JP5286788B2 - Organic electroluminescence element, display device and lighting device - Google Patents

Abstract

This invention provides an organic electroluminescent element, which has high luminescence brightness, has high external takeout quantum efficiency, has a prolonged service life, and is improved in a voltage rise in constant-current driving, and a lighting system, and a display device. This organic electroluminescent element comprises a substrate and an electrode and at least one organic layer provided on the substrate and is characterized in that the organic layer comprises at least one luminescent layer, and the luminescent layer (or at least one luminescent layer when two or more luminescent layers are provided) contains a phosphorescent compound represented by general formula (1) and a host compound having a band gap of 3.45 eV to 3.70 eV.

Description

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

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

  On the other hand, an organic EL 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. The device emits light using the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of about several V to several tens of V, and is self-luminous. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type complete solid-state device, it has attracted attention from the viewpoints of space saving and portability.

  For the development of organic EL elements for practical use in the future, organic EL elements that emit light efficiently and with high luminance with lower power consumption are desired. For example, stilbene derivatives, distyrylarylene derivatives or A technique for doping a trisstyrylarylene derivative with a small amount of a phosphor to improve emission luminance and extend the lifetime of the device (see, for example, Patent Document 1), and using 8-hydroxyquinoline aluminum complex as a host compound. A device having an organic light emitting layer doped with a trace amount of a phosphor (see, for example, Patent Document 2), a device having an organic light emitting layer doped with a quinacridone dye as a host compound using 8-hydroxyquinoline aluminum complex ( For example, see Patent Document 3).

  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, since Princeton University has reported on organic EL devices that use phosphorescence from excited triplets (see, for example, Non-Patent Document 1), research on materials that exhibit phosphorescence at room temperature has become active. (For example, refer nonpatent literature 2.). When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so in principle the luminous efficiency is four times that of excited singlets, and the performance is almost the same as that of cold cathode tubes. It can be applied to and attracts attention. For example, many compounds have been studied for synthesis centering on heavy metal complexes such as iridium complexes (see, for example, Non-Patent Document 3).

Further, studies using tris (2-phenylpyridine) iridium as a dopant have been made (for example, see Non-Patent Document 2). In addition, L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac) (see, for example, Non-Patent Document 4) as a dopant, and tris (2- (p-tolyl) pyridine) iridium (as a dopant) Examination using Ir (ptpy) ₃ ), tris (benzo [h] quinoline) iridium (Ir (bzq) ₃ ), Ir (bzq) ₂ ClP (Bu) ₃ (for example, see Non-Patent Document 5). Studies using iridium complexes using phenylpyrazole as a ligand have been conducted (for example, see Patent Document 4).

  In addition, in order to obtain high luminous efficiency, a hole transporting compound is used as a host of the phosphorescent compound (see, for example, Non-Patent Document 6).

Furthermore, a specific host has been proposed for improving the efficiency of phosphorescent devices that emit blue light. (For example, refer to Patent Document 5.)
However, in the conventional organic electroluminescence device, high luminous efficiency, particularly improvement in blue light emission is desired. In addition, further improvements are desired in terms of voltage rise when driving at constant voltage, and compatibility between light emission luminance and lifetime.
Japanese Patent No. 3093796 Japanese Unexamined Patent Publication No. 63-264692 JP-A-3-255190 International Publication No. 04/085450 Pamphlet JP 2002-1000047 A M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) M.M. E. Thompson et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu) Moon-Jae Youn. 0 g, Tsutsuo Tsutsui et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu) Ikai et al. , The 10th International Works on Organic and Organic Electroluminescence (EL'00, Hamamatsu)

An object of the present invention is to provide an organic electroluminescence element, an illuminating device, and a display device that have high emission luminance, high external extraction quantum efficiency, long life, and improved voltage increase when driven by a constant current. is there.

The above object of the present invention is Ru is solved by the configuration of 1 to 10 below.

1. In an organic electroluminescence device having a substrate and an electrode and at least one organic layer on the substrate,
The organic layer has at least one light emitting layer, and at least one layer of the light emitting layer includes a phosphorescent compound represented by the following general formula (1) and the general formula (2), (3) or (4). ) And a host compound having a band gap of 3.45 to 3.70 eV .

[Wherein R ₁ represents a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered ring to a 7-membered ring. n1 represents the integer of 0-5. B _{1 to} B ₄ each represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. M ₁ represents a group 8-10 transition metal element in the periodic table. X ₁ and X ₂ each represent a carbon atom, a nitrogen atom or an oxygen atom, and L ₁ represents an atomic group which 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. ]
_Wherein, R 1 to R ₄ represents a substituent. n1 and n2 represent the integer of 0-3. A ₁ and A ₂ each represent a group represented by the following general formula (a). ]
[Wherein, Z ₁ and Z ₂ each represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring, and Z ₃ represents a divalent linking group or a simple bond. L ₁ represents a divalent linking group or a simple bond. ]
[Wherein R ₁₁ represents a substituent. n11 represents an integer of 0 to 4. A ₁₁ and A ₁₂ represent a group represented by the general formula (a). ]
[Wherein R ₃₁ and R ₃₂ represent _a substituent. n31 and n32 represent an integer of 0 to 3.
Y represents an oxygen atom, a sulfur atom, an imino group, a sulfoxide group or a sulfonyl group. A ₃₁ and A ₃₂ each represent a group represented by the general formula (a). ]

2 . The organic electroluminescence device according to 1, wherein you wherein m2 of the general formula (1) is zero.

3. The organic electroluminescence device according to item 1 or 2 wherein you wherein the nitrogen-containing heterocyclic ring formed by the B1~B4 and the nitrogen atom in the general formula (1) is an imidazole ring

4). Wherein the host compound, a carbazole ring as a partial structure, an organic electroluminescent device according to any one of item 1 to 3 wherein you comprising a carboline ring or diazacarbazole ring.

5. The organic electroluminescent device according to any one of item 1 to 4 wherein said substrate is you characterized by having a gas barrier layer.

6). The organic electroluminescent device according to any one of item 1 to 5 wherein you characterized in that emits blue light.

7). The organic electroluminescent device according to any one of item 1 to 6 wherein you characterized in that emits white light.

8 . Display device characterized by having an organic electroluminescent device according to any one of item 1 to 7 wherein.

9 . Lighting apparatus characterized by having an organic electroluminescent device according to any one of item 1 to 7 wherein.

