WO2010004887A1 - Élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairement et matière d'élément électroluminescent organique - Google Patents

Élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairement et matière d'élément électroluminescent organique Download PDF

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WO2010004887A1
WO2010004887A1 PCT/JP2009/061731 JP2009061731W WO2010004887A1 WO 2010004887 A1 WO2010004887 A1 WO 2010004887A1 JP 2009061731 W JP2009061731 W JP 2009061731W WO 2010004887 A1 WO2010004887 A1 WO 2010004887A1
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大 池水
栄作 加藤
智寛 押山
雅人 西関
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コニカミノルタホールディングス株式会社
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Definitions

  • the present invention relates to an organic electroluminescence element, a display device, a lighting device, and an organic electroluminescence element material.
  • ELD electroluminescence display
  • 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.
  • an organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them.
  • It is an element that emits light by using light emission (fluorescence / phosphorescence) when the 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.
  • a small amount of a phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to achieve improvement in light emission luminance and a longer device lifetime.
  • an element having an organic light-emitting layer in which 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped to the host compound for example, Japanese Patent Laid-Open No. 63-264692
  • 8-hydroxyquinoline aluminum complex is used as a host compound.
  • an element having an organic light emitting layer doped with a quinacridone dye for example, JP-A-3-255190 is known.
  • the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of luminescent excited species is 25%. Since the efficiency is about 20%, the limit of the external extraction quantum efficiency ( ⁇ ) is set to 5%.
  • the upper limit of the internal quantum efficiency is 100%.
  • the luminous efficiency is four times that of the excited singlet, and there is a possibility that almost the same performance as a cold cathode tube can be obtained. Therefore, it is attracting attention as a lighting application.
  • Ikai et al Uses a hole transporting compound as a host of a phosphorescent compound.
  • M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.
  • the light emission brightness and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element.
  • wavelength shortening introduction of an electron withdrawing group such as a fluorine atom, a trifluoromethyl group, a cyano group or the like into phenylpyridine as a substituent, and picolinic acid or a pyrazabole-based ligand as a ligand. It is known to introduce.
  • an electron withdrawing group such as a fluorine atom, a trifluoromethyl group, a cyano group or the like into phenylpyridine as a substituent, and picolinic acid or a pyrazabole-based ligand as a ligand. It is known to introduce.
  • the emission wavelength of the light-emitting material is shortened to achieve blue, and a high-efficiency device can be achieved.
  • the light-emitting lifetime of the device is greatly deteriorated, so an improvement in the trade-off is required. It was.
  • a metal complex having phenylpyrazole as a ligand is a light emitting material having a short emission wavelength (see, for example, Patent Documents 1 and 2). Furthermore, a metal complex formed from a ligand having a partial structure in which a 6-membered ring is condensed to a 5-membered ring of phenylpyrazole is disclosed (for example, see Patent Documents 3 and 4). There is a disclosure about a metal complex having a phenanthridine skeleton (see, for example, Patent Documents 5 and 6).
  • triarylamine compounds are known as good hole transport materials, and examples of combined use of the above-mentioned compounds having a phenanthridine skeleton and ⁇ -NPD are disclosed.
  • the present invention has been made in view of such problems, and an object of the present invention is to provide an organic electroluminescence element material that exhibits specific short-wave emission, exhibits high emission efficiency, and has a long emission lifetime.
  • An organic EL element, a lighting device, and a display device In particular, it is to provide an organic electroluminescence device material which exhibits high luminous efficiency with a short wavelength light emission of blue to blue green, a low driving voltage, and a long emission lifetime.
  • the light emitting layer is a partial structure represented by the following general formula (1), (2), (3) or (4) And an organic layer containing at least one compound represented by the following general formula (5).
  • E1a to E1q represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and the skeleton composed of E1a to E1q has a total of 18 ⁇ electrons.
  • E1a and E1p are different from each other, and are each a carbon atom or a nitrogen atom.
  • R1a to R1i each represents a hydrogen atom or a substituent, and M represents a group 8-10 transition metal element in the periodic table.
  • R 1 to R 10 each represents a hydrogen atom or a substituent
  • A represents an alkyl group, an aromatic hydrocarbon ring group, or an aromatic heterocyclic group.
  • M represents an integer of 1 to 4)
  • R 1 to R 20 each represents a hydrogen atom or a substituent
  • B represents a linking group composed of an alkyl group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • M and p are 1) Represents an integer of ⁇ 2.
  • 3. 3 The organic electroluminescence device according to 2 above, wherein the linking group represented by B in the general formula (6) is an aromatic heterocyclic group or an aromatic heterocyclic group.
  • the linking group represented by B in the general formula (6) is a phenyl group, a biphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group or an anthracenyl group, 3.
  • R1a and R1b represents a substituent, Organic electroluminescent element of any one of these.
  • R1a or R1b is represented by the following general formula (1A), 9.
