WO2007060826A1 - Organic electroluminescent element, display device, and lighting system - Google Patents

Abstract

This invention provides an organic EL element, which exhibits good luminescence brightness, causes no significant voltage rise and dark spots during constant-current drive, and has high temporal stability under high temperature and high humidity conditions, and a display device and a lighting system using the same. The organic electroluminescent element is characterized in that at least one of organic layers constituting the element is a luminescent layer containing a phosphorescent compound represented by general formula (1) and the organic layer contains 10-2 ppm to 103 ppm of an organic solvent.

Description

 Specification

 Organic electoluminescence device, display device and lighting device

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent mouth luminescence element, and a display device and an illumination device using the organic electroluminescent mouth luminescence element.

 Background art

 [0002] Conventionally, as a light-emitting electronic display device, there is an electoric luminescence display (ELD). Examples of ELD constituent elements include inorganic electoluminescence devices and organic electroluminescence devices (hereinafter also referred to as organic EL devices).

 [0003] An organic EL device has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode. By injecting electrons and holes into the light emitting layer and recombining them, excitons (exciton) Is a device that emits light using the emission of light (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it is a thin-film, completely solid element that has a wide viewing angle and high visibility, and has attracted attention from the viewpoints of space saving and portability.

[0004] In recent years, Princeton University has reported organic EL devices that use phosphorescence from excited triplets (see, for example, Non-Patent Document 1), and research on materials that exhibit phosphorescence at room temperature has become active. (For example, see Non-Patent Document 2.) Since the upper limit of the internal quantum efficiency is 100% when the ₀ excited triplet is used, the luminous efficiency is doubled in principle compared to the case of the excited singlet. It has attracted attention because it has almost the same performance as a tube and can be applied to lighting. For example, there have been many compounds are synthesized and studied about the heavy metal complexes such as iridium complexes (e.g., Non-Patent Documents 3 and Patent Document 1.) ₀

[0005] Currently, high efficiency of the further light emission of the organic EL device using the phosphorescent, long life has been studied (see, for example, Patent Documents 2 and 3.) ₀

[0006] For the green light emission, the external extraction efficiency of nearly 20%, which is the theoretical limit, has been achieved! However, for other colors of light emission, sufficient efficiency has not yet been obtained and improvement is necessary. In particular, there has been a demand for an element that emits blue light with high efficiency. [0007] On the other hand, organic light-emitting elements that achieve high-intensity light emission are elements in which organic substances are stacked by vacuum deposition. From the viewpoints of simplification of manufacturing process, processability, large area, etc. Device fabrication by coating method is also disclosed (for example, see Patent Document 4) ₀ Patent Document 1: International Publication No. 04Z085450 Specification

 Patent Document 2: JP 2002-100476 A

 Patent Document 3: JP 2002-117978 A

 Patent Document 4: Japanese Unexamined Patent Application Publication No. 2002-299061

 Non-Patent Document 1: M. A. Baldo et al., Nature, 395 卷, 151–154 (1998)

 Non-Patent Document 2: M. A. Baldo et al., Nature, 403 卷, 17, 750-753 (2000)

 Non-Patent Document 3: S. Lamansky et al., J. Am. Chem. Soc., 123 卷, 4304 (2001)

 Disclosure of the invention

 Problems to be solved by the invention

 [0008] However, the conventional organic-electric-mouth luminescence device is desired to be improved in voltage rise when driven at a low voltage, generation of dark spots, and stability over time at high temperature and high humidity. Yes. In addition, further improvement in light emission luminance is desired.

 [0009] The present invention has been made in view of the related problems, and an object of the present invention is to exhibit a favorable light emission luminance, increase in voltage when driven at a constant current, further increase in temperature and humidity with fewer dark spots. It is to provide an organic EL element having high stability with time, a display device using the same, and a lighting device.

 Means for solving the problem

[0010] The above object of the present invention has been achieved by the following constitutions 1 to 9.

 [0011] 1. An organic electroluminescent device having at least one organic layer between an anode and a cathode on a substrate,

At least one of the organic layers is a light emitting layer containing a phosphorescent compound represented by the following general formula (1), and the organic layer contains 10-pm to 10 ³ ppm of an organic solvent. With features Organic-elect luminescence element.

 [Chemical 1] General formula ("

[Wherein, R represents a substituent. Z is a group of nonmetallic atoms necessary to form a 5- to 7-membered ring

 1

 Represents. nl represents an integer of 0 to 5. B to B are carbon atom, nitrogen atom and oxygen atom, respectively.

 1 5

 Alternatively, it represents a sulfur atom, and at least one of B to B represents a nitrogen atom. M is the element circumference

 1 5 1 Represents Group 8 to Group 10 metals in the Periodic Table. X and X are carbon atoms and nitrogen atoms, respectively.

 1 2

 Or an oxygen atom, and L represents a group of atoms that form a bidentate ligand with X and X.

 1 1 2

 The ml represents an integer of 1, 2 or 3, m2 represents a force of 0, 1 or 2 and ml + m2 represents 2 or 3. ]

 2. The organic electroluminescent device according to 1 above, wherein the organic layer contains an organic solvent in an amount of 0.1 ppm to LOOppm.

[0014] 3. The organic electroluminescent device according to 1 or 2 above, wherein the light-emitting layer contains a polymer compound having a weight average molecular weight of 5000 or more as a host compound.

 [0015] 4. The organic electoluminescence device according to any one of the above items 1 to 3, further comprising a gas barrier layer on the substrate.

[0016] 5. The organic electroluminescent element according to any one of 1 to 4, wherein the light emission is blue.

 [0017] 6. The organic electroluminescent element according to any one of 1 to 4, wherein the light emission is white.

[0018] 7. A display device comprising the organic electoluminescence element according to any one of 1 to 6 above. [0019] 8. An illuminating device comprising the organic electoluminescence element according to any one of 1 to 6 above.

[0020] 9. A display device comprising the illumination device according to 8 and a liquid crystal element as display means.

