds with a phosphorescence lifetime shorter than 100 ms, measurement may be performed with a shorter delay time, but phosphorescence and fluorescence cannot be separated if the delay time is shortened so that it cannot be distinguished from fluorescence. Since this is a problem, it is necessary to select a delay time that can be separated.

  In addition, for a compound that cannot be dissolved in the solvent system, any solvent that can dissolve the compound may be used (substantially, the solvent effect of the phosphorescence wavelength is negligible in the above measurement method).

  Next, the 0-0 transition band is obtained. In the present invention, the emission maximum wavelength appearing on the shortest wavelength side in the phosphorescence spectrum chart obtained by the measurement method is defined as the 0-0 transition band. To do.

  Since the phosphorescence spectrum is usually weak in intensity, it may be difficult to distinguish between noise and peak when enlarged. In such a case, the emission spectrum immediately after the excitation light irradiation (for convenience, this is referred to as a steady light spectrum) is expanded, and the emission spectrum 100 ms after the excitation light irradiation (for convenience, this is referred to as a phosphorescence spectrum) is superimposed on the phosphorous. It can be determined by reading the peak wavelength from the stationary light spectrum part derived from the light spectrum.

  Further, by performing a smoothing process on the phosphorescence spectrum, it is possible to separate the noise and the peak and read the peak wavelength. As the smoothing process, a smoothing method of Savitzky & Golay can be applied.

  The ionization potential (Ip) of the phosphorescent dopant according to the present invention is preferably 5.5 eV or less, more preferably 4.5 to 5.5 eV. Here, the ionization potential according to the present invention is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level. Energy) required to extract electrons from the compound in the (state), which can be directly measured by photoelectron spectroscopy. In the present invention, values measured with ESCA 5600 UPS (ultraviolet photoemission spectroscopy) manufactured by ULVAC-PHI Co., Ltd. are used.

  Moreover, as a preferable phosphorescence-emitting dopant in this invention, the metal complex represented by the said General formula (1) is preferable.

  Here, the metal complex represented by the general formula (1) will be described.

  In the general formula (1), Z is a hydrocarbon ring in which a substituent having a steric parameter value (Es value) of −0.5 or less is bonded to at least one of the third atoms counted from the bonding nitrogen atom. Alternatively, it represents a heterocyclic ring (including each tautomer). Here, the Es value is a steric parameter derived from chemical reactivity. The smaller this value, the more sterically bulky substituent can be said.

  Hereinafter, the Es value will be described. In general, in ester hydrolysis under acidic conditions, it is known that the influence of substituents on the progress of the reaction may only be considered as steric hindrance. The Es value is obtained by quantifying the steric hindrance.

The Es value of the substituent X is expressed by the following chemical reaction formula: X—CH ₂ COORX + H ₂ O → X—CH ₂ COOH + RXOH
The reaction rate constant kX for hydrolyzing an α-monosubstituted acetic acid ester derived from α-monosubstituted acetic acid in which one hydrogen atom of the methyl group of acetic acid is substituted with the substituent X represented by the formula And the following chemical reaction formula CH ₃ COORY + H ₂ O → CH ₃ COOH + RYOH
(RX is the same as RY) represented by the following formula from the reaction rate constant kH when the acetate corresponding to the α-monosubstituted acetate described above is hydrolyzed under acidic conditions.

Es = log (kX / kH)
The reaction rate decreases due to the steric hindrance of the substituent X, and as a result, kX <kH, so the Es value is usually negative. When the Es value is actually obtained, the above two reaction rate constants kX and kH are obtained and calculated by the above formula.

  Specific examples of Es values are given by Unger, S. et al. H. Hansch, C .; , Prog. Phys. Org. Chem. 12, 91 (1976). The specific numerical values are also described in “Structure-activity relationship of drugs” (Regional Chemistry Special Issue 122, Nankodo) and “American Chemical Society Reference Book, 'Exploring QSAR' p.81 Table 3-3”. There is. Next, a part is shown in Table 1.

  Here, it should be noted that the Es value as defined in this specification is not defined by defining that of a methyl group as 0, but by assuming that a hydrogen atom is 0, and an Es value where a methyl group is 0. Minus 1.24.

  In the present invention, the Es value is −0.5 or less. Preferably it is -7.0 or more and -0.6 or less. Most preferably, it is -7.0 or more and -1.0 or less.