  • Z represents a 5- or 6-membered aromatic hydrocarbon group or aromatic heterocyclic group
  • A represents a nitrogen atom or a carbon atom
  • Ra represents a steric parameter value (Es value) of ⁇ 0.5).
  • Rb represents a hydrogen atom or a substituent
  • n represents an integer of 1 to 4. 11.
  • Ra represents a substituent having a steric parameter value (Es value) of ⁇ 0.5 or less.
  • Rb represents a hydrogen atom or a substituent, and n represents an integer of 1 to 4.
  • Ra and Rc represent a substituent having a steric parameter value (Es value) of ⁇ 0.5 or less.
  • Rb represents a hydrogen atom or a substituent, and n represents an integer of 1 to 4.
  • 13 As a constituent layer, it has an organic layer containing at least one compound containing a partial structure represented by any one of the general formulas (1) to (4) described in 1 above, and the organic layer is formed using a wet process. 13.
  • a constituent layer it has an organic layer containing at least one compound represented by the general formula (5) or (6) described in any one of the above 1 to 7, and the organic layer is formed using a wet process. 14.
  • the organic layer containing at least one compound represented by the general formula (5) or (6) described in any one of the above 1 to 7 as a constituent layer is a hole transport layer, 14.
  • a display device comprising the organic electroluminescence element according to any one of 1 to 17 above.
  • An illuminating device comprising the organic electroluminescence element as described in any one of 1 to 17 above.
  • An organic electroluminescence device material which is a compound including a partial structure represented by any one of the general formulas (1) to (4) described in 1 above.
  • 21 The organic electroluminescent element material as described in 20 above, wherein M in the general formulas (1) to (4) is platinum or iridium.
  • the present invention it was possible to provide an organic electroluminescence device that showed specific short-wave light emission, high light emission efficiency, low driving voltage, and long light emission lifetime. Further, as a result of the study by the present inventors, the present invention can greatly reduce the initial deterioration during device driving, and has succeeded in greatly reducing the dark spots of the light emitting device.
  • An EL element could be provided.
  • an illumination device and a display device using the element could be provided.
  • the organic electroluminescent element of the present invention has the structure defined in any one of claims 1 to 13 and exhibits a high luminous efficiency and a long emission lifetime, and an illumination device using the element And a display device could be provided.
  • the present inventors have succeeded in molecular design of an organic EL element material useful for the organic electroluminescence element of the present invention.
  • the organic electroluminescence device material of the present invention was observed to emit light with a specific short wave, and the lifetime of the organic electroluminescence device of the present invention could be remarkably improved.
  • Metal complex also called metal complex compound
  • the present inventors focused on the organic EL element material used for the light emitting layer of the organic EL element, and in particular, studied various metal complex compounds used as the light emitting dopant.
  • the present inventors do not use a conventionally known approach of introducing a substituent into the basic skeleton of a metal complex to control the wavelength or improve the lifetime, but expanding the ⁇ -conjugated surface of the condensed ring can stabilize the compound.
  • Various complexes were examined under the focus of increasing the properties. As a result, the improvement tendency of lifetime was found in several condensed ring structures. However, when a fused ring as known so far is introduced, the red shift of the emission wavelength is remarkable, resulting in green and red emission.
  • the present inventors have further studied, and compounds (metal complex, metal having introduced a condensed ring as shown in the partial structure represented by any one of the general formulas (1) to (4) according to the present invention.
  • a complex compound metal having introduced a condensed ring as shown in the partial structure represented by any one of the general formulas (1) to (4) according to the present invention.
  • a complex compound is applied to a light emitting material, a light emitting dopant having a small emission wavelength shift and a long lifetime at a desired emission wavelength has been successfully developed.
  • R1a in a transition metal complex compound containing at least one substituent in the ligand portion particularly a partial structure represented by any one of the general formulas (1) to (4) according to the present invention.
  • R1b it has been found that by introducing a substituent into R1b, the oxidative degradation is greatly reduced and the stability of the compound is greatly improved.
  • the metal complex compound including the partial structure represented by any one of the general formulas (1) to (4) according to the present invention has a plurality of ligands depending on the valence of the transition metal element represented by M.
  • the ligands may all be the same or may have ligands each having a different structure.
  • the ligand is a portion obtained by removing the transition metal element M from the partial structure represented by any one of the general formulas (1) to (4).
  • the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.
  • ligands used in conventionally known metal complexes.
  • ligands eg, halogen ligands (preferably chlorine ligands), etc., published in 1987, published by Yersin, “Organometallic Chemistry-Fundamentals and Applications-” Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands).
  • Transition metal elements of groups 8 to 10 of the periodic table As a metal used for forming a compound (also referred to as a transition metal complex, a metal complex, or a metal complex compound) containing a partial structure represented by any one of the general formulas (1) to (4) according to the present invention, an element is Transition metal elements belonging to Group 8 to 10 of the periodic table (also simply referred to as transition metals) are used. Among them, iridium and platinum are preferable transition metal elements.