 The invention's effect

 [0021] According to the present invention, an organic EL device that exhibits good light emission luminance, increases voltage when driven at a constant current, has less dark spots, has higher temperature stability under high temperature and high humidity, and the same is used. A display device and a lighting device could be provided.

 Brief Description of Drawings

FIG. 1 is a schematic view showing a layer structure of a transparent gas noria film according to the present invention.

 FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus of a type that treats a substrate between counter electrodes useful for the present invention.

 FIG. 3 is a diagram showing a discharge and film forming process of an organic EL element OLED1-1.

 FIG. 4 is a schematic view showing an example of a display device constituted by an organic EL element cover.

 FIG. 5 is a schematic diagram of a display unit.

 Explanation of symbols

[0023] 30 Plasma discharge treatment chamber

 35 Roll electrode

 36 electrodes

 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 Substrate having a gas barrier layer 10 Inkjet head

 D droplet

 1 display

 3 pixels

 5 scan lines

 6 Data line

 A Display section

 B Control unit

 BEST MODE FOR CARRYING OUT THE INVENTION

[0024] In the organic EL device of the present invention, the structure defined in any one of claims 1 to 6 exhibits good light emission luminance and voltage increase when driven at a constant current. We were able to provide an organic EL device with less dark spots and high stability over time at high temperatures and high humidity. In addition, a display device and a lighting device provided with the organic EL element could be provided.

[0025] Hereinafter, details of each component according to the present invention will be sequentially described.

[0026] As a result of various studies on the above problems, the present inventors have provided at least one organic layer between the anode and the cathode on the substrate as described in claim 1. In the organic electroluminescence device having at least one organic layer, the organic layer is a light emitting layer containing the phosphorescent compound represented by the general formula (1), and the organic layer contains an organic solvent. By adjusting it to contain ² ppm to 10 pm, it exhibits good light emission brightness, voltage rise when driven at constant current, high darkness with fewer dark spots, high temporal stability under high humidity, and organic EL It was found that an element can be obtained.

[0027] << Organic solvent and organic solvent content in organic layer >>

The organic layer according to the present invention, at the constituting layers of the organic EL device to be mentioned is described in detail, the organic layer according to the present invention is a feature may contain organic solvents 10- ² ppm~10 pm Preferably, the organic solvent contains 0.1 lppm to: LOOppm

[0028] By containing the organic solvent in the above-mentioned range, the voltage rise when driven at a constant current is reduced. The effect of further improving the stability over time at high temperature and high humidity can be obtained.

 [0029] The organic solvent according to the present invention is not particularly limited. For example, alcohols (methanol, ethanol, etc.), carboxylic acid esters (ethyl acetate, propyl acetate, etc.), nitriles (acetonitrile) Etc.), ethers (isopropyl ether, THF, etc.), aromatic hydrocarbons (cyclohexylbenzene, toluene, xylene, etc.), halogenated alkyls (salt methylene, etc.), saturated hydrocarbons (heptane, etc.) ).

[0030] Of these, preferred are: carboxylic acid esters, nitriles, ethers, aromatic hydrocarbons, alkyl halides, and saturated hydrocarbons, and more preferably carboxylic acid esters. , Ethers and aromatic hydrocarbons.

 [0031] The boiling point of the organic solvent used in the present invention is preferably 200 ° C or less, more preferably 150 ° C or less.

 [0032] (Measurement of organic solvent content)

 A method for measuring the organic solvent content in the organic layer will be described.

 [0033] The volatile organic solvent contained in the organic layer according to the present invention can be measured by gas chromatography (GC) mass spectrometry (MS) equipped with a purge & trap sampler. (PT-GCZMS) Specifically, a 10cm x 10cm square organic EL device was fabricated, and the residual solvent was adsorbed in the gas recovery chamber and the organic gas adsorption tube (TENAX GR), and PT-GCZMS measurement was performed. It was. The solvent concentration was determined from a calibration curve prepared using a reference sample with a known concentration.

 [0034] << Phosphorescent compound (also phosphorescent compound!) >>

 The organic layer according to the present invention has at least one light emitting layer, and the light emitting layer is characterized by containing the phosphorescent compound represented by the general formula (1).

 [0035] (Phosphorescent compound represented by the general formula (1))

 The phosphorescent compound represented by the general formula (1) will be described.

 [0036] In the general formula (1), examples of the substituent represented by R include an alkyl group (for example,

 1

, Methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl Group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkke

-Group (for example, vinyl group, aryl group, etc.), alkynyl group (for example, etulyl group, propargyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc., for example, Phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenyl group), aromatic Group heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, virazolyl group, pyrazol group, triazolyl group (for example, 1, 2, 4 triazole-1-yl group, 1, 2, 3 triazole-1yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, iso Azolyl group, furazanyl group, chenyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzocenyl group, dibenzocenyl group, indolyl group, carbazolyl group, carboryl group, diazacarbazolyl group (see above) One of the carbon atoms constituting the carboline group's carboline ring is replaced by a nitrogen atom), quinoxalinyl group, pyridazyl group, triazinyl group, quinazolinyl group, phthalazyl group, etc.), heterocyclic group ( For example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy Group (e.g., cyclopentyloxy group, cyclohexyloxy group) Group), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio Groups (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio groups (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl groups (for example, methyloxycarbonyl group, ethyloxycarbonyl group, etc.) , Butyoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenylcarbol group, naphthyloxycarbonyl group, etc.), Sulfamoyl group (eg, aminosulfol group, methylaminosulfur group) Hole group, dimethylaminosulfol group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group Group, octylaminosulfol group, dodecylaminosulfol group, phenolaminosulfol