  Here, in the present invention, when a steric parameter value (Es value) is −0.5 or less, for example, when keto-enol tautomers may exist in R and R ′, the keto moiety is enol. Es values are converted as isomers. Even when other tautomerism exists, the Es value is converted by the same conversion method. Furthermore, the substituent having an Es value of −0.5 or less is preferably an electron-donating substituent in terms of electronic effect.

  In the present invention, the electron-donating substituent is a substituent having a negative Hammett σp value as described below, and such a substituent has an electron on the bonding atom side compared to a hydrogen atom. Easy to give.

  Specific examples of the substituent exhibiting an electron donating property include a hydroxyl group, an alkoxy group (for example, methoxy group), an acetyloxy group, an amino group, a dimethylamino group, an acetylamino group, and an alkyl group (for example, methyl group, ethyl group). Group, propyl group, t-butyl group and the like) and aryl group (for example, phenyl group, mesityl group and the like). For the Hammett σp value, for example, the following documents can be referred to.

  The Hammett σp value according to the present invention refers to Hammett's substituent constant σp. Hammett's σp value is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the hydrolysis of ethyl benzoate. “Structure-activity relationship of drugs” (Nanedo: 1979), “Substituent” The groups described in “Constants for Correlation Analysis in Chemistry and Biology” (C. Hansch and A. Leo, John Wiley & Sons, New York, 1979) can be cited.

  Although the preferable example of Z in General formula (1) is given to the following, Z is not limited to these examples, and may have a substituent other than the following illustration. Note that * represents a bonding position.

In General formula (1), Y represents a carbon atom or a nitrogen atom, Preferably it is a carbon atom. B represents -C (R ₀₁ ) = C (R ₀₂ )-, -N = C (R ₀₂ )-, -C (R ₀₁ ) = N- or -N = N-.

  Preferred examples of the nitrogen-containing heterocyclic group containing Y include a 2-imidazolyl group, a 2- (1,3,4-triazolyl) group, a 2- (1,3,5-triazolyl) group, a 2-tetrazolyl group, and the like. Is mentioned. Of these nitrogen-containing heterocyclic groups, a 2-imidazolyl group is most preferred.

R ₀₁ and R ₀₂ represent a hydrogen atom or a substituent. Examples of substituents are alkyl groups (for example, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.) , A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), an aromatic hydrocarbon ring group (aromatic Also referred to as 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, Lysyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazole- 1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl Group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group , Phthalazinyl group, etc.) Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Etc.), cycloalkoxy groups (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy groups (eg phenoxy group, naphthyloxy group etc.), alkylthio groups (eg methylthio group, ethylthio group, propylthio group, pentylthio group) Hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group ( For example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (For example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl Group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl) Group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyl) Oxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, Cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino Group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, 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, octyl) Ureido group, dodecylureido group, phenylureido 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, naphthylsulfinyl 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 heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.) Amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecyl group) Mino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg 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 (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.) Can be mentioned. 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 hydrocarbon ring group or heterocyclic group represented by A-C-X in the general formula (1), X represents a carbon atom or a nitrogen atom, preferably a carbon atom.

When the hydrocarbon ring group represented by A-C-X is an aromatic hydrocarbon ring group, one hydrogen atom at an arbitrary position is removed from the 4n + 2π aromatic hydrocarbon compound, specifically Includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 1-anthryl group, a 9-phenanthryl group, a 2-triphenylenyl group, and a 3-perylenyl group. Further, the hydrocarbon ring group may be substituted with, for example, the substituent described in R ₀₁ , and further a condensed ring (for example, a 9-pyrenyl group obtained by condensing a hydrocarbon ring to a 9-phenanthryl group, a phenyl group) Or an 8-quinolyl group condensed with a heterocyclic ring.

When the heterocyclic group represented by A-C-X is an aromatic heterocyclic group, the aromatic heterocyclic group is a carbon atom in at least one adjacent position of the portion bonded to the nitrogen-containing aromatic heterocyclic ring, and Although there is no particular limitation as long as it is a 4n + 2π-type aromatic group, it is preferable that both adjacent positions of the portion bonded to the nitrogen-containing aromatic heterocyclic ring are carbon atoms. Specifically, 3-pyridyl group, 5-pyrimidyl group, 4-pyridazyl group, 5-pyridazyl group, 4-isoxazolyl group, 4-isothiazolyl group, 4-pyrazolyl group, 3-pyrrolo group, 3-furyl group, 3-thienyl group etc. are mentioned. Further, the heterocyclic ring may be substituted with, for example, the substituent described for R ₀₁ , and may further form a condensed ring.