  • the layer containing the metal complex compound containing the partial structure represented by any one of the general formulas (1) to (4) according to the present invention is not particularly limited as long as it is a layer that transports charges (charge transport layer).
  • a hole transport layer or a light emitting layer, a light emitting layer or an electron blocking layer is preferable, a light emitting layer or an electron blocking layer is more preferable, and a light emitting layer is particularly preferable.
  • the efficiency improvement (high brightness) of the external extraction quantum efficiency of the organic EL element of this invention and the lifetime improvement of a light emission lifetime are achieved. be able to.
  • the constituent layers of the organic EL element of the present invention will be described in detail later.
  • Partial structure represented by any one of general formulas (1) to (4) >> The partial structure represented by any one of the general formulas (1) to (4) according to the present invention will be described.
  • the ring formed by E1a to E1e represents a 5-membered aromatic heterocycle, such as an oxazole ring, a thiazole ring, or an oxadiazole
  • examples include a ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, a thiatriazole ring, an isothiazole ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, and a triazole ring.
  • a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring are preferable, and a pyrazole ring and an imidazole ring are particularly preferable.
  • Each of these rings may further have a substituent described later.
  • the ring formed by E1f to E1k is a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle Represents.
  • Examples of the 6-membered aromatic hydrocarbon ring formed by E1f to E1k include a benzene ring. Furthermore, you may have the substituent mentioned later.
  • Examples of the 5- or 6-membered aromatic heterocycle formed by E1f to E1k include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. Can be mentioned. Each of these rings may further have a substituent described later.
  • the ring formed by E1l to E1q is a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle
  • These rings are each synonymous with a 6-membered aromatic hydrocarbon ring formed by E1f to E1k, or a 5-membered or 6-membered aromatic heterocycle.
  • each of the substituents represented by R1a to R1i includes an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg, vinyl group, Allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chloropheny
  • a plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. It may be formed.
  • the substituents represented by R1a to R1i are styryl group, epoxy group, oxetanyl group, acrylic group in addition to the alkenyl group described above. , And may have a polymerizable group such as a tacryl group. Furthermore, the compound represented by the partial structure represented by any one of the general formulas (1) to (4) can react with the polymerizable groups or other polymerizable monomers to form a polymer. .
  • the partial structures represented by any one of the general formulas (1) to (4) may be the same or different.
  • R1a or R1b is preferably an alkyl group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group
  • a more preferred form of the aromatic hydrocarbon ring group and the aromatic heterocyclic group is a group represented by the general formula (1A), more preferably a group represented by the general formula (2A), and particularly preferred.
  • the substituent represented by Rb has the same meaning as the substituents represented by R1a to R1i in the partial structure represented by the general formula (1) or (2).
  • a substituent having a steric parameter value (Es value) represented by Ra of ⁇ 0.5 or less will be described in detail below.
  • the substituent is preferably bonded to an atom adjacent to A constituting a 6-membered aromatic hydrocarbon ring or a 5-membered to 6-membered aromatic heterocycle formed by the Z. Furthermore, this is preferably an electron donating group which will be described in detail below.
  • the Es value is a steric parameter derived from chemical reactivity. The smaller this value, the more sterically bulky substituent can be said.
  • 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
  • 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.
  • the above two reaction rate constants kX and kH are obtained and calculated by the above formula.
  • Es values include Unger, S. H. Hansch, C .; , Prog. Phys. Org. Chem. 12, 91 (1976). Also, the specific numerical values are described in “Structure-activity relationship of drugs” (Chemical domain extra number 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.
  • 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.
  • the Es value according to the present invention is ⁇ 0.5 or less. Preferably, it is -7.0 to -0.6. Most preferably, it is -7.0 to -1.0.
  • a substituent having a steric parameter value (Es value) of ⁇ 0.5 or less for example, a keto-enol tautomer may exist in Z
  • the keto moiety is an Esol isomer as Es.
  • the value is converted. Even when other tautomerism exists, the Es value is converted by the same conversion method.
  • the substituent having an Es value of ⁇ 0.5 or less is preferably an electron-donating substituent in terms of electronic effect.
  • the electron-donating substituent is a substituent having a negative Hammett ⁇ p value as described below, and such a substituent has an electron on the bonding atom side compared to a hydrogen atom. Easy to give.
  • substituent exhibiting an electron donating property examples include a hydroxy group, a thiol group, an alkoxy group (for example, methoxy group), an alkylthio group, an arylthio group, an acetyloxy group, an amino group, a dimethylamino group, an acetylamino group, Examples thereof include an alkyl group (for example, methyl group, ethyl group, propyl group, t-butyl group) and an aryl group (for example, phenyl group, mesityl group, etc.).
  • alkyl group for example, methyl group, ethyl group, propyl group, t-butyl group
  • aryl group for example, phenyl group, mesityl group, etc.