Group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbon group, pentylcarbonyl group, cyclohexylcarboxyl group). Group, octylcarbol group, 2-ethylhexylcarbol group, dodecylcarpol group, phenolcarol group, naphthylcarbol group, pyridylcarbol group, etc.), acyloxy group (for example, acetylyloxy group) , Ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbolamino group, ethylcarbo- group) Luamino group, dimethyl carbolumino group, propyl carbolumino group, pentyl carbolumino group, cyclohexyl Carboxylamino group, 2-ethylhexylcarbolamino group, octylcarbolamino group, dodecylcarbolamino group, phenylcarbolumino group, naphthylcarbolumino group, etc.), rubamoyl group (for example, aminocarbol group) Group, methylaminocarbol group, dimethylaminocarbol group, propylaminocarbol group, pentylaminocarbol group, cyclohexaminocarbol group, octylaminocarbol group , 2-ethylhexylaminocarbonyl group, dodecylaminocarbol group, phenolaminocarbol group, naphthylaminocarbo ol group, 2-pyridylaminocarbo ol group, etc.), ureido group (for example, methyl) Lureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group , Furureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfier group (eg methylsulfuryl group, ethylsulfuryl group, butylsulfuryl group, cyclohexylsulfuryl group, 2-ethylhexylhexyl). Sylsulfuric group, dodecylsulfuric group, phenylsulfuric group, naphthylsulfuric group, 2-pyridylsulfiferic group, etc.), alkylsulfuric group (for example, methinolesnorehoninole group, Ethinolesnole-nole group, butinolesnolehoninole group, cyclohexenolesnoleol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc.), arylsulfol group or heteroarylsulfol group (For example, a phenylsulfol group, a naphthylsulfol group, a 2-pyridylsulfol group, etc.), an amino group (for example, amino Group, Echirua amino group, Jimechiruamino group, Buchiruamino group, cyclopentyl Rua amino group, a 2-Echiru carboxymethyl Ruamino group, dodecylamino group, arlino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropyl silyl group, triphenylsilyl) Group, a ferroethyl silyl group, etc.).

 [0037] Among these substituents, an alkyl group or an aryl group is preferable, and an unsubstituted alkyl group or an aryl group is more preferable.

 [0038] Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring. Examples of the 5- 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, oxazole ring, and thiazole ring. It is done. Of these, a benzene ring is preferred.

 [0039] In the general formula (1), B to B are each a carbon atom, a nitrogen atom, an oxygen atom or sulfur.

 1 5

 Represents an atom and at least one represents a nitrogen atom. A monocyclic ring is preferred as the aromatic nitrogen-containing heterocycle formed by these five atoms. Examples thereof include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, and a thiadiazole ring. Among these, a pyrazole ring and an imidazole ring are preferable, and an imidazole ring is more preferable.

 [0040] These rings may be further substituted with the above substituents. Preferred as substituents are unsubstituted alkyl groups and unsubstituted aryl groups.

 In the general formula (1), L represents an atomic group that forms a bidentate ligand with X and X. X

 As specific examples of the bidentate ligand represented by 1 1 2 1 L -X, for example, substituted or unsubstituted

1 2

 Examples thereof include phenyl pyridine, vinyl virazole, phenol imidazole, phenol triazole, phenol tetrazole, virazol ball, picolinic acid, and acetylacetone. In addition, these groups may be further substituted with the above substituents.

 [0042] ml represents an integer of 1, 2 or 3, m2 represents a force representing an integer of 0, 1 or 2 ml + m2 is

2 or 3. Of these, m2 is preferably 0.

[0043] In the general formula (1), the metal represented by M (including the field of metal ions) is an element.

 1

Transition metal elements from Group 8 to Group 10 of the periodic table (also referred to simply as transition metals) are used. However, iridium and platinum are preferred, and iridium is more preferred.

 [0044] The phosphorescent compound represented by the general formula (1) of the present invention may have a polymerizable group or a reactive group! .

[0045] Specific examples of the phosphorescent compound represented by the general formula (1) of the present invention are given below, but the present invention is not limited thereto.

[0046] [Chemical 2]

i [8 ^ 00]

 Vi-i

[ε ^] [oo]

ZnilZI9midillDA VV 9Z8090 / .00Z OAV

ivu 賺 soifcld 9S09 OA ε_

Tomb [0003

S2—

1 -73 1 -74

 These metal complexes are described in, for example, Organic Letter, vol3, No. 16, 2579-258, 1 (2001), Inorganic Chemistry, No. 30, Vol. 8, 1685-1687 (1991)

J. Am. Chem. Soc., 123 卷, 4304 (2001), Inorganic Chemistry, No. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, No. 41, No. 12, 3055-3066 (2002), New Journal of Chemistry., Vol. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, 695 ˜709 pages (2004), and further by applying methods such as references described in these documents.

 [0055] << Host compound (simply a luminescent host!) >>

 The host compound preferably contained in the light emitting layer according to the present invention will be described.

 [0056] The host compound used in the present invention includes, for example, a force rubazole derivative, a carboline derivative, a diaza force rubazole derivative (here, diaza force rubazole has at least one carbon atom constituting a carboline ring. Represents substituted with a nitrogen atom.), Triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, phenanthoracin derivatives, oxazoles Derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, organometallic compounds, arylene methane derivatives, and the like.

 Among these, more preferred are compounds represented by the following general formula (2), (3), (4) or (5).

[0058] [Chemical 10] General

[0059] In the formula, R to R each represents a substituent. nl and n2 represent an integer of 0 to 3. A, A

 1 4 1: each represents a group represented by the following general formula (a).

[0060] [Chemical Formula 11] General formula (a)

[0061] In the formula, Z and Z represent an aromatic heterocyclic group or an aromatic hydrocarbon ring group, and Z represents 2 Represents a valent linking group or a simple bond. L is a divalent linking group or a simple bond

 1

 Represents a hand.

 [0062] [Chemical 12] General formula (3J

[0063] In the formula, R represents a substituent. ni l is 0

 Represents an integer from 11 to 4. A and A are the above general

 11 12

 Represents a group represented by the formula (a).