In the general formula _{(1), X 1 -L1-} X 2 represents a bidentate ligand, X _1, X ₂ each independently represents a carbon atom, a nitrogen atom or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with X ₁ and X ₂ . Specific examples of the bidentate ligand represented by X ₁ -L ₁ -X ₂ include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, picolinic acid, etc. Is mentioned. m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3. Especially, the case where m2 is 0 is preferable.

In the general formula (1), M ₁ which is a central metal represents a group 8 to 10 metal in the periodic table, and among them, iridium or platinum is preferable.

  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.

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

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

  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 represented by lithium, alkali metal compound buffer layer represented by lithium fluoride, alkaline earth metal compound buffer layer represented by magnesium fluoride, oxide buffer layer represented 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 *. The reason why this calculated value is effective is that there is a high correlation between the calculated value obtained by this method and the experimental value.

  (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, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  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. it can. 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 substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

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

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 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, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

The sheet resistance as 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 emission luminance is advantageously improved.

  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.

An inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film, and the water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. And a relative humidity (90 ± 2)% RH) of 0.01 g / (m ² · 24 h) or less is preferable, and oxygen measured by a method according to JIS K 7126-1987. Transmittance is 10 ⁻³ cm ³ / (m ² · 24 h · M
Pa) or less, and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because the 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 element, or between the transparent electrode or the 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 of improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate and preventing total reflection at the transparent substrate and the air interface (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

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

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

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

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

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

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

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

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

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

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

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

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 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 / electron transport layer / electron injection layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate 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, an electron transport layer, an electron injection layer, and a hole blocking 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, a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a homogeneous film and a pinhole is generated. In view of difficulty, etc., film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.

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

  After these layers are formed, a thin film made of a cathode material is formed thereon by 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.

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

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

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

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

Example 1
<< Preparation of Organic EL Element 1-1 >>: Comparative Example A substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) in which ITO (indium tin oxide) was formed to a thickness of 100 nm 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. Then, the film was formed by spin coating and then dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound A0 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. Ultraviolet light was irradiated for 180 seconds, photopolymerization and crosslinking were performed, and a second hole transport layer having a thickness of about 25 nm was obtained.

  On this second hole transport layer, a solution obtained by dissolving 100 mg of Comparative Compound 1 and 10 mg of Compound 2-2 in 10 ml of toluene was formed into a film by a spin coating method at 1000 rpm for 30 seconds. Ultraviolet light was irradiated for 15 seconds, photopolymerization / crosslinking was performed, and further heating was performed in vacuum at 150 ° C. for 1 hour to obtain a light emitting layer having a film thickness of about 50 nm.

  Next, a solution obtained by dissolving 50 mg of tBu-PBD in 10 ml of toluene was formed on this light emitting layer by spin coating at 1000 rpm for 30 seconds, and vacuum-dried at 60 ° C. for 1 hour. The electron transport layer was 25 nm.

This was attached to a vacuum deposition apparatus, and then the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, lithium cathode 1.0 nm was deposited as a cathode buffer layer and aluminum 110 nm was deposited as a cathode to form a cathode, and an organic EL device 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-8 >>
In the production of the organic EL element 1-1, organic EL elements 1-2 to 1-8 were produced in the same manner except that the compounds shown in Table 2 were used as the comparative compound 1 and tBu-PBD.

<< Evaluation of organic EL elements >>
About the obtained organic EL elements 1-1 to 1-8, the external extraction quantum efficiency and the light emission lifetime were evaluated as follows.

《External extraction quantum efficiency》
About the produced organic EL element, the external extraction quantum efficiency (%) when a ^2.5 mA / cm ² constant current was applied in a dry nitrogen gas atmosphere at 23 ° C. was measured. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used.

  The obtained results are shown in Table 2. The measurement result of the external extraction quantum efficiency was expressed as a relative value when the measurement value of the organic EL element 1-1 was 100.

<Luminescent life>
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 ^1/2 ) As an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used. The obtained results are shown in Table 2. In addition, the measurement result of the light emission lifetime of Table 2 was represented by the relative value when the organic EL element 1-1 was set to 100.