10 . A display device comprising the lighting device according to item 9 and a liquid crystal element as a display unit.

The present invention, high emission luminance, high external extraction quantum efficiency, a long life, improved organic EL device of the voltage rise when the constant current drive, Ru can provide a lighting device and a display device.

It is a schematic diagram which shows the layer structure of the transparent gas barrier film which concerns on this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the system which processes a base material between counter electrodes. It is a figure which shows the discharge and film-forming process of an organic EL element. It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 30 Plasma discharge process chamber 35 Roll electrode 36 Electrode 41, 42 Power supply 51 Gas supply device 55 Electrode cooling unit 100 ITO substrate 111 Hole transport layer 112 Light emitting layer 113 Electron transport layer 114 Cathode 115 Gas barrier layer 10 Inkjet head D Droplet 1 Display 3 Pixel 5 Scan line 6 Data line A Display unit B Control unit 107 Glass substrate with transparent electrode 106 Organic EL layer 105 Cathode 102 Glass cover 108 Nitrogen gas 109 Water trapping agent

  In the organic EL device of the present invention, the structure defined in any one of claims 1 to 7 shows high emission luminance, high external extraction quantum efficiency, long life, constant It was possible to provide an organic EL device with improved voltage rise when driven by current. In addition, a display device and a lighting device provided with the organic EL element can be provided.

  Hereinafter, each component of the present invention will be described in detail.

<< Phosphorescent compound (also called phosphorescent compound) >>
The organic layer according to the present invention has at least one light emitting layer, and at least one of the light emitting layers contains the phosphorescent compound represented by the general formula (1). The organic layer according to the present invention will be described in detail later.

<< Phosphorescent Compound Represented by Formula (1) >>
The phosphorescent compound represented by the general formula (1) will be described.

In the general formula (1), examples of the substituent represented by R ₁ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl etc.) 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, bif Nitryl group, etc.), aromatic heterocyclic groups (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole- 1-yl group, 1,2,3-triazol-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 (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyl) Oxy group, octyloxy 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) Group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphtho group, etc.) Ruthio group etc.), alkoxycarbonyl group (eg 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, ethyl group) Carbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group) Pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcal Bonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octyl) Aminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group) Cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), Finyl 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) 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, Triphenylsilyl group, phenyldiethylsilyl group, etc.).

  Among these substituents, preferred are an alkyl group and an aryl group, and more preferred are an unsubstituted alkyl group and an aryl group.

  In the general formula (1), examples of the 5-membered ring to 7-membered ring formed by Z include a benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, and oxazole ring. And a thiazole ring. Of these, a benzene ring is preferred.

In the general formula (1), the aromatic nitrogen-containing heterocyclic ring formed by B _{1 to} B ₄ and the nitrogen atom may be a condensed ring or a monocyclic ring, but is preferably a monocyclic ring, more preferably a monocyclic ring. Nitrogen aromatic rings are preferred. Examples of the monocyclic nitrogen-containing aromatic ring include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, oxadiazole ring and thiadiazo ring. And the like. Among these, a pyrazole ring and an imidazole ring are preferable, and an imidazole ring is particularly preferable.

  These rings may be further substituted with the above substituents. Preferred as a substituent are an unsubstituted alkyl group and an unsubstituted aryl group.

In the general formula (1), L ₁ represents an atomic group forming 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 phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabole, picolinic acid and acetylacetone. It is done. These bidentate ligands may be further substituted with the above substituents.

  In the general formula (1), 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 represents a group 8 to group 10 transition metal element (also simply referred to as a transition metal) in the periodic table, and among them, iridium and platinum are preferable, and iridium is more preferable.

  The phosphorescent compound represented by the general formula (1) may or may not have a polymerizable group or a reactive group.

  Hereinafter, although the specific example of the phosphorescent compound represented by General formula (1) is given, this invention is not limited to these.

  Examples of the phosphorescent compound represented by the general formula (1) include Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and further synthesized by applying methods such as references described in these documents. it can.

《Host compound (simply called luminescent host)》
The organic layer according to the present invention has at least one light emitting layer, and at least one of the light emitting layers includes the phosphorescent compound represented by the general formula (1) and 3.45 eV to 3.70 eV. A host compound (light-emitting host) having the following band gap is contained. The organic layer and the light emitting layer according to the present invention will be described in detail later.

(Band gap)
The band gap according to the present invention is the difference between the ionization potential and the electron affinity of the host compound. 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 the electron affinity is the LUMO (lowest vacancy) of the electron at the vacuum level. It is defined as the energy that falls to the molecular orbital level and stabilizes.

  In the present invention, the band gap is determined by measuring the absorption spectrum of the deposited film when the host compound is deposited on glass to a thickness of 100 nm and converting the wavelength Ynm at the absorption edge to XeV. At this time, the following conversion formula is used.

(Conversion formula)
Y = 10 ⁷ /(8066.541×(X))
The specific measurement of the band gap was a value measured by a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  As the compound having the above band gap, a host compound preferably contained in the light emitting layer according to the present invention will be described.

  Examples of the host compound used in the present invention include carbazole derivatives, carboline derivatives, diazacarbazole derivatives (here, diazacarbazole is a compound in which at least one carbon atom constituting the carboline ring is substituted with a nitrogen atom) ), Triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, phenanthroline derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives , Stilbene derivatives, organometallic compounds, arylmethane derivatives and the like.

  Of these, more preferred are compounds represented by the following general formula (2), (3) or (4).

[In formula, R < ₁ > -R < ₄ > represents a substituent. n1 and n2 represent the integer of 0-3. A ₁ and A ₂ each represent a group represented by the following general formula (a). ]

[Wherein, Z ₁ and Z ₂ each represents an atomic group forming an aromatic heterocyclic ring or an aromatic hydrocarbon ring, and Z ₃ represents a divalent linking group or a simple bond. L ₁ represents a divalent linking group or a simple bond. ]

[Wherein R ₁₁ represents a substituent. n11 represents an integer of 0 to 4. A ₁₁ and A ₁₂ represent a group represented by the general formula (a). ]