[0064] [Chemical 13]

—General formula (4)

[0065] where R

 23-R represents a substituent. n21 and n22 are 0

 Represents an integer from 24 to 3. A and

 twenty one

A represents a group represented by the general formula (a). L represents a divalent linking group.

 twenty two

[0066] [Chem. 14] General formula 1

 [0067] In the formula, R 1 and R 2 represent a substituent. n31 and n32 are 0

 31 represents an integer of 32 to 3. Y represents an oxygen atom, an ion atom, an imino group, a sulfinyl group, an alkylsulfonyl group or an arylsulfonyl group. A and A represent a compound represented by the above general formula (a)

 31 32

[0068] Among the compounds represented by the general formulas (2), (3), (4), and (5), preferred are those in which Z and Z in the general formula (a) are aromatic hydrocarbon rings. It is the time of the group. In the general formulas (2), (3), (4) and (5), R 1 to R 4, R 4, R 5, R 5

Examples of the substituent represented by 1 4 11 23 24 31 32 include alkyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. methyl group, Echiru group, i _so - propyl, tert- butyl group, n- Okuchiru group, n- decyl group, Kisadeshi to n- group, a cyclopropyl group, a cyclopentyl group, cyclohexyl group and the like cyclohexylene. ), Alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butur group, 3-pentene An alkyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a propargyl group, 3— Pentynyl group, etc.), aromatic hydrocarbon ring group (Also known as an aromatic hydrocarbon group or aryl group, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. For example, a phenyl group, p-methylphenol, Group, naphthyl group, etc .;), amino group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 10 carbon atoms, particularly preferably having 0 to 6 carbon atoms. For example, amino group, methylamino group, etc. , A dimethylamino group, a jetylamino group, a dibenzylamino group, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms. D Oxy group, 2-naphthyloxy group, etc.), acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl group , Benzoyl group, formyl group, bivaloyl group, etc.), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms) Examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, etc.), an aryloxycarbol group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably carbon atoms). Formula 7-: L0, for example, a phenylcarbonyl group. ), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to carbon atoms: L0, and examples thereof include an acetoxy group and a benzoyloxy group). An acylamino group (preferably having 2 to 20 carbon atoms, more preferably Preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to carbon atoms: LO, and examples thereof include acetylamino groups and benzoylamino groups. ), An alkoxycarbolumino 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 methoxycarbolamino group). , Aryloxy-carboamino groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenylcarbocarboamino groups and the like. ), A sulfo-lumino 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 a methanesulfo-lumino group and a benzenesulfo-lumino group. ), A sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 16, particularly preferably a carbon number of 0 to 12, such as sulfamoyl group, methylsulfamoy Group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), rubamoyl group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms). For example, a strong rubamoyl group, a methylcarbamoyl group, a jet carbamoyl group, a phenylcarbamoyl group, etc.), an alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, etc.), an arylthio group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably carbon atoms). 6 to 12, for example, a phenylthio group), an alkylsulfonyl group or an arylsulfonyl group (preferably having a carbon number of 1 to 20, more preferably carbon. 1 to 16, particularly preferably 1 to 12 carbon atoms such as mesyl group and tosyl group), sulfyl group (preferably 1 to 20 carbon atoms, more preferably 1 carbon atom) To 16, particularly preferably 1 to 12 carbon atoms, such as methane sulfier group, benzene sulfier group, etc.), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 carbon atom) To 16, particularly preferably 1 to 12 carbon atoms, such as ureido group, methylureido group, and ferureido group), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, and more). Preferably it is C1-C16, Most preferably, it is C1-C12, for example, a jetyl phosphoric acid amide group, a phenylphosphoric acid amide group, etc. are mentioned. ), Hydroxy group, mercapto group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyan group, sulfo group, carbo group Xyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (including hetero atoms such as nitrogen atom, oxygen atom, sulfur atom, selenium atom, preferably 1 to 30 and more preferably those having 1 to 20 carbon atoms, such as imidazolyl, pyridyl, furyl group, piperidyl group, morpholino group, etc.). These substituents may be further substituted. If possible, connect them to form a ring.

 [0070] Among these, preferred are an alkyl group and an aryl group.

 In the general formulas (a) and (4), the divalent linking group represented by L and L is al

 1

 In addition to hydrocarbon groups such as a alkylene group, an alkylene group, an alkylene group, and an arylene group, those containing a hetero atom (eg, a heteroarylene group) may be used, and thiophene-2, 5 A divalent linking group derived from a compound having an aromatic heterocycle (also referred to as a heteroaromatic compound) such as a diyl group or a pyrazine-2,3-diyl group, or oxygen Or a chalcogen atom such as sulfur. In addition, it may be a group that meets and links heteroatoms such as an alkylimino group, a dialkylsilane diyl group, or a diarylgermandyl group.

 [0072] As the host compound according to the present invention, a force capable of using either a low molecular compound or a high molecular compound is preferable, and a high molecular compound is particularly preferable.

[0073] The polymer compound is a compound 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, a isocyanate group, Examples include thioisocyanate groups. Of these, preferred is a vinyl group.

 [0074] Among them, the compounds represented by the above general formulas (2) to (5) have these polymerizable groups in the molecule! A polymer formed by using a monomer at any position (in this case, either a homopolymer or a copolymer) is preferred.

[0075] 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 carried out either in the solution before the device fabrication or during the device fabrication.

[0076] Furthermore, a bond may be formed after the organic EL element is fabricated! When a polymerization reaction occurs, external It is possible to supply energy such as heat (light 'light' ultrasonic waves, etc.) or to add a polymerization initiator, acid catalyst or base catalyst to cause the reaction. On the other hand, when a polymerization reaction is caused when the light emitting device contains the compound according to the present invention, the reaction may be caused by a current supplied at the time of driving the light emitting device, generated light or heat. Two or more polymerizable compounds may be polymerized to form a copolymer.

 [0077] The polymer formed by polymerization preferably has a weight average molecular weight of 5000 to 100,000, more preferably 5000 to 200,000. As a result, the luminous brightness and dark spots are further improved.

 Here, the weight average molecular weight according to the present invention can be measured by a commercially available GPC (gel permeation chromatography) measuring apparatus.