  From Table 2, compared with each of the organic EL elements 1-3 to 1-8 of the present invention, both the external extraction quantum efficiency and the emission lifetime are remarkably better than those of the comparative organic EL element 1-1. I understand that.

  Moreover, in the comparative organic EL element 1-2 produced using the comparative compound 2 having no reactive group, the constituent components of the light emitting layer are eluted when the electron transport layer is applied, and the electron transport layer is formed. As a result, an organic element could not be produced.

  On the other hand, each of the organic EL elements 1-3 to 1-9 of the present invention can be laminated by a coating method because an organic thin film having a high crosslinking resistance and a crosslinking density can be formed. In addition, in terms of device performance, it was possible to obtain a device having a high emission efficiency and a long emission lifetime.

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

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

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound A0 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. Ultraviolet light was irradiated for 180 seconds, photopolymerization and crosslinking were performed, and a second hole transport layer having a thickness of about 25 nm was obtained.

  On this second hole transport layer, a solution prepared by dissolving 50 mg of polyvinylcarbazole and 5 mg of Ir-1 in 10 ml of dichloroethane was deposited by spin coating at 1000 rpm for 30 seconds to form a light emitting layer.

Next, this substrate is attached to a vacuum deposition apparatus, and then 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, Organic EL element 2-1 was produced.

<< Production of Organic EL Element 2-2 >>
In the production of the organic EL element 2-1, 2-2 was produced by the same method as the organic EL element 2-1, except that polyvinyl carbazole was replaced with the compound 1-22 (using a polymer of n = 22000).

<< Evaluation of organic EL elements >>
The organic EL elements 2-1 and 2-2 produced as follows are evaluated, and the results are shown below.

《External extraction quantum efficiency》
About the produced organic EL element, the external extraction quantum efficiency (%) when a ^2.5 mA / cm ² constant current was applied in a dry nitrogen gas atmosphere at 23 ° C. was measured. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used in the same manner.

  The measurement result of the external extraction quantum efficiency was expressed as a relative value when the measurement value of the organic EL element 2-1 was 100.

<Luminescent life>
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 ^1/2 ) As an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used. The measurement result of the lifetime was expressed as a relative value when the organic EL element 2-1 was set to 100.

  The results obtained are shown below.

Organic EL element No. External extraction quantum efficiency Luminescence lifetime Remarks 2-1 100 100 Comparison 2-2 132 1350 Invention From the above, Compound 1-22 (a repeating unit of a carbazole ring, which is an embodiment of the polymer of Compound A according to the present invention) The organic EL device 2-2 of the present invention containing a dibenzofuran ring as a partial structure) has a significantly improved external extraction quantum efficiency and emission lifetime as compared with the comparative organic EL device 2-1. I understand.

Example 3
<< Production of organic EL full-color display device >>
FIG. 1 shows a schematic configuration diagram of an organic EL full-color display device. After patterning at a pitch of 100 μm on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) having a 100 nm thick ITO transparent electrode (102) formed on a glass substrate 101 as an anode, non-between the ITO transparent electrodes on this glass substrate. A photosensitive polyimide partition 103 (width 20 μm, thickness 2.0 μm) was formed by photolithography.

  A hole injection layer composition having the following composition is ejected and injected between polyimide partition walls on the ITO electrode using an inkjet head (manufactured by Epson Corporation; MJ800C), irradiated with ultraviolet light for 30 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, irradiated with ultraviolet light for 30 seconds, 60 Drying treatment was performed at a temperature of 10 ° C. for 10 minutes to form respective light emitting layers (105B, 105G, 105R). Finally, Al (106) was vacuum-deposited as a cathode so as to cover the light emitting layer 105, and an organic EL element was produced.

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

(Hole injection layer composition)
Compound A0 20 parts by mass Cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass (Blue light emitting layer composition)
Compound 1-26 0.7 parts by mass Ir-15 0.04 parts by mass Cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass (green light emitting layer composition)
Compound 1-26 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)
Compound 1-26 0.7 parts by mass Ir-14 0.04 parts by mass Cyclohexylbenzene 50 parts by mass Isopropylbiphenyl 50 parts by mass Also, instead of Ir-15, Ir-1, Ir-14, compounds 2-1-2- 16 is the same in an organic EL device prepared by using Compound 1-1 to 1-7, 1-25 or Compound 1-8 to 1-23, 1-27 to 1-35 instead of Compound 1-26. It can be used as a full-color display device.