  • the Hammett ⁇ p value according to the present invention refers to Hammett's substituent constant ⁇ p.
  • Hammett's ⁇ p 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.
  • the group represented by the general formula (2A) is preferable.
  • the substituent represented by Rb has the same meaning as the substituents represented by R1a to R1i in the partial structure represented by the general formula (1) or (2).
  • the substituent represented by Rb has the same meaning as the substituents represented by R1a to R1i in the partial structure represented by the general formula (1) or (2).
  • the polymer (polymer) of the partial structure represented by any one of the general formulas (1) to (4) is “Revised Polymer Synthesis Chemistry” Chemistry “Polymer Synthesis Experimental Method” Chemistry Doujin “4th Edition Experiment It can be synthesized using the method described in Chemistry Lecture 28 “Polymer Synthesis” Maruzen et al.
  • Preferred polymerization methods include 1) polycondensation, 2) radical polymerization, 3) ionic polymerization, 4) polyaddition, addition condensation, etc., which can be used properly depending on the type of polymerizable group.
  • the polymer having a partial structure represented by any one of the general formulas (1) to (4) can be made into a homopolymer using the above method, or can be made into a copolymer in combination with a plurality of monomers. is there.
  • Step 1 Synthesis of complex C
  • 0.9 g (0.003875 mol) of 2-methylimidazo [1,2-f] phenanthridine, 13 ml of 2-ethoxyethanol, and 3 ml of water were blown with nitrogen.
  • a tube, a thermometer and a condenser were attached and set on an oil bath stirrer.
  • 0.55 g (0.001560 mol) of IrCl 3 3H 2 O and 0.16 g (0.001560 mol) of triethylamine were added, and the mixture was boiled and refluxed at an internal temperature of about 100 ° C. for 6 hours to complete the reaction. It was.
  • Step 2 Synthesis of Complex D
  • 1.0 g (0.0007244 mol) of Complex C 0.29 g of acetylacetone, 1.0 g of sodium carbonate, and 24 ml of 2-ethoxyethanol were introduced, and nitrogen was blown into the flask.
  • a tube, a thermometer and a condenser were attached and set on an oil bath stirrer. The mixture was heated and stirred for 1.5 hours at a nitrogen gas stream inner temperature of around 80 ° C.
  • reaction solution was cooled to room temperature, methanol was added to the reaction solution, and the precipitated crystals were filtered. The crystals were washed with 30 ml of water and 10 ml of MeOH and dried to obtain 0.73 g of Complex D, 0.42 g (38.5%).
  • Step 3 Synthesis of Exemplary Compound A-97
  • 0.386 g (0.0005120 mol) of Complex D 0.357 g of 2-methylimidazo [1,2-f] phenanthridine, glycerin 20 ml was added, and a nitrogen blowing tube, a thermometer, and an air cooling tube were attached and set on an oil bath stirrer.
  • the reaction was completed by heating and stirring for 4.5 hours at an internal temperature of 150 ° C. under nitrogen flow. After completion of the reaction, the mixture was cooled to room temperature, methanol was added and dispersed, and the crystals were collected by filtration to obtain 0.38 g of crude crystals.
  • Exemplified Compound A-97 was confirmed using 1H-NMR (nuclear magnetic resonance spectrum). Measurement conditions, chemical shift of each peak of the obtained spectrum, proton number, etc. are shown below.
  • R 1 to R 10 each represent a hydrogen atom or a substituent.
  • Examples of the substituent represented by R 1 to R 10 include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group).
  • an alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group.
  • Aromatic hydrocarbon ring group also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, Fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.) Group heterocyclic group (for example, pyridyl group, pyrimi
  • Ruamino group dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, diphenylamino group, phenylnaphthylamino group, etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon Group (for example, 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.), phosphono group and the like. These substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. It may be formed.
  • A is an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, Pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group , Tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyren
  • alkyl group
  • m represents an integer of 1 to 4.
  • R 1 to R 20 each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5).
  • B represents a linking group composed of an alkyl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group. Examples of the alkyl group, the aromatic hydrocarbon ring group, and the aromatic heterocyclic group Is synonymous with the description in the general formula (5). These substituents may be further substituted with the above substituents.
  • the linking group composed of an alkyl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group each may have one substituent as a linking group, and may be a plurality of alkyl groups, aromatic hydrocarbon groups, aromatic groups.
  • Group heterocyclic groups may be connected to each other.
  • the connecting groups formed by connecting may be the same or different.
  • the linking group may be substituted with a substituent in the general formula (5), and may be linked to each other to form a ring.
  • the linking group represented by B is preferably a phenyl group, a biphenyl group, a terphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, or an anthracenyl group.
  • the molecular weight of the linking group represented by B is preferably 180 or more and 500 or less. More preferably, it is 180-300.
  • the molecular weight of the linking group is (molecular weight of the linking group itself ⁇ (m + p)).