[0079] Examples of the radical polymerization initiator include 2,2'-azobisbutyoxy-tolyl, 2,2'-azobiscyclohexanecarbonitryl, 1,1'-azobis (cyclohexane-1 carbotolyl), 2, 2 '— Azobis (2-methylbutyryl-tolyl), 2, 2 ′ — Azobis (2, 4-dimethyl valerine-tolyl), 2, 2' — Azobis (4-methoxy-1,4-dimethyl valerine-tolyl) Ril), 4, 4'-azobis (4-cyananovaleric acid), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropionamidoxime), 2, 2'-azobis (2-(2--imi) 1-yl) propane), 2,2'-azobis (2,4,4 trimethylpentane) and other initiators, benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperu Development of peracid compounds such as oxides and tamen hydroperoxides Agent, diethoxyacetophenone, 2-hydroxy-2-methyl 1-phenylpropane monoone, benzyldimethylketal, benzyl-β-methoxyethylacetal, 1- (4-isopropylphenol) 2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-1-2-propyl) ketone, 1-hydroxycyclohexyl phenol ketone, 4-phenoxydichloroacetophenone Aromatic initiators such as 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, 1- (4 dodecylphenol) 2 hydroxy-2-methylpropane 1-on, etc. Can be mentioned. Also, disulfide initiators such as tetraethylthiilamdisulfide, -troxyl initiators such as 2,2,6,6-tetramethylbiperidine 1-oxyl, 4,4'-di-tert-butyl-2 Living radical polymerization initiators such as, 2'-bipyridine copper complex-trichloromethyl acetate complex can also be used.

 [0080] Acid catalysts include activated clays, clays such as acid clays, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as ρ-toluenesulfonic acid and trifluoroacetic acid, aluminum chloride, ferric chloride, chloride Lewis acids such as stannic, titanium trichloride, titanium tetrachloride, boron trifluoride, hydrogen fluoride, boron trifluoride, aluminum bromide, gallium chloride, gallium bromide, solid acids such as Various materials such as zeolite, silica, alumina, silica'alumina, cation exchange resin, and heteropolyacid (for example, phosphotungstic acid, phosphomolybdic acid, key tungstic acid, and chemolybdenic acid) can be used.

 [0081] Examples of the basic catalyst used in the present invention include Li CO, Na CO, and K CO.

 2 3 2 3 2 3

 Li metal carbonate, alkaline earth metal carbonate such as BaCO, CaCO, Li 0, Na 0, K O

 Alkali metal oxides such as 3 3 2 2 2, 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 Examples thereof include alkoxides such as sodium, potassium, rubidium and cesium.

 [0082] Specific examples of the polymerizable compound capable of forming the host compound according to the present invention will be given below.

1S The present invention is not limited to these. The host compound according to the present invention may be a polymer formed by polymerizing the polymerizable compound, which may be used alone.

[0083] [Chemical 15]

[0084] [Chemical 16]

[0085] [Chemical 17]

[0086] [Chemical 18]

[0087] [Chemical 19]

[0088] [Chemical 20]

 [0089] <Layer structure of organic electoluminescence device>

 The layer structure of the organic electoluminescence device (organic EL device) according to the present invention will be described.

 [0090] The organic EL 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 contains a phosphorescent compound. It is.

[0091] In a broad sense, the light emitting layer according to the present invention is a layer that emits light when an electric current is applied to an electrode having a cathode and an anodic force. This refers to a layer containing a compound that emits light.

[0092] The organic layer according to the present invention is sandwiched between a cathode and an anode, which may have a hole transport layer, an electron transport layer, a cathode buffer layer, a cathode buffer layer, etc. in addition to the light emitting layer, if necessary. Take the structure. Specific examples include the structures shown below.

[0093] (i) Anode Z hole transport layer Z light emitting layer Z cathode

 (ii) Anode Z light emitting layer Z electron transport layer Z cathode

 (iii) Anode Z hole transport layer Z light emitting layer Z electron transport layer Z cathode

 (iv) Anode Z Anode buffer layer Z Hole transport layer Z Light emitting layer Z Electron transport layer Z Cathode buffer layer Z cathode

In the organic layer according to the present invention, the light emitting layer is formed by a coating method, but the other layers are vapor deposition methods, It may be formed by any coating method. In the coating method, spin coating, dip coating, roll coating, bar coating, flexographic printing, screen printing, offset printing, and ink jetting are used, and an inkjet method is preferable.

 [0094] Of the plural layers sandwiched between the electrodes (anode and cathode) constituting the organic EL device of the present invention, the organic layer is preferably 2 layers or more, more preferably 3 layers or more. .

[0095] << Light-emitting layer >>

 The light emitting layer of the organic EL device of the present invention contains a phosphorescent compound represented by the above general formula (1), and examples of the host compound include the above general formulas (2), (3), (4 And a compound selected from the group consisting of compounds (5) and (5).

 [0096] The phosphorescent compound according to the present invention is a compound in which luminescence with an excited triplet force is observed, and is a compound that emits phosphorescence at room temperature (25 ° C). A compound having a rate of 0.01 or more at 25 ° C. The phosphorescence quantum yield is preferably 0.1 or more.

 [0097] The phosphorescent quantum yield can be measured by the method described in the fourth edition of Experimental Chemistry Course 7, Spectroscopy II, page 398 (1992 edition, Maruzen). Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum compound used in the present invention can achieve the above phosphorescence quantum yield in any solvent. If you do.

 [0098] In the present invention, the host compound is a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.01 at room temperature (25 ° C) among the compounds contained in the light emitting layer. Defined as a compound.

 [0099] Furthermore, a plurality of host compounds may be used in combination. By using multiple types of host compounds, it is possible to adjust the movement of electric charge, and the organic EL device can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the type of phosphorescent compound and the amount of doping, and it can also be applied to lighting and knocklights.