Wherein, R ₃₁ and R _{32 represents} a substituent. n31 and n32 represent an integer of 0 to 3. Y represents an oxygen atom, a sulfur atom, an imino group, a sulfoxide group or a sulfonyl group. A ₃₁ and A ₃₂ each represent a group represented by the general formula (a). ]
In the general formulas (2), (3), and (4), the substituents represented by R _{1 to} R ₄ , R ₁₁ , R ₃₁ , and R ₃₂ are alkyl groups (preferably having 1 to 20 carbon atoms, Preferably it is C1-C12, Most preferably, it is C1-C8, for example, a methyl group, an ethyl group, iso-propyl group, a tert- butyl group, n-octyl group, n-decyl group, n-hexadecyl Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, , Vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 2 carbon atoms). 8 Yes, for example, a propargyl group, a 3-pentynyl group, etc.), an aromatic hydrocarbon ring group (also referred to as an aromatic hydrocarbon group or an aryl group, preferably 6 to 30 carbon atoms, more preferably 6 carbon atoms) -20, particularly preferably 6 to 12 carbon atoms, for example, phenyl group, p-methylphenyl 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, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, di Azacarbazolyl group (indicating that one of the carbon atoms 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) Group), an amino group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 10, particularly preferably a carbon number of 0 to 6, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group. , Dibenzylamino group, etc.), alkoxy groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy group, ethoxy group, etc. , Butoxy groups, etc.), aryloxy groups (preferably having 6 to 20 carbon atoms, more preferably 6 carbon atoms). 16, particularly preferably 6 to 12 carbon atoms, for example, a phenyl group, 2-naphthyloxy group and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group). An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms. , A benzoyloxy group, etc.), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetylamino group, A benzoylamino group, etc.), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group) An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group). ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferred). Is a C1-C12, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably C0-20, more preferably C0-16, especially preferably). The number of carbon atoms is 0 to 12, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group.), A carbamoyl group (preferably having a carbon number of 1 to 20, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group, and the like, and an alkylthio group (preferably having 1 to 1 carbon atoms). 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, Examples thereof include a methylthio group and an ethylthio group. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), an alkylsulfonyl group or an arylsulfonyl group A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl group, tosyl group, etc.), sulfinyl group (preferably carbon 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group, and a ureido group (preferably having a carbon number of 1 to 1. 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, ureido group, methylureido group, A ureido group, etc.), a phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a diethylphosphoric acid amide group, Phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, sulfo group, carboxy group, nitro group, hydroxam Acid group, sulfino group, hydrazino group, imino group, heterocyclic group (including hetero atoms such as nitrogen atom, oxygen atom, sulfur atom, selenium atom, etc., preferably 1-30 carbon atoms, more preferably carbon atoms 1-20, for example, imidazolyl, pyridyl, furyl group, piperidyl group, morpholino group, etc.). These substituents may be further substituted. If possible, they may be linked to form a ring. [Wherein A31 and A32 each represent a substituent. n31 and n32 represent an integer of 0 to 3. Y represents an oxygen atom, a sulfur atom, an imino group, a sulfoxide group or a sulfonyl group. R31 and R32 each represent a compound represented by the general formula (a). ]
In the general formulas (2), (3), and (4), the substituents represented by R _{1 to} R ₄ , R ₁₁ , R ₃₁ , and R ₃₂ are alkyl groups (preferably having 1 to 20 carbon atoms, Preferably it is C1-C12, Most preferably, it is C1-C8, for example, a methyl group, an ethyl group, iso-propyl group, a tert- butyl group, n-octyl group, n-decyl group, n-hexadecyl Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, , Vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 2 carbon atoms). 8 Yes, for example, a propargyl group, a 3-pentynyl group, etc.), an aromatic hydrocarbon ring group (also referred to as an aromatic hydrocarbon group or an aryl group, preferably 6 to 30 carbon atoms, more preferably 6 carbon atoms) -20, particularly preferably 6 to 12 carbon atoms, for example, phenyl group, p-methylphenyl 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, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, di Azacarbazolyl group (indicating that one of the carbon atoms 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) Group), an amino group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 10, particularly preferably a carbon number of 0 to 6, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group. , Dibenzylamino group, etc.), alkoxy groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy group, ethoxy group, etc. , Butoxy groups, etc.), aryloxy groups (preferably having 6 to 20 carbon atoms, more preferably 6 carbon atoms). 16, particularly preferably 6 to 12 carbon atoms, for example, a phenyl group, 2-naphthyloxy group and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group). An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group ( Preferably it has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms. , A benzoyloxy group, etc.), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as an acetylamino group, A benzoylamino group, etc.), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group) An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group). ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferred). Is a C1-C12, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably C0-20, more preferably C0-16, especially preferably). The number of carbon atoms is 0 to 12, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group.), A carbamoyl group (preferably having a carbon number of 1 to 20, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group, and the like, and an alkylthio group (preferably having 1 to 1 carbon atoms). 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, Examples thereof include a methylthio group and an ethylthio group. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), an alkylsulfonyl group or an arylsulfonyl group A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl group, tosyl group, etc.), sulfinyl group (preferably carbon 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group, and a ureido group (preferably having a carbon number of 1 to 1. 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, ureido group, methylureido group, A ureido group, etc.), a phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a diethylphosphoric acid amide group, Phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, sulfo group, carboxy group, nitro group, hydroxam Acid group, sulfino group, hydrazino group, imino group, heterocyclic group (including hetero atoms such as nitrogen atom, oxygen atom, sulfur atom, selenium atom, etc., preferably 1-30 carbon atoms, more preferably carbon atoms 1-20, for example, imidazolyl, pyridyl, furyl group, piperidyl group, morpholino group, etc.). These substituents may be further substituted. If possible, they may be linked to form a ring.

  Of these, preferred are an alkyl group and an aryl group.

In the general formula (a), the divalent linking group represented by L ₁ or Z ₃ includes a hydrocarbon group such as an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and a hetero atom (for example, Or a heteroarylene group or the like, and a compound having an aromatic heterocycle (also referred to as a heteroaromatic compound) such as a thiophene-2,5-diyl group or a pyrazine-2,3-diyl group. 2) or a chalcogen atom such as oxygen or sulfur. Further, it may be a group that meets and links heteroatoms such as an alkylimino group, a dialkylsilanediyl group, a diarylgermandiyl group, and the like.

In the general formula (a), examples of the aromatic heterocycle formed by the atomic groups represented by Z ₁ and Z ₂ include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, and a pyrimidine ring. , Pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine A ring, a carbazole ring, a carboline ring, a 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), and the like. Furthermore, the aromatic heterocycle may have the above substituent.