Example 4
<< Preparation of white organic EL element 4-1 >>
After patterning on a substrate (NH-Techno Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

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

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of compound A0 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to carry out photopolymerization / crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.

  Next, spin coating was performed under the conditions of 1000 rpm and 30 seconds using a solution in which compound 1-26 (60 mg), compound 2-6 (3.0 mg) and compound 2-7 (3.0 mg) were dissolved in 6 ml of toluene. The film was formed by the method. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization / crosslinking, and further heated in vacuum at 150 ° C. for 1 hour to obtain a light emitting layer.

  Further, a film in which Compound B (20 mg) was dissolved in 6 ml of toluene was used, and a film was formed by spin coating under conditions of 1000 rpm and 30 seconds. Ultraviolet light was irradiated for 15 seconds, photopolymerization / crosslinking was performed, and further heating was performed in vacuum at 80 ° C. for 1 hour to form a hole blocking layer.

Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of Alq ₃ was placed in a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus. After reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing Alq ₃ was heated by heating, evaporated onto the electron transport layer at a deposition rate of 0.1 nm / second, and further coated with a film. An electron transport layer having a thickness of 40 nm was provided.

  In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element 4-1 was produced.

  When this element 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 with the other compound of illustration.

Example 5
<< Preparation of Organic EL Element 5-1 >>: 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 of the present invention. 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) -polystyrenesulfonate (PEDOT / PSS, Baytron, Baytron P Al 4083) to 70% by mass with pure water at 3000 rpm, 30 After forming a film by spin coating in seconds, the film was dried at 200 ° C. for 1 hour to provide a hole injection / transport layer having a thickness of 30 nm.

  On this hole injecting / transporting layer, a solution prepared by dissolving 30 mg of compound 1-37 in 3 ml of toluene was formed into a film by spin coating under conditions of 1000 rpm and 30 seconds, and vacuum-dried at 60 ° C. for 1 hour, A light emitting layer having a thickness of 80 nm was formed.

This was attached to a vacuum deposition apparatus, and then the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, calcium 10 nm as a cathode buffer layer and aluminum 110 nm as a cathode were deposited to form a cathode, and the organic EL element 5-1 was formed. Produced.

<< Preparation of Organic EL Element 5-2 >>: Comparative Example Organic EL element was manufactured in the same manner as in the preparation of organic EL element 5-1, except that 3 ml of the solution of compound 1-37 was replaced with the following solution [A]. Element 5-2 was produced.

(Preparation of solution [A])
A solution prepared by dissolving 30 mg of polyvinylcarbazole (also referred to as PVCz) and 1.5 mg of Ir-13 (blue light-emitting orthometalated complex), which are conventionally known light-emitting layer forming materials, in 3 ml of toluene << Organic EL element 5 Evaluation of -1 to 5-2 >>
When evaluating the obtained organic EL elements 5-1 to 5-2, the non-light-emitting surface of each organic EL element after fabrication is covered with a glass case, and a glass substrate having a thickness of 300 μm is 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. 2 and 3 was formed and evaluated.

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

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

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

《External extraction quantum efficiency》
About the produced organic EL element, the external extraction quantum efficiency (%) when a ^2.5 mA / cm ² constant current was applied in a dry nitrogen gas atmosphere at 23 ° C. was measured. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used.

<Luminescent life>
When driving at a constant current of ^2.5 mA / cm ^{2 in} a dry nitrogen gas atmosphere at 23 ° C., the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured. Was used as an index of life as half-life time (τ ^1/2 ). For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used in the same manner.

  The measurement results of the external extraction quantum efficiency and the light emission lifetime of the organic EL elements 5-1 to 5-2 were evaluated relative to the data of the organic EL element 5-2 as 100.

  The results obtained are shown below.

Organic EL Light emitting layer External extraction Luminous life Luminous color Remarks Element No. Forming material Quantum efficiency (%)
(Relative value)
5-1 1-37 143 150 Blue Invention 5-2 PVCz 100 100 Blue Comparative Example
+ Ir-13
From the above evaluation results, it is clear that the organic EL element 5-1 of the present invention has significantly improved external extraction quantum efficiency, reduced power consumption, and improved light emission lifetime as compared with the comparison. .