  • m and p each represents an integer of 1 to 2.
  • the glass transition temperature of the compound represented by the general formula (5) or (6) is preferably 100 ° C. or higher and lower than 400 ° C. More preferably, it is 100 degreeC or more and less than 350 degreeC.
  • the glass transition temperature (also referred to as glass transition point) according to the present invention can be determined using a commercially available DSC (Differential Scanning Calorimetry) measuring device.
  • the molecular weight of the compound represented by the general formula (5) or (6) is preferably 600 or more and less than 2000. However, when the compound represented by the general formula (5) or (6) forms a polymer, the molecular weight of the monomer is preferably 600 or more and less than 2000.
  • R 1 to R 15 each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5).
  • Each substituent may be the same or different.
  • each substituent may be further substituted with the substituent in General formula (5).
  • each adjacent substituent may be linked to each other to form a ring.
  • R 1 to R 20 each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5).
  • Each substituent may be the same or different.
  • Each substituent may be further substituted with a substituent in the general formula (5). Further, each adjacent substituent may be linked to each other to form a ring.
  • Ar 1 and Ar 2 represent an aromatic hydrocarbon ring group and an aromatic heterocyclic group, and examples of the aromatic hydrocarbon ring group and the aromatic heterocyclic group are explained in the general formula (5). It is synonymous with.
  • the aromatic hydrocarbon ring group and aromatic heterocyclic group preferably a phenyl group, a biphenyl group, a terphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, and an anthracenyl group. is there.
  • the aromatic hydrocarbon ring group and aromatic heterocyclic group may be further substituted with a substituent described in the general formula (5).
  • Ra, Rb, Rc, Re, and Re represent a hydrogen atom or a substituent, and description of the substituent is synonymous with the description in General formula (5).
  • q represents an integer of 0 to 3, and when q is 0, J 1 -Ar 2 represents a bond.
  • R 1 to R 28 each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). Each substituent may be the same or different. Each substituent may be further substituted with a substituent in the general formula (5). Further, each adjacent substituent may be linked to each other to form a ring. R 22 and R 25 and / or R 24 and R 27 may be linked to each other to form a ring.
  • R 1 to R 32 each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). Each substituent may be the same or different. Each substituent may be further substituted with a substituent in the general formula (5). Further, each adjacent substituent may be linked to each other to form a ring. R 26 and R 29 , and / or R 28 and R 31 may be connected to each other to form a ring.
  • X and Y represent an oxygen atom, a sulfur atom, a selenium atom, and —NRf—
  • Rf represents a hydrogen atom, an alkyl group, an aromatic hydrocarbon ring group, or an aromatic heterocyclic group.
  • the description of the alkyl group, aromatic hydrocarbon ring group, and aromatic heterocyclic group in Rf has the same meaning as in General Formula (5).
  • Each alkyl group, aromatic hydrocarbon ring group, and aromatic heterocyclic group may be further substituted with a substituent in the general formula (5).
  • the compounds represented by the general formulas (5) to (10) may have a polymerizable group such as a styryl group, an epoxy group, an oxetanyl group, an acrylic group, and a methacryl group in addition to the alkenyl group described above. . Furthermore, the compounds represented by the general formulas (5) to (10) can react with the polymerizable groups or with other polymerizable monomers to form a polymer.
  • the partial structures represented by any one of the general formulas (5) to (10) may be the same or different.
  • the polymer (polymer) of the compounds represented by the general formulas (5) to (10) can be synthesized according to the polymerization method of the partial structure represented by any one of the general formulas (1) to (4). it can.
  • the polymer (polymer) of the compounds represented by the general formulas (5) to (10) can be made into a homopolymer using the above method, or can be made into a copolymer combined with a plurality of monomers. .
  • 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.
  • the light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
  • the total thickness of the light emitting layer is not particularly limited, but from the viewpoint of preventing the application of a high voltage unnecessary for the film uniformity and light emission, and improving the stability of the emitted color with respect to the driving current. It is preferable to adjust to a range of 5 ⁇ m, more preferably to a range of 2 to 200 nm, and particularly preferably in a range of 10 to 20 nm.
  • 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 a light emitting dopant (such as a phosphorescent dopant (also referred to as a phosphorescent dopant) or a fluorescent dopant).
  • a light emitting dopant such as a phosphorescent dopant (also referred to as a phosphorescent dopant) or a fluorescent dopant.
  • the host compound in the present invention is 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.
  • the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.
  • the host compound a known host compound may be used alone, or a plurality of types may be used in combination. By using a plurality of types of host compounds, the movement of charges can be adjusted, 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 light emission 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 compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.
  • Specific examples of known host compounds include compounds described in the following documents.
  • Luminescent dopant The light emitting dopant according to the present invention will be described.