[0100] The host compound according to the present invention may be used in combination with a conventionally known compound. For example, the host compound has a hole transporting ability and an electron transporting ability, and prevents the emission of light from being increased in wavelength. A compound having a Tg (glass transition temperature) is preferred. The host compound has one of hole injection or transport and electron barrier properties. For example, a force rubazole derivative, a carboline derivative, a diaza force rubazole derivative, a triazole derivative, an oxadiazole derivative. , Imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazophane derivatives, fluorenedamine derivatives, arylamine derivatives, phanantorin derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, organometallics Compounds, arylmethane derivatives, etc.

[0101] Among these, it is preferable to use a force rubazole derivative, a carboline derivative, or a diaza force rubazole derivative.

 [0102] Further, as the light-emitting compound, a conventionally known phosphorescent compound or a fluorescent compound (also referred to as a fluorescent compound) may be used in combination.

[0103] Specific examples of phosphorescent compounds that can be used in combination are shown below, but are not limited thereto. In addition, these compounds can be synthesized by, for example, the method described in Inorg. Chem. 40 卷, 1704-1711. Furthermore, these compounds may or may not have a polymerizable group or a reactive group.

[0104] [Chemical 21]

[0105] [Chemical 22]

[ZZ ^ [9010]

[0107] [Chemical 24]

D-1

D-4

Five]

D—5 D-6

[0109] The fluorescent compound used in the present invention is a compound that, by containing a fluorescent compound, can emit fluorescent light having a maximum emission wavelength different from the case where it does not contain, preferably in a solution state. The fluorescence quantum yield is high. Here, the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more. Specific fluorescent compounds include, for example, coumarin dyes, anthracene dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes. Examples thereof include dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors. The fluorescence quantum yield here can be measured by the method described on page 362 (1992 edition, Maruzen) of Spectroscopy II, 4th edition, Experimental Chemistry Course 7.

 [0110] Specific examples of the fluorescent compound used in the present invention are shown below, but the present invention is not limited thereto.

[0111] [Chemical 26]

 [0112] The film thickness of the light emitting layer thus formed can be appropriately selected according to the situation where there is no limit. It is preferable to adjust the film thickness to a range of ˜5 μm.

Next, other layers constituting the organic EL device 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. [0114] << 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, the electron injection layer, or the electron transport layer are injected into the light emitting layer and the hole. An electron barrier existing at the interface of the layer or the hole transport layer is accumulated at the interface in the light emitting layer, and the light emitting efficiency is improved.

 [0115] <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 a property of transmitting the holes injected from the anode to the light emitting layer. Conventionally, in photoconductive materials, those conventionally used as hole charge injecting and transporting materials, and known materials used in hole injection layers and hole transporting layers of EL devices are not particularly limited. Any one can be selected and used.

 [0116] The hole injecting material and the hole transporting material have either hole injection or transport and 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 pyrazophan derivatives, furan diamine derivatives, arylamine derivatives, and amino-substituted chalcone derivatives. Oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazole derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, or conductive polymer oligomers, particularly thiophene oligomers.

[0117] The ability to use the above-mentioned materials as the hole injection material and the hole transport material. Use of porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly aromatic tertiary amine compounds. Preferred.

[0118] Representative examples of the above aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N' —tetraphenyl 4,4 ′ — diaminophenol; N , N ′ —Diphenyl N, N ′ —Bis (3-methylphenol) 1 [1, 1 ′ —Biphenyl] 4,4 ′ —Diamine (TPD); 2, 2—Bis ( 4-di-p-tolylaminophenol) propane; 1, 1-bis (4-di-p —Tolylaminophenyl) cyclohexane; N, N, N ′, N ′ —tetra-l-tril-l, 4,4′-diaminobiphenyl; 1, 1 bis (4-di-l-r-tri-laminophenyl) 4 phenyl cyclo Hexane; Bis (4-dimethylamino-2-methylphenol) phenylmethane; Bis (4-di-tri-triaminophenol) phenolmethane; Ν, N'-Diphenyl Ν, N'-Di (4-methoxyphenol- 1) 4, 4 '— Diaminobiphenyl; Ν, Ν, Ν', N '— Tetraphenyl diru 4, 4' — Diaminodiphenyl ether; 4, 4 '— Bis (diphenylamino) quadriphenyl; —, Ν, ト リ Tri (ρ-trilyl) amine; 4— (Di-ρ-trilylamino) — 4 ′ — [4 -— (Di-ρ-trilylamino) styryl] stilbene; 4-— Ν, フ Diphenylamine (2-diphenyl) -Ruby) benzene; 3-Methoxy-4 '— Ν, Ν Diphenylaminos Benzene, Ν-carbcarbazole, and those having two condensed aromatic rings described in US Pat. No. 5,061,569, for example, 4, 4 ′ bis [Ν- ( 1-Naphthyl) [Fulumino] bifural (α-NPD), described in Japanese Patent Application Laid-Open No. 4 308688, three triphenylamine units connected in a starburst type 4, 4 ' , "-Tris [? ^-(3-methylphenol) -l-phenolamino] triphenylamine (MTDATA), etc. These materials have been introduced into polymer chains, or these A polymer material in which the material is a polymer main chain can also be used.

 [0119] Alternatively, inorganic compounds such as ρ-type Si and p-type SiC can also be used as the hole injection material and the hole transport material. For this hole injection layer and hole transport layer, the above hole injection material and hole transport material are formed into a thin film by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Can be formed.

 [0120] (Hole injection layer thickness, hole transport layer thickness)

 The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are preferably adjusted to a range of 5 nm to 5 μm @. The hole injection layer and the hole transport layer may be a single layer structure of one or more of the above materials, or may be a laminated structure including a plurality of layers having the same composition or different compositions.

 [0121] << Electron Transport Layer, Electron Transport Material >>

The electron transport layer according to the present invention is not particularly limited as long as it has a function of transmitting electrons injected from the cathode to the light emitting layer. Can be used.