In the general formula (a), the aromatic hydrocarbon ring formed by each of the atomic groups represented by Z ₁ and Z ₂ includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, and 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, pyranthrene ring, anthraanthrene ring and the like. Furthermore, the aromatic hydrocarbon ring may have the above substituent.

  As the host compound according to the present invention, both a low molecular compound and a high molecular compound can be used.

  The polymer compound is obtained by polymerizing a compound having at least one polymerizable group (polymerizable compound). Examples of the polymerizable group include a vinyl group, an epoxy group, an oxetane group, an isocyanate group, and a thioisocyanate group. Is mentioned. Among these, a vinyl group is preferable. The host compound represented by the general formula (2), (3) or (4) may have these polymerizable groups at any position in the molecule.

  The polymerization reaction of the polymerizable compound will be described. As the time at which the polymerization is formed, a polymer that has been polymerized in advance may be used, or polymerization may be performed in a solution before device preparation or during device preparation. Further, a bond may be formed after the device is manufactured.

  When a polymerization reaction occurs, external energy (heat, light, ultrasonic waves, etc.) may be supplied, or a polymerization initiator, acid catalyst or base catalyst may be added to cause the reaction. Alternatively, when the polymerization reaction is caused when the compound according to the present invention is contained in the light emitting element, the reaction may be caused by a current supplied at the time of driving the light emitting element or generated light or heat. Two or more polymerizable compounds may be polymerized to form a copolymer.

  The polymerized polymer compound preferably has a weight average molecular weight of 5,000 to 1,000,000, more preferably 5,000 to 200,000. Here, the weight average molecular weight can be measured and analyzed by a commercially available GPC (gel permeation chromatography) method using a commercially available GPC apparatus.

  Examples of the radical polymerization initiator include 2,2′-azobisbutyronitrile, 2,2′-azobiscyclohexanecarbonitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′. -Azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4 '-Azobis (4-cyanovaleric acid), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropionamidoxime), 2,2'-azobis (2- (2-imidazoline-2- Yl) propane), azo initiators such as 2,2'-azobis (2,4,4-trimethylpentane), benzoyl peroxide, di-t-butyl peroxide, t-butyl Peroxide initiators such as droperoxide and cumene hydroperoxide, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 4- Aromatic carbonyl initiators such as phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one Is mentioned. Further, disulfide initiators such as tetraethylthiilam disulfide, nitroxyl initiators such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4,4′-di-t-butyl-2,2′- Living radical polymerization initiators such as a bipyridine copper complex-methyl trichloroacetate complex can also be used.

  Acid catalysts include activated clays, clays such as acidic clays, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid and trifluoroacetic acid, aluminum chloride, ferric chloride, stannic chloride, Lewis acids such as titanium trichloride, titanium tetrachloride, boron trifluoride, hydrogen fluoride, boron tribromide, aluminum bromide, gallium chloride, gallium bromide, and solid acids such as zeolite, silica, alumina, silica Various types such as alumina, cation exchange resin, heteropolyacid (for example, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid) can be used.

Basic catalysts include alkali metal carbonates such as Li ₂ CO ₃ , Na ₂ CO ₃ and K ₂ CO ₃ , alkaline earth metal carbonates such as BaCO ₃ and CaCO ₃ , Li ₂ O, Na ₂ O and K Alkali metal oxides such as ₂ O, alkaline earth metal oxides such as BaO and CaO, alkali metals such as Na and K, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or sodium, potassium and rubidium And alkoxides such as cesium.

  In addition, in the host compounds represented by the general formulas (2), (3), and (4), preferred is a compound (host compound) represented by the general formula (3) or the general formula (4). And more preferably a compound (host compound) represented by the general formula (4).

  Specific examples of the host compound represented by the general formula (2), (3) or (4) are given below, but the present invention is not limited to these.

<< Fluorescent compounds and phosphorescent compounds that may be used in combination >>
The fluorescent compound and phosphorescent compound used in the present invention will be described.

  The phosphorescent compound represented by the above general formula (1) is used for at least one of the light emitting layers of the organic EL device of the present invention. However, in the present invention, conventionally known phosphorescent compounds and fluorescent compounds are used. You may use together with a compound etc. Preferred as the fluorescent compound is one having a high fluorescence quantum yield in a solution state. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more.

  Specific fluorescent compounds 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, rare earth complex phosphors, and the like.

  Here, the fluorescence quantum yield of the fluorescent compound used in the present invention can be measured by the method described in Spectroscopic II, page 362 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7.

  Next, specific examples of the phosphorescent compound that can be used in combination with the phosphorescent compound used in the present invention will be shown, but the invention is not limited thereto. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like. In addition, the fluorescent compound and phosphorescent compound to be contained may or may not have a polymerizable group or a reactive group.

<< Layer structure of organic electroluminescence element >>
The layer structure of the organic electroluminescence element (organic EL element) according to the present invention will be described.

  The organic electroluminescence device of the present invention has an electrode (cathode and anode) and at least one organic layer on a substrate, and at least one of the organic layers is a light emitting layer containing a phosphorescent compound.

  In a broad sense, the light emitting layer according to the present invention is a layer that emits light when a current is passed through an electrode composed of a cathode and an anode. Specifically, when a current is passed through an electrode composed of a cathode and an anode, A layer containing a compound that emits light.

  The organic layer according to the present invention may have a hole transport layer, an electron transport layer, an anode buffer layer, a cathode buffer layer, and the like in addition to the light emitting layer as necessary, and has a structure sandwiched between a cathode and an anode. . Specific examples include the structures shown below.

(I) Anode / hole transport layer / light emitting layer / cathode (ii) Anode / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iv) Anode / Anode buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode Of the plural layers sandwiched between electrodes (anode and cathode) constituting the organic EL element, two organic layers are provided. It is preferable that it is above, and more preferably it is three or more layers.

<Light emitting layer>
The light emitting layer according to the organic EL device of the present invention will be described. The light emitting layer 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 adjacent to the light emitting layer even in the layer of the light emitting layer. It may be an interface with the layer.

(Film thickness of the light emitting layer)
There is no restriction | limiting in particular about the film thickness of the light emitting layer formed in this way, Although it can select suitably according to a condition, It is preferable to adjust film thickness in the range of 5 nm-5 micrometers.

  Next, other layers constituting the organic EL element in combination with the light emitting layer, such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer, will be described.