  • a fluorescent dopant also referred to as a fluorescent compound
  • a phosphorescent dopant also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like
  • the above-mentioned host compound is used as a light emitting dopant (sometimes simply referred to as a light emitting material) used in the light emitting layer or light emitting unit of the organic EL device of the present invention. It is preferable to contain a phosphorescence dopant simultaneously with containing.
  • the phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed.
  • the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 25 ° C.
  • the preferred phosphorescence quantum yield is 0.1 or more.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.
  • phosphorescent dopants 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, and this energy is transferred to the phosphorescent dopant. Energy transfer type to obtain light emission from the phosphorescent dopant, another is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained In any case, the excited state energy of the phosphorescent dopant is required to be 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 element.
  • the phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), Rare earth complexes, most preferably iridium compounds.
  • the compound used as the phosphorescent dopant according to the present invention is preferably a transition metal complex compound containing a partial structure represented by any one of the general formulas (1) to (4) according to the present invention.
  • Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, or rare earth complex phosphors.
  • 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).
  • anode buffer layer hole injection layer
  • 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.
  • cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc.
  • the buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m, 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 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. 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 carbazole derivative, carboline derivative, diazacarbazole derivative shown by replacing one of the carbon atoms constituting the carboline ring of the carboline derivative with a nitrogen atom
  • the host compound described above It is preferable to contain.
  • the light emitting layer whose emission maximum wavelength is the shortest is the closest to the anode among all the light emitting layers.
  • a hole blocking layer is additionally provided between the shortest wave layer and the light emitting layer next to the anode next to the shortest wave layer.
  • 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 electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by, for example, the following method.
  • 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, is used as a keyword.
  • the ionization potential can be obtained as a value obtained by rounding off the second decimal place of the calculated value (eV unit converted value). 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.
  • the ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy.
  • a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be suitably used.
  • 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.
  • the structure of the hole transport layer described later can be used as an electron blocking layer as necessary.
  • the aromatic tertiary amine compound according to any one of the general formulas (5) to (10) according to the present invention can be used as the electron blocking layer, in addition to the hole transport layer described later.
  • the film thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • 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 either hole injection or transport or electron barrier properties, and may be either organic or inorganic.
  • 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, and any of the porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly any one of the general formulas (5) to (10) according to the present invention.
  • the aromatic tertiary amine compounds described are preferably used.
  • 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.
  • 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 described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.
  • 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.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
  • a hole transport layer having such a high p property because a device with lower power consumption can be produced.
  • 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.
  • 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 can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • an electron transport layer having a high n property doped with impurities 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.
  • an electron transport layer having such a high n property because an element with lower power consumption can be produced.
  • 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.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • 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 ⁇ m 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.
  • a wet film forming method such as a printing method or a coating method can be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode 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.
  • 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.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
  • a transparent or semi-transparent cathode can be produced by producing the conductive metal mentioned in the description of the anode on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode.
  • 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.
  • 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, polysulfone , Polyetherimide, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (manufactured by J
  • an inorganic film, an organic film or a hybrid film of both may be formed on the surface of the resin film.
  • a high barrier film having a degree of 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material for forming the barrier film may be any material that has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, or the like can be used.
  • the method for forming the barrier film is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • the external extraction quantum 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.
  • 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.
  • 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 may be used in combination.
  • the ⁇ max 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
  • the sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.
  • Specific examples include a glass plate, a polymer plate / film, and a metal plate / film.
  • the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • 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.
  • a polymer film and a metal film can be preferably used because the element can be thinned.
  • the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and a method according to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured in (1) is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • sealing member For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.
  • the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to.
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • an organic EL element may deteriorate by heat processing, what can be adhesively cured from room temperature to 80 ° C. is preferable.
  • a desiccant may be dispersed in the adhesive.
  • Application of the adhesive to the sealing portion may be performed using a commercially available dispenser or may be printed like screen printing.
  • 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.
  • silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
  • vacuum deposition sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma
  • a combination method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • 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.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside.
  • Examples of the hygroscopic compound include metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (eg, 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.
  • metal oxides eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt
  • 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.
  • the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
  • 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.
  • 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 ⁇ 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.
  • 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 for improving efficiency by giving light condensing property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from the 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.
  • these methods can be used in combination with the organic EL device of the present invention.
  • 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.
  • the low refractive index layer examples 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.
  • Bragg diffraction such as first-order diffraction and second-order diffraction.
  • light that cannot be emitted due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode), and the light is removed. I want to take it out.
  • the diffraction grating to be introduced 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.
  • the refractive index distribution a two-dimensional distribution
  • the light traveling in all directions is diffracted, and the light extraction efficiency is increased.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • 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.
  • 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.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 to 100 ⁇ m. If it becomes smaller than this, the effect of diffraction will generate
  • the condensing sheet it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device.
  • a sheet for example, Sumitomo 3M brightness enhancement film (BEF) can be used.