 [0122] Examples of materials used in this electron transport layer (hereinafter referred to as electron transport materials) include: -to-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, and heterocyclic rings such as naphthalene perylene. Examples thereof include tetracarboxylic anhydride, carbodiimide, fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxadiazole derivative, and organometallic complex. Further, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxaziazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transporting 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.

 [0123] or 8 Metal complexes of quinolinol derivatives, for example, tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-dibromone 8 The central metal of these metal complexes is quinolinol) aluminum, tris (2methyl 8-quinolinol) aluminum, tris (5-methyl 8-quinolinol) aluminum, bis (8-quinolinol) zinc (Zn q), etc. Metal complexes replacing In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials.

 [0124] In addition, metal-free or metal phthalocyanine, and those having a terminal substituted with an alkyl group or a sulfonic acid group can be preferably used as an electron transporting material. Alternatively, the distyrylvirazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, n-type mono-Si, n-type—such as SiC A semiconductor can also be used as an electron transport material.

 [0125] (film thickness of electron transport layer)

 The thickness of the electron transport layer is not particularly limited, but is preferably adjusted to a range of 5ηπι to 5 / ζm. The electron transport layer may have a single layer structure that is one or two or more of these electron transport materials, or may have a laminated structure that includes a plurality of layers having the same composition or different compositions.

Furthermore, in the present invention, a buffer layer (electrode interface layer) may exist between the anode and the light emitting layer or hole injection layer and between the cathode and the light emitting layer or electron injection layer. [0127] The nofer 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 industrial front line (November 30, 1998) 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “Nuichi” Co., Ltd.), and has an anode buffer layer and a cathode buffer layer.

 [0128] The details of the anode buffer layer are also described in JP-A-9-45479, JP-A-9260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is described in detail. One representative phthalocyanine buffer, one acid buffer such as acid vanadium, one buffer buffer, one amorphous carbon buffer, one polymer buffer using a conductive polymer such as polyarrin (emeraldine) polythiophene, etc. Is mentioned.

 [0129] The details of the cathode buffer layer are also described in JP-A-6-325871, JP-A-917574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. A metal buffer layer represented by lithium fluoride, an alkali metal compound layer represented by lithium fluoride, an alkaline earth metal compound represented by magnesium fluoride, a nofer layer, an aluminum oxide, and an acid salt represented by lithium oxide. For example, a single layer buffer.

 [0130] The thickness of the buffer layer is preferably in the range of 0.1 nm to LOOnm, although it depends on the material desired to be a very thin film.

 [0131] 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” Device and its industrialization front line (November 30, 1998, issued by NTT S) ", page 237, etc., and has a functional layer such as a hole blocking layer. Te hey.

 [0132] << Electrode >>

Next, the electrodes of organic EL elements will be explained. The electrode of the organic EL element consists of a cathode and an anode. As the anode in this organic EL device, 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 Cul, indium tin oxide (ITO), SnO, and ZnO. [0133] The anode may be formed by forming 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 pattern accuracy is not required. If not (about 100 m or more), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. In the case where light emission is extracted from this anode, it is desirable that the transmittance be greater than 10%, or the sheet resistance as the anode is preferably several hundred Ω / mouth 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.

 [0134] On the other hand, as the cathode, those having a small work function! / E (4 eV or less) metal (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 Z copper mixture, magnesium Z silver mixture, magnesium z aluminum mixture, magnesium Z indium mixture, aluminum Z aluminum oxide.

 -UM (Al 2 O 3) mixture, indium, lithium

 3 Z aluminum mixture, rare earth metal etc.

2

 Is mentioned. Among these, from the viewpoint of electron injectability and durability against acids, etc., a mixture of an electron injectable metal and a second metal, which is a stable metal having a larger work function value than this, for example, magnesium Z Silver mixture, magnesium Z aluminum mixture, magnesium Z indium mixture, aluminum Z acid aluminum (Al o) mixture, lithium

 twenty three

 Z aluminum mixtures and the like are preferred.

 [0135] The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Alternatively, the sheet resistance as the cathode is preferably several hundred ΩΖ 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 order to transmit light, if either the anode or the cathode of the organic EL element is transparent or translucent, it is advantageous because the light emission efficiency is improved.

 [0136] << Base material >>

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

[0137] Examples of the base material that can be used in the organic EL device of the present invention include glass and plastic. The type is not particularly limited, and is not particularly limited as long as it is transparent. Examples of the substrate preferably used include glass, quartz, and a transparent film. Particularly preferably, the base material is a transparent film capable of giving flexibility to the organic EL element.

 [0138] Specifically, a homopolymer or copolymer such as ethylene, polypropylene, or butene, or a polyolefin (PO) resin such as a copolymer, or an amorphous polyolefin resin such as a cyclic polyolefin (APO). ), Polyethylene terephthalate (PET), polyethylene 2, 6 naphthalate (PEN), etc., polyamide 6, nylon 12, copolymer nylon (PA), such as copolymer nylon, polybula alcohol (PVA) ) Resin, Polybulal alcohol-based resin such as ethylene butyl alcohol copolymer (EVOH), Polyimide (PI) resin, Polyterimide (PEI) resin, Polysulfone (PS) resin, Polyethersulfone (PES) resin, Polyetheretherketone (PEEK) resin, Polycarbonate (PC) resin, Polybutyl butyrate (PVB) resin, Polyarylate (PAR) resin, Ethylene tetrafluoride Copolymer (ETFE), Ethylene Trifluoride Chloride (PFA), Tetrafluorinated Tylene Perfluorinated Alkyl Bulle Ether Copolymer (FEP), Vinylidene Fluoride (PVDF), Vinylene Fluoride (PVF) Fluorine-based resins such as ethylene / perfluoroethylene / perfluoropropylene / perfluorobiene-reutero copolymer (EPA) can be used.

 [0139] In addition to the above-mentioned rosins, a rosin composition comprising an acrylate compound having a radical-reactive unsaturated compound, or a mercapto compound having a thiol group and the acrylate resin compound. A photocurable resin such as a resin composition prepared by dissolving an oligomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, etc. in a polyfunctional acrylate monomer, and a mixture thereof. Etc. can also be used. Furthermore, it is also possible to use as a base film a film obtained by laminating one or more of these resins with a means such as laminating or coating.