<< Hole injection layer, hole transport layer, electron injection layer, electron transport layer >>
The hole injection layer and hole transport layer used in the present invention have a function of transmitting holes injected from the anode to the light emitting layer. The hole injection layer and hole transport layer are formed of an anode and a light emitting layer. By interposing them, many holes are injected into the light emitting layer with a lower electric field, and electrons injected into the light emitting layer from the cathode, electron injection layer, or electron transport layer are injected into the light emitting layer and holes. Due to the barrier of electrons existing at the interface of the layer or the hole transport layer, it is accumulated at the interface in the light emitting layer and the light emitting efficiency is improved.

《Hole injection material, hole transport material》
The material of the hole injection layer and hole transport layer (hereinafter referred to as hole injection material and hole transport material) has the property of transmitting holes injected from the anode to the light emitting layer. If it is a thing, there will be no restriction | limiting in particular, In a photoconductive material, what is conventionally used as a charge injection transport material of a hole, and well-known used for the hole injection layer of a EL element, a hole transport layer Any one can be selected and used.

  The hole injection material and the hole transport material have either hole injection or transport or electron barrier properties, and may be either organic or inorganic. Examples of the hole injection material and hole transport material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, An oxazole derivative, a styryl anthracene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aniline-based copolymer, or a conductive polymer oligomer, particularly a thiophene oligomer can be used.

  The above-mentioned materials can be used as the hole injection material and 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 the aromatic tertiary amine compound and styrylamine compound 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; Bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p- Tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N′-diphenyl-N, N -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadri N; N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD), JP-A-4-30 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8688 are linked in a starburst type ( MTDATA) etc. Further, 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.

  Alternatively, 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. The hole injection layer and the hole transport layer are formed by thinning the hole injection material and the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Can be formed.

(Hole injection layer thickness, hole transport layer thickness)
Although there is no restriction | limiting in particular about the film thickness of a positive hole injection layer and a positive hole transport layer, It is preferable to adjust to the range about 5 nm-5 micrometers. The hole injection layer and hole transport layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<< Electron transport layer, electron transport material >>
The electron transport layer according to the present invention is only required to have a function of transmitting electrons injected from the cathode to the light emitting layer, and as the material thereof, any one of conventionally known compounds can be selected and used. Can do.

  Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, Examples include fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and organometallic complexes. 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.

  Or 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), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as an electron transport material.

  In addition, metal-free or metal phthalocyanine, and those in which the terminal is substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. Alternatively, the distyrylpyrazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and inorganic semiconductors such as n-type-Si and n-type-SiC can be used as well as the hole injection layer and the hole transport layer. It can be used as an electron transport material.

  The electron transport material may be used in combination with a donor compound. Examples of the donor compound include those of an periodic table (also referred to simply as a periodic table) as alkali metals and alkaline earth metals. Examples of salts thereof include carboxylates (acetates, etc.), sulfonates ( Methanesulfonate, tosylate, etc.), halides (fluoride, chloride, bromide and iodide), hydroxides, carbonates, nitrates and sulfates. Among these, cesium and its salt (for example, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium acetate, cesium carbonate) are more preferable. More preferred are cesium and cesium fluoride.

  The addition ratio of the donor to the electron transport material is preferably 1% by mass to 100% by mass.

(Film thickness of electron transport layer)
Although the film thickness of an electron carrying layer does not have a restriction | limiting in particular, It is preferable to adjust to the range of 5 nm-5 micrometers. This electron transport layer may have a single layer structure composed of one or two or more of these electron transport materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

  Further, in the present invention, a buffer layer (electrode interface layer) may exist between the anode and the light emitting layer or the hole injection layer and between the cathode and the light emitting layer or the electron injection layer.

  The buffer layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminous efficiency. “The organic EL element and its forefront of industrialization (published by NTS Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes an anode buffer layer and a cathode buffer layer.

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

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

  The buffer layer is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 100 nm, although it depends on the material.

  Further, in addition to the above basic constituent layers, layers having other functions may be laminated as required. For example, JP-A-11-204258, JP-A-11-204359, and “Organic EL element” And its industrialization front line (published by NTT Corporation on November 30, 1998) ”even if it has a functional layer such as a hole blocking layer described on page 237 Good.

  The organic layers (for example, anode buffer layer, hole transport layer, light emitting layer, electron transport layer, cathode buffer layer, hole blocking layer, electron blocking layer, etc.) constituting the organic EL device of the present invention are formed by coating. It is preferable to do this. In the application, spin coating, dip coating, roll coating, bar coating, flexographic printing, screen printing, offset printing, and an inkjet method are preferable, and an inkjet method is preferable.

"electrode"
Next, the electrode of the organic EL element will be described. The electrode of the organic EL element consists of a cathode and an anode. As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO.

  The anode may be formed by depositing a thin film of these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) ) May form a pattern through a mask having a desired shape during vapor deposition or sputtering of the electrode material. When light emission is extracted from the anode, it is desirable that the transmittance is greater than 10%, or 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 1 μm, preferably 10 nm to 200 nm.

On the other hand, as the cathode, those having an electrode substance of a metal having a low work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof are preferably 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 (Al2O3) mixture. , Indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron injecting property and durability against oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, magnesium An aluminum / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, and the like are preferable.

  The cathode can be produced by forming a thin film from these electrode materials by a method such as vapor deposition or sputtering. Alternatively, the sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 nm to 200 nm. In addition, in order to transmit light emission, if either one of the anode or the cathode of the organic EL element is transparent or translucent, it is advantageous because the light emission efficiency is improved.

"Base material"
The organic EL element of the present invention is preferably formed on a substrate (hereinafter also referred to as a substrate, a substrate, a support, a film, etc.).

  As a base material that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic and the like, and there is no particular limitation as long as it is transparent. For example, glass, quartz, and a transparent film can be mentioned. A particularly preferable substrate is a transparent film that can give flexibility to the organic EL element.

  Specifically, homopolymers or copolymers such as ethylene, polypropylene and butene, polyolefin (PO) resins such as copolymers, amorphous polyolefin resins (APO) such as cyclic polyolefins, polyethylene terephthalate (PET), Polyester resins such as polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) Polyvinyl alcohol resins such as polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvini Butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP) Fluorine-based resins such as vinylidene fluoride (PVDF), vinyl fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA) can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyether acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a base film.

  These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON CORPORATION), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film pure ace (manufactured by Teijin Ltd.), and cellulose triacetate film Konicakat Commercially available products such as KC4UX and KC8UX (manufactured by Konica Minolta Opto Co., Ltd.) can be preferably used.