  • BEF Sumitomo 3M brightness enhancement film
  • the base material may be formed by forming a ⁇ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ m, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
  • a light diffusion plate / film may be used in combination with the light collecting sheet.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • a desired electrode material for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably 10 to 200 nm, thereby producing an anode. .
  • organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed thereon.
  • 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) and the like as described above, but it is easy to obtain a homogeneous film and it is difficult to generate pinholes.
  • 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.
  • liquid medium for dissolving or dispersing the organic EL material according to the present invention examples 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.
  • a dispersion method it can disperse
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • 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.
  • the organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
  • 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
  • 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.
  • patterning may be performed by a metal mask, an ink jet printing method, or the like during film formation, if necessary.
  • 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, and a conventionally known method may be used in the fabrication of the element. it can.
  • 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 a total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.
  • Example 1 Production of Organic EL Element 1-1 >> A transparent support substrate provided with this ITO transparent electrode after patterning a substrate (NH45 made of NH technoglass) 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 was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • a substrate NH45 made of NH technoglass
  • This transparent support substrate was fixed to a substrate holder of a commercially available vacuum evaporation apparatus. Meanwhile, 200 mg of ⁇ -NPD was put in a molybdenum resistance heating boat, and 200 mg of H-1 as a host compound was put in another resistance heating boat made of molybdenum. 200 mg of BAlq was put into another molybdenum resistance heating boat, 100 mg of FIr (pic) was put into another resistance heating boat made of molybdenum, and 200 mg of Alq 3 was put into another resistance heating boat made of molybdenum, and attached to the vacuum deposition apparatus. .
  • the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing ⁇ -NPD, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec.
  • the hole transport layer was provided.
  • the heating boat containing H-1 and FIr (pic) is energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively.
  • a light emitting layer having a thickness of 40 nm was provided.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the heating boat containing BAlq was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.
  • the heating boat containing Alq 3 was further energized and heated, and was deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • FIG. 3 is a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more).
  • FIG. 4 shows a cross-sectional view of the lighting device.
  • 105 denotes a cathode
  • 106 denotes an organic EL layer
  • 107 denotes a glass substrate with a transparent electrode.
  • the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.
  • the half-life was evaluated according to the measurement method shown below. Each organic EL device driven with a constant current at a current giving an initial luminance 1000 cd / m 2, obtains the time to be 1/2 (500cd / m 2) of the initial luminance, which was used as a measure of the half-life. The half life was expressed as a relative value when the comparative organic EL element 1-1 was set to 100.
  • the initial deterioration was evaluated according to the following measurement method. The time for the luminance to reach 90% during the half-life measurement was measured, and this was used as a measure of initial deterioration. The initial deterioration was 100 for the comparative organic EL element 1-1. The initial deterioration was calculated based on the following formula.
  • Initial degradation (luminance 90% arrival time of organic EL element 1-1) / (luminance 90% arrival time of each element) ⁇ 100 That is, the smaller the initial deterioration value, the smaller the initial deterioration.
  • ⁇ When the number of confirmed dark spots is 5 or more ⁇ : When the number of confirmed dark spots is 1 to 4 ⁇ : When the number of confirmed dark spots is 0
  • the organic EL device of the present invention has a high external extraction quantum efficiency, less initial luminance deterioration, and has a long life as a result, as compared with the comparative device. It can also be seen that the generation of dark spots is suppressed. Furthermore, it has been found that the organic EL device of the present invention can greatly suppress an increase in drive voltage after storage.
  • Example 2 Production of organic EL elements 2-1 to 2-9 >>
  • the dopant compound FIr (pic) is changed to A-97 and F-40, and the hole transport material is represented by the glass transition temperature shown in Table 2 and B in the general formula (6).
  • Organic EL devices 2-1 to 2-9 were produced in the same manner except that the exemplified compound having the molecular weight of the linking group represented was used.
  • the organic EL device of the present invention has a high external extraction quantum efficiency depending on the glass transition temperature of the hole transport material and the molecular weight of the linking group, and the initial luminance degradation is low. It can be seen that there is little and a long life. It can also be seen that the generation of dark spots is suppressed.
  • Example 3 Provide of full-color display device> (Production of blue light emitting element)
  • the organic EL element 2-4 of Example 2 was used as a blue light emitting element.
  • a green light emitting device was produced in the same manner as in the organic EL device 1-1 of Example 1, except that Comparative 1 was changed to Ir-1, and this was used as the green light emitting device.
  • a red light emitting device was produced in the same manner as in the organic EL device 1-1 of Example 1 except that Comparative 1 was changed to Ir-9, and this was used as a red light emitting device.
  • the red, green, and blue light emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full color display device having a configuration as shown in FIG. In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown.
  • a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate.
  • the scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (for details, see FIG. Not shown).
  • the plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5.
  • the image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was produced by appropriately juxtaposing red, green, and blue pixels.