[0140] These materials may be used alone or in appropriate mixture. Among them, ZE NEX, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by GSJ), amorphous cyclopolyolefin resin film, Pure Ace of polycarbonate film (manufactured by Teijin), cellulose triacetate film Co-katak KC4UX, KC8UX (Co-power Commercial products such as Minoltaput Co., Ltd.) can be preferably used.

 [0141] In addition, the base material according to the present invention using the above-described resin or the like may be an unstretched film or a stretched film.

 [0142] The substrate 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 the resin as a material with an extruder, extruding it with an annular die or T-die, and quenching it. In addition, an unstretched base material is subjected to a known method such as -axial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. Alternatively, 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.

 [0143] Further, 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, etc. is performed before forming the deposited film. May be.

[0144] Furthermore, an anchor coat agent layer may be formed on the surface of the substrate according to the present invention for the purpose of improving the adhesion to the deposited film. The anchor coating agent used in this anchor coating agent layer includes polyester resin, isocyanate resin, urethane resin, acrylic resin, ethyl butyl alcohol resin, bur modified resin, epoxy resin, modified resin. Styrene resin, modified silicone resin, alkyl titanate, etc. can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The 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 the solvent, diluent, etc. are removed by drying to remove the anchor coating. can do. The coating amount of the anchor coat agent is preferably about 0.1 lg / m ^{2 to 5} g / m ² (dry state).

[0145] The substrate is conveniently a long product rolled up. Although the thickness of the base material varies depending on the use of the film obtained, it cannot be specified unconditionally. However, when the film is used for packaging, it is 3 π! ~ 40 It is preferably 0 / zm, particularly in the range of 6 μm to 30 μm.

 [0146] Further, the film thickness of the substrate used in the present invention is preferably 10 m to 200 μm, more preferably 50 μm to 100 μm.

 [0147] <Display device>

 The organic EL element 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 type that directly recognizes a still image or a moving image. It may be used as a display device (display). When used as a display device for video playback, the drive method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full color display device can be produced by using two or more kinds of the organic EL elements of the present invention having different emission colors.

 [0148] 《Light extraction technology》

 In order to improve the light extraction efficiency of the light emitted from the light emitting layer, the organic EL device of the present invention performs prism-like or lens-like processing on the surface of the substrate, or attaches a prism sheet or lens sheet to the surface of the substrate. May be.

 [0149] 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 air mouth gel, porous silica, magnesium fluoride, and fluorine-based polymer.

 [0150] 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. Further, it is preferably 1.35 or less. The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.

[0151] The organic EL device 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 one direction, only light traveling in a specific direction is diffracted. The light extraction efficiency is improved Absent. However, by making the refractive index distribution a two-dimensional distribution, the light traveling in all directions is diffracted, and the light extraction efficiency increases. As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or 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 1Z2 to 3 times the wavelength of light in the medium. The arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a Herman lattice.

 [0152] The substrate according to the present invention preferably has a gas noria layer. This has the effect of further improving the stability over time in dark spots and at high temperatures and high humidity.

 [0153] Gas barrier layer

The gas nolia 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. It is preferred that the oxygen permeability is 0.005 mlZm ² Z days or less at 23 ° C. and 0% RH. The water vapor permeability measured according to the JIS K7129 B method is preferably 0.1 lgZm ² Z days or less. Specific examples of the material constituting the gas barrier layer according to the present invention include silicon oxide, acid aluminum, acid silicon nitride, acid aluminum nitride, magnesium oxide, zinc oxide, and oxide, which are preferably inorganic oxides. Examples thereof include indium and oxide tin.

 [0154] In addition, the thickness of the gas nolia layer in the present invention varies depending on the type and configuration of the material used, and the force selected as appropriate is 5ηπ! It is preferable to be within a range of ˜2000 nm. This is because when the thickness of the gas noria layer is smaller than the above range, a uniform film cannot be obtained, and it is difficult to obtain noria properties for the gas. If the thickness of the gas noria layer is larger than the above range, it is difficult to maintain the flexibility of the gas noria film, and the gas barrier film cracks due to external factors such as bending and pulling after film formation. This is because there is a risk of occurrence.

 [0155] The gas nore layer according to the present invention comprises a raw material described later using a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method described later, a plasma under atmospheric pressure or a pressure near atmospheric pressure described later. It can be formed by applying a CVD method or the like.

FIG. 1 is an example showing the configuration of a substrate having a gas barrier layer according to the present invention. [0157] The structure and density of the substrate having the gas nolia layer according to the present invention will be described.

[0158] The gas nolia layer 21 according to the present invention has a structure in which layers having different densities are laminated on a base material 22, and an adhesive film 23, a ceramic film 24, and a protective film 25 are laminated. Fig. 1 shows an example in which three layers are stacked. 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. It should be noted that in FIG. 1, each layer is shown as one layer. If necessary, each layer may have two or more layers.

 [0159] As a method for forming an adhesion film, a ceramic film and a protective film on a substrate, a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method, atmospheric pressure or a pressure near atmospheric pressure is used. It can be formed by applying a plasma CVD method or the like. Example

 [0160] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

[0161] Example 1

 << Production of organic EL element OLED1-1 >>

 As a base material, a polyethylene naphthalate film having a thickness of 100 μm (Teijin's DuPont film, hereinafter abbreviated as PEN) (base material 1) is subjected to the following atmospheric pressure plasma discharge treatment equipment and discharge conditions. A substrate 1 having a gas barrier layer with the profile configuration shown in Fig. 1 was produced.

 [0162] (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 prepared as follows.

 [0163] The roll electrode serving as the first electrode is coated with a high-density, high-adhesion alumina sprayed film by atmospheric plasma on a titanium alloy T64 jacket roll metal base material that has cooling means using cooling water