  In addition, the base material according to the present invention using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  In addition, in the base material according to the present invention, surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment and the like may be performed before forming the deposited film.

Further, an anchor coating agent layer may be formed on the surface of the substrate according to the present invention for the purpose of improving the adhesion with the vapor deposition film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 g / m ^{2 to} 5 g / m ² (dry state).

  The substrate is conveniently a long product wound up in a roll. Since the thickness of the base material varies depending on the use of the film to be obtained, it cannot be defined unconditionally. However, when the film is used for packaging, it is not particularly limited, and is suitable as a packaging material, 3 μm to 400 μm, Especially, it is preferable to set it in the range of 6 micrometers-30 micrometers.

  Moreover, as for the base material used for this invention, 10 micrometers-200 micrometers are preferable as a film thickness of a film-shaped thing, More preferably, they are 50 micrometers-100 micrometers.

<Display device>
The organic EL device of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image. (Display) may be used. The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

《Light extraction technology》
In the organic EL device of the present invention, in order to improve the extraction efficiency of light emitted from the light emitting layer, a prism or lens-like process is applied to the surface of the substrate, or a prism sheet or a lens sheet is attached to the surface of the substrate. Also good.

  The organic EL device of the present invention may have a low refractive index layer between the electrode and the substrate. Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer.

  Since the refractive index of the 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. Furthermore, it is preferable that it is 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 organic EL element of the present invention may have a diffraction grating in any layer or in a medium (in a transparent substrate or a transparent electrode). It is desirable that 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. 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 one 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. 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.

  The substrate according to the present invention preferably has a gas barrier layer. Thereby, it has the further improvement effect of the aging stability in a dark spot and high temperature and high humidity.

《Gas barrier layer》
The composition of the gas barrier layer according to the present invention is not particularly limited as long as it is a layer that blocks permeation of oxygen and water vapor. The oxygen permeability is preferably 0.005 ml / m ² / day or less at 23 ° C. and 0% RH, and the water vapor permeability measured by a method according to JIS K7129-1992 (25 ± 0.5 ° C. relative humidity ( 90 ± 2)% RH) is preferably 0.1 g / (m ² · 24 hr) or less. Specifically, an inorganic oxide is preferable as the material constituting the gas barrier layer according to the present invention, and examples include silicon oxide, aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, and tin oxide. be able to.

  In addition, the thickness of the gas barrier layer in the present invention varies depending on the type and configuration of the material used and is selected as appropriate, but is preferably in the range of 5 nm to 2000 nm. This is because when the thickness of the gas barrier layer is thinner than the above range, a uniform film cannot be obtained, and it is difficult to obtain a barrier property against gas. Further, when the thickness of the gas barrier layer is larger than the above range, it is difficult to maintain the flexibility of the gas barrier film, and the gas barrier film is cracked due to external factors such as bending and pulling after film formation. This is because it may occur.

  The gas barrier layer according to the present invention is formed by spraying a raw material, which will be described later, a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method, which will be described later, a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, which will be described later. Can be formed by applying.

  FIG. 1 is an example showing the configuration of a substrate 21 having a gas barrier layer according to the present invention.

  The structure and density of the base material 21 having the gas barrier layer according to the present invention will be described.

  A base material 21 having a gas barrier layer according to the present invention has layers having different densities laminated on a base material 22, and a structure in which an adhesion film 23, a ceramic film 24, and a protective film 25 are laminated as one unit. Shows an example in which three layers are stacked (one unit). The density distribution in each layer is uniform, and the density of the ceramic film is set higher than the densities of the adhesion film and the protective film positioned above and below the ceramic film. In addition, although the example which laminated | stacked three layers was shown in FIG. 1, you may take the structure which consists of several units which have each two layers or more as needed.

  As a method of forming the adhesion film 23, the ceramic film 24, and the protective film 25 on the substrate 22, a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method described later, an atmospheric pressure or an atmospheric pressure described later. It can be formed by applying a plasma CVD method or the like under a nearby pressure.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”. The structural formulas of the compounds used in the examples are shown below.

Example 1
As a base material, a gas barrier layer shown in FIG. 1 is formed on a polyethylene naphthalate film having a thickness of 100 μm (a film made by Teijin-Dyupon Co., Ltd., hereinafter abbreviated as PEN) with the following atmospheric pressure plasma discharge treatment apparatus and discharge conditions. The base material 21 which has was produced.

(Atmospheric pressure plasma discharge treatment equipment)
Using the atmospheric pressure plasma discharge treatment apparatus of FIG. 2, a set of a roll electrode covered with a dielectric and a plurality of rectangular tube electrodes was produced as follows.

  The roll electrode serving as the first electrode is coated with a high-density, high-adhesion alumina sprayed film by an atmospheric plasma method on a jacket roll metallic base material made of titanium alloy T64 having cooling means by cooling water, and roll diameter It was set to 1000 mmφ. On the other hand, the square electrode of the second electrode is a hollow rectangular tube-shaped titanium alloy T64 covered with 1 mm of the same dielectric material with the same thickness under the same conditions, and the opposing rectangular tube-shaped fixed electrode group and did.

Ten square tube electrodes were arranged around the roll rotating electrode with a counter electrode gap of 1 mm. The total discharge area of the rectangular tube type fixed electrode group was 150 cm (length in the width direction) × 4 cm (length in the transport direction) × 10 (number of electrodes) = 6000 cm ² . In all cases, an appropriate filter was installed.

  During plasma discharge, the first electrode (roll rotating electrode) is kept at a temperature of 120 ° C. and the second electrode (square tube fixed electrode group) is adjusted to 80 ° C., and the roll rotating electrode is rotated by a drive to form a thin film. went. Among the 10 rectangular tube-shaped fixed electrodes, two from the upstream side are used for forming the following first layer (adhesion layer), and the following six are used for forming the following second layer (ceramic layer). The following two were used for film formation of the third layer (protective layer), each condition was set, and three layers were laminated in one pass.

(First layer: adhesion layer)
Plasma discharge was performed under the following conditions to form an adhesion layer having a thickness of about 50 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 94.5% by volume
Thin film forming gas: Hexamethyldisiloxane (vaporized by mixing with nitrogen gas in a vaporizer manufactured by Lintec) 0.5% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed first layer (adhesion layer) was 1.90 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

(Second layer: Ceramic layer)
Plasma discharge was performed under the following conditions to form a ceramic layer having a thickness of about 30 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 94.9% by volume
Thin film forming gas: Hexamethyldisiloxane (vaporized by mixing with nitrogen gas with a vaporizer manufactured by Lintec) 0.1% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 10W / cm ²
The density of the formed second layer (ceramic layer) was 2.20 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science.