  • Example 4 Preparation of white light emitting element and white lighting device >> The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm ⁇ 20 mm, and an exemplary compound 187 was formed thereon with a thickness of 25 nm as a hole injecting / transporting layer in the same manner as in Example 1.
  • H The heating boat containing 1 and the boat containing Exemplified Compound A-97 and the boat containing Ir-9 are energized independently, and CBP as a light emitting host and Illustrative Compound A-97 as Ir emitting dopant and Ir
  • the vapor deposition rate of ⁇ 9 was adjusted to 100: 5: 0.6, vapor deposition was performed to a thickness of 30 nm, and a light emitting layer was provided.
  • Example 2 a square perforated mask having the same shape as the transparent electrode made of stainless steel was placed on the electron transport layer, and lithium fluoride 0.5 nm as the cathode buffer layer and aluminum 150 nm as the cathode. Vapor deposition and film formation were performed.
  • This device was equipped with a sealing can having the same method and the same structure as in Example 1, and a flat lamp as shown in FIGS. 3 and 4 was produced. When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.
  • Example 5 Production of White Light Emitting Element and White Lighting Device-2 >> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • a solution of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) diluted to 70% with pure water at 3000 rpm for 30 seconds. After film formation by a spin coating method, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.
  • the substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of the exemplary compound 131 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 perform photopolymerization and crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to obtain a second hole transport layer.
  • a film in which Compound E (20 mg) was dissolved in 6 ml of toluene was used to form a film by spin coating under conditions of 1000 rpm and 30 seconds. It was irradiated with ultraviolet light for 15 seconds to cause photopolymerization and crosslinking, and further heated in vacuum at 80 ° C. for 1 hour to form a hole blocking layer.
  • this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, and 200 mg of Alq 3 was put into a molybdenum resistance heating boat and attached to the vacuum vapor deposition apparatus.
  • the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, and then heated by energizing the heating boat containing Alq 3 , and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second.
  • An electron transport layer having a thickness of 40 nm was provided.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • Example 6 Production of Organic EL Element 6-1 >> A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm ⁇ 100 mm ⁇ 1.1 mm glass substrate as an anode.
  • the supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • the substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg ⁇ -NPD dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds.
  • the above film was vacuum dried at 60 ° C. for 1 hour to form a second hole transport layer.
  • the second hole transport material has a polymerizable group
  • vacuum drying is performed at 60 ° C. for 1 hour, did.
  • this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, 200 mg of BAlq was placed in a molybdenum resistance heating boat, and attached to the vacuum vapor deposition apparatus.
  • the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa, heated by energizing the heating boat containing BAlq, evaporated onto the light emitting layer at a deposition rate of 0.1 nm / second, and further a film thickness of 40 nm.
  • the electron transport layer was provided.
  • 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 white light emitting organic EL element was produced.
  • the device of the comparative example has ⁇ -NPD dissolved at the time of application of the light emitting layer and diffused to the light emitting layer, thereby greatly degrading the device performance. It can be seen that the hole transport material does not diffuse to other layers, the external extraction quantum efficiency is high, the initial luminance degradation is small, and the lifetime is accordingly increased. It can also be seen that the generation of dark spots is suppressed.

Abstract

L'invention porte sur une matière d'élément électroluminescent organique qui émet de façon spécifique une lumière d'une courte longueur d'onde, tout en ayant un rendement lumineux élevé et une longue durée de vie d'émission. L'invention porte également sur un élément EL organique utilisant le matériau d'élément électroluminescent organique, un dispositif d'éclairement et un dispositif d'affichage. L'élément EL organique comprend au moins une couche d'émission de lumière prise en sandwich entre une anode et une cathode, et est caractérisé par le fait que la couche émettant de la lumière comprend une couche organique contenant au moins un composé contenant une structure partielle représentée par la formule générale (1), (2), (3) ou (4) et au moins un composé représenté par la formule générale (5).
PCT/JP2009/061731 2008-07-07 2009-06-26 Élément électroluminescent organique, dispositif d'affichage, dispositif d'éclairement et matière d'élément électroluminescent organique WO2010004887A1 (fr)

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US9331290B2 (en) 2010-07-16 2016-05-03 Merck Patent Gmbh Metal complexes
US9373802B2 (en) 2011-02-07 2016-06-21 Idemitsu Kosan Co., Ltd. Biscarbazole derivatives and organic electroluminescence device employing the same
WO2016101250A1 (fr) * 2014-12-26 2016-06-30 Dow Global Technologies Llc Composé organique et dispositif électronique comprenant une couche organique le contenant
US9748492B2 (en) 2012-11-02 2017-08-29 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
US10868254B2 (en) * 2012-10-17 2020-12-15 Novaled Gmbh Phosphorescent OLED and hole transporting materials for phosphorescent OLEDS
JP2022022386A (ja) * 2010-01-15 2022-02-03 住友化学株式会社 有機半導体素子用の液状組成物の保管方法

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