Claims (22)

In an organic electroluminescence device having at least an anode and a cathode on a support substrate, and having at least one light emitting layer between the anode and the cathode,
Containing at least a part of the compound A having a partial structure and a reactive group represented by the following general formula (a), and containing a polymer obtained by polymerizing the compound A via the reactive group An organic electroluminescence device characterized by the above.

[Wherein, X represents O, S, CR′R ″ or SiR′R ″. R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring.] The organic electroluminescence device according to claim 1, wherein X represents O or S. 2. The organic electroluminescence element according to claim 1, wherein X represents O. The organic electroluminescence device according to any one of claims 1 to 3, wherein the organic electroluminescence device is the Ar, a carbazole ring, a carboline ring, or a benzene ring. The organic electroluminescent element according to any one of claims 1 to 4, wherein Ar is a benzene ring having a substituent. The organic electroluminescent element according to any one of claims 1 to 5, wherein Ar is a benzene ring having a carbazolyl group. The organic electroluminescent element according to any one of claims 1 to 6, wherein the general formula (a) is represented by the following general formula (a ').

[Wherein, X represents O, S, CR′R ″ or SiR′R ″. R ′ and R ″ each represent a hydrogen atom or a substituent. Ar represents an aromatic ring.] The organic electroluminescence device according to any one of claims 1 to 7, wherein the reactive group is represented by any one of the following general formulas (2) to (5). .

[Wherein, R represents a hydrogen atom or a methyl group, and Q represents one selected from a divalent linking group group consisting of the following general formulas (c), (d) and (e), or the divalent A group represented by a plurality of combinations of linking groups is represented. ]

[Wherein, R ₁ and R ₂ each represent a hydrogen atom or a methyl group, and Cy represents a 3-membered or 4-membered cyclic ether. n represents an integer of 1 or more. ] The organic electroluminescence device according to any one of claims 1 to 8, wherein the compound A or a polymer of the compound A is contained in a light emitting layer. The organic light-emitting device according to any one of claims 1 to 9, wherein the light-emitting layer contains the polymer and a phosphorescent dopant. The organic electroluminescence device according to any one of claims 1 to 9, wherein the polymer is a copolymer of the compound A and a phosphorescent dopant. The organic electroluminescence device according to claim 10 or 11, wherein the phosphorescent dopant is an Ir complex. The organic electroluminescence device according to any one of claims 10 to 12, wherein a 0-0 transition band of a phosphorescence wavelength of the phosphorescent dopant is 485 nm or less. The organic electroluminescent device according to claim 13, wherein the phosphorescent dopant is a metal complex represented by the following general formula (1).

[In the formula, Z represents a hydrocarbon ring or a heterocyclic ring in which a substituent having a steric parameter value (Es value) of −0.5 or less is bonded to at least one of the third atoms counted from the nitrogen atom to be bonded. Represents. X and Y represent a carbon atom or a nitrogen atom, and A represents an atomic group necessary for forming a 5- or 6-membered hydrocarbon ring or heterocyclic ring together with X-C. B 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. X ₁ -L ₁ -X ₂ represents a bidentate ligand, and X ₁ and X ₂ 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 X ₁ and X ₂ . m1 represents an integer of 1, 2 or 3, m2 represents an integer of 0, 1 or 2, and m1 + m2 is 2 or 3. M ₁ which is the central metal represents a group 8 to 10 metal in the periodic table. ] The organic electro according to any one of claims 1 to 14, wherein the compound A or a polymer of the compound A has a 0-0 transition band of phosphorescence wavelength of 460 nm or less. Luminescence element. 16. The organic electroluminescence device according to claim 1, wherein the layer containing the compound A or the polymer of the compound A is formed by a wet method. The organic electroluminescence device according to any one of claims 1 to 16, wherein the compound A is polymerized after being applied. The organic electroluminescent element according to any one of claims 1 to 17, wherein the organic electroluminescent element has a plurality of organic compound layers as a constituent layer. It has at least one anode buffer layer between the anode and the light emitting layer or at least one cathode buffer layer between the cathode and the light emitting layer, and at least one layer of the light emitting layer is 19. The organic electroluminescence device according to claim 1, comprising a compound or a polymer of the compound, and the light emitting layer is formed by a wet method. . The organic electroluminescence element according to any one of claims 1 to 19, wherein the organic electroluminescence element emits white light. A display device comprising the organic electroluminescence element according to any one of claims 1 to 20. An illuminating device comprising the organic electroluminescent element according to any one of claims 1 to 20.