(3rd layer: protective layer)
Plasma discharge was performed under the following conditions to form a protective layer having a thickness of about 200 nm.

<Gas conditions>
Discharge gas: Nitrogen gas 93.0% by volume
Thin film forming gas: Hexamethyldisiloxane (vaporized by mixing with nitrogen gas with a vaporizer manufactured by Lintec Corporation) 2.0% by volume
Additive gas: Oxygen gas 5.0% by volume
<Power supply conditions: Only the power supply on the first electrode side was used>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
The density of the formed third layer (protective layer) was 1.95 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.

As a result of measuring water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) by a method based on JIS-K-7129-1992, 10 ⁻³ g / (m ² · 24 hr) or less Met. As a result of measuring the oxygen transmission rate by a method based on JIS-K-7126-1987, it was 10 ⁻³ ml / (m ² · 24 hr · MPa) or less.

Next, after patterning a substrate having a 120 nm ITO (Indium Tin Oxide) film formed on a base material 21 having a gas barrier layer, the substrate with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol and dried nitrogen gas. And UV ozone cleaning was performed for 5 minutes. The ITO substrate 100 was manufactured by fixing to a substrate holder of a commercially available vacuum deposition apparatus and reducing the pressure to 4 × 10 ⁻⁴ Pa.

<< Production of Organic EL Element OLED1-1 >>
Using the inkjet recording method as shown in FIG. 3, the organic EL element OLED1-1 of the present invention was produced. Hereinafter, the process will be described with reference to FIG.

  Using a commercially available inkjet head 10 (KM512S non-aqueous head manufactured by Konica Minolta), fluid D1 (not shown) containing α-NPD and THF (tetrahydrofuran) as a hole transport material is discharged onto the ITO substrate 100. The hole transport layer 111 having a film thickness of 50 nm was formed under the conditions of 100 ° C. for 60 minutes.

  Next, using the inkjet head 10, a fluid of the following exemplary compound A19, phosphorescent compound 1-1 (mass ratio 100: 5) and fluid D2 (not shown) containing THF as a host are used as holes. A light emitting layer 112 having a thickness of 50 nm was formed on the transport layer 111 by being discharged at 100 ° C. for 60 minutes.

Next, a fluid containing Alq ₃ and THF (tetrahydrofuran) was discharged onto the light emitting layer 112 to form an electron transport layer 113 having a thickness of 50 nm under the conditions of 100 ° C. and 60 minutes. Next, an aluminum layer 114 (cathode) having a thickness of 200 nm was formed on the electron transport layer 113 by vapor deposition. The base material 21 having the gas barrier layer shown in FIG. 1 was attached as the gas barrier layer 115 on the aluminum 114 (cathode) to produce an organic EL element OLED1-1.

(Synthesis of polymer of exemplary compound A19)
In a reaction vessel, 1.4 g (2.5 mmol) of Exemplified Compound A19 (2.5 mmol), 2,2′-azobis (isobutyronitrile) (AIBN) 0.010 g (0.061 mmol), and butyl acetate 30 ml were added. After carrying out nitrogen substitution, it was made to react at 80 degreeC for 10 hours.

  After the reaction, it was poured into acetone for reprecipitation, and the polymer was recovered by filtration. The recovered polymer chloroform solution is purified by adding it into methanol and reprecipitating twice, and after recovery, vacuum drying is performed to obtain 1.1 g of the target Exemplified Compound A26 as a powder. It was. The copolymer had a weight average molecular weight of 25000 in terms of polystyrene (analyzed by GPC measurement using HFIP (hexafluoroisopropanol) as an eluent).

<< Production of Organic EL Elements OLED1-2 to 1-8 >>
In the production of the organic EL element OLED1-1, the organic EL element OLED1-2 is the same as the production method of the organic EL element OLED1-1 except that the material of the light emitting layer is changed to the material shown in Table 1 below. 1-8 was produced.

<< Evaluation of organic EL elements >>
The organic EL device obtained as described below was evaluated, and the results are shown in Table 2.

<Emission brightness>
The emission luminance (cd / m ² ) of the organic EL device at a temperature of 23 ° C. and a 10 V DC voltage was measured. The light emission luminance is expressed as a relative value when the organic electroluminescence element OLED1-10 is 100. The light emission luminance was measured using CS-1000 (manufactured by Konica Minolta Sensing).

《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. Similarly, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used for the measurement. In addition, 50 degreeC drive lifetime was represented by the relative value when the comparative organic electroluminescent element OLED1-8 is set to 100. FIG.

<Drive voltage>
The driving voltage is a voltage when driving at 2.5 mA / cm ² , and is expressed as a relative value when the organic electroluminescence element OLED1-8 is set to 100.

<Voltage increase rate>
When driven at a constant current of 10 mA / cm ² , the initial voltage and the voltage after 150 hours were measured. The relative value of the voltage after 100 hours with respect to the initial voltage was defined as the voltage increase rate.

《Driving life》
Each organic EL element is driven at a constant current with a current that gives an initial luminance of 1000 cd / m ² under a constant condition of 50 ° C., and a time that is ½ (500 cd / m ² ) of the initial luminance is obtained. It was used as a measure of the ℃ driving life. In addition, 50 degreeC drive lifetime was represented by the relative value when the comparative organic electroluminescent element OLED1-8 is set to 100. FIG.

  As is clear from the results in Table 2, the organic EL device of the present invention has good emission luminance, external extraction quantum efficiency, and drive voltage characteristics, little voltage increase when driven at constant current, and good drive life. It turned out to be an element.

Example 2
<< Preparation of Organic EL Element 2-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was put in a molybdenum resistance heating boat, and 200 mg of M-1 as a host compound was put in another molybdenum resistance heating boat, Another molybdenum resistance heating boat was charged with 100 mg of dopant 1-32, and another molybdenum resistance heating boat was charged with 200 mg of Alq ₃ and attached to a vacuum deposition apparatus.

Then, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was heated by heating and deposited on the transparent support substrate at a deposition rate of 0.1 nm / second. A 10 nm hole transport layer was provided. Further, the heating boat containing M1 and 1-21 is energized and heated, and a light emitting layer is provided by co-deposition on the hole transport layer at a deposition rate of 0.2 nm / second and 0.010 nm / second, respectively. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature. Furthermore, the heating boat containing Alq ₃ was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide an electron transport layer having a thickness of 10 nm. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Subsequently, aluminum 110 nm was vapor-deposited to form a cathode, and further, the base material 21 having a gas barrier layer produced in Example 1 was attached thereon to form an organic EL element OLED2-1.

<< Production of Organic EL Elements 2-2 to 2-7 >>
Organic EL elements 2-2 to 2-7 were prepared in the same manner except that the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 3 in the preparation of the organic EL element 2-1.

  The obtained organic EL elements 2-1 to 2-7 were evaluated in the same manner as described in Example 1. The light emission luminance, the external extraction quantum efficiency, and the drive life are expressed as relative values when the organic EL element OLED2-2 is 100.

  Table 4 shows the obtained results.

  From the results shown in Table 4, the organic EL device of the present invention has better emission luminance, external extraction quantum efficiency, and driving voltage characteristics than those of the comparison, less voltage rise when driven at constant current, and better driving life. It is clear that this is a simple element.

Example 3
<Production of full-color display device>
Fabricated in the same manner except that the phosphorescent compound of the organic EL device 2-3 of the present invention produced in Example 2 and the organic EL device OLED2-3 of the present invention produced in Example 2 was replaced with Ir-1. The green light-emitting organic EL element and the red light-emitting organic EL element produced in the same manner except that the phosphorescent compound of the organic EL element OLED2-3 of the present invention was replaced with Ir-9, were juxtaposed on the same substrate. The active matrix type full-color display device shown in FIG. FIG. 5 shows only a schematic diagram of the display portion A of the produced full-color display device. That is, a wiring portion including a plurality of scanning lines 5 and data lines 6 and a plurality of juxtaposed pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) on the same substrate. Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is 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 (details). Is 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. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, full-color display is possible by appropriately juxtaposing the red, green, and blue pixels.

  By driving the full-color display device, a clear full-color moving image display was obtained.

Example 4
<Production of lighting device>
The non-light-emitting surface of each of the blue, green, and red light-emitting organic EL elements produced in Example 3 was covered with a glass case to obtain a lighting device. The lighting device has high luminous efficiency and can be used as a thin lighting device that emits white light with a long emission life. FIG. 6 is a schematic view of the lighting device, and FIG. 7 is a cross-sectional view of the lighting device. The organic EL element 101 was covered with a glass cover 102. Reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 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.

Example 5
<< Production of Organic EL Element OLED5-1 >>
In the production of the organic EL element OLED2-1 of Example 2, an organic EL element OLED5-1 was produced in the same manner except that the materials (compounds) and film thickness configurations shown in Table 5 below were changed. In Table 5, “%” represents a mass ratio (%). The intermediate layer 1 and the intermediate layer 2 were produced as follows.

  In addition, about the intermediate | middle layer 1 and the intermediate | middle layer 2, it produced on the conditions similar to a positive hole transport layer. That is, 200 mg of compound A1 was placed in a molybdenum resistance heating boat and attached to a vacuum deposition apparatus.

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound A1 was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. The intermediate layer 1 and the intermediate layer 2 were provided.

  Next, aluminum having a thickness of 200 nm was deposited thereon. In sealing, the base material 21 which has a gas barrier layer was affixed similarly to organic EL element OLED1-1.

  The obtained organic EL element OLED5-1 was made into the illuminating device as shown in FIG. 6, FIG. The obtained lighting device has high luminous efficiency and could be used as a thin lighting device that emits white light having a long light emission lifetime.

  Subsequently, the color gamut when the color filter marketed for displays was combined was evaluated. It was confirmed that the combination of the organic EL element 5-1 and the color filter has a wide color reproduction range and excellent performance in color reproducibility.

Claims (10)

In an organic electroluminescence device having a substrate and an electrode and at least one organic layer on the substrate,
The organic layer has at least one light emitting layer, and at least one layer of the light emitting layer includes a phosphorescent compound represented by the following general formula (1) and the general formula (2), (3) or (4). ) And a host compound having a band gap of 3.45 to 3.70 eV .
[Wherein R ₁ represents a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered ring to a 7-membered ring. n1 represents the integer of 0-5. B _{1 to} B ₄ each represent a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. M ₁ represents a group 8-10 transition metal element in the periodic table. X ₁ and X ₂ each represent a carbon atom, a nitrogen atom or an oxygen atom, and L ₁ represents an atomic group which 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. ]
_Wherein, R 1 to R ₄ represents a substituent. n1 and n2 represent the integer of 0-3. A ₁ and A ₂ each represent a group represented by the following general formula (a). ]
[Wherein, Z ₁ and Z ₂ each represents an aromatic heterocyclic ring or an aromatic hydrocarbon ring, and Z ₃ represents a divalent linking group or a simple bond. L ₁ represents a divalent linking group or a simple bond. ]
[Wherein R ₁₁ represents a substituent. n11 represents an integer of 0 to 4. A ₁₁ and A ₁₂ represent a group represented by the general formula (a). ]
[Wherein R ₃₁ and R ₃₂ represent _a substituent. n31 and n32 represent an integer of 0 to 3.
Y represents an oxygen atom, a sulfur atom, an imino group, a sulfoxide group or a sulfonyl group. A ₃₁ and A ₃₂ each represent a group represented by the general formula (a). ] The organic electroluminescent device according to請Motomeko 1, wherein the general formula (1) m @ 2 is zero. The organic electroluminescent device according to claim 1 or 2 nitrogen-containing heterocyclic ring formed by the B1~B4 and nitrogen atoms and wherein the imidazole ring of the formula (1). Wherein the host compound, a partial structure as a carbazole ring, an organic electroluminescent device according to claim 1, characterized in that it comprises a carboline ring or diazacarbazole ring. The organic electroluminescent device according to claim 1, wherein the substrate is characterized by having a gas barrier layer. The organic electroluminescent device according to any one of claims 1 to 5, characterized in that emits blue light. The organic electroluminescent device according to any one of claims 1 to 6, characterized in that emits white light. Display device characterized by having an organic electroluminescent device according to any one of claims 1 to 7. It has an organic electroluminescent element as described in any one of Claims 1-7, The illuminating device characterized by the above-mentioned. A display device comprising the illumination device according to claim 9 and a liquid crystal element as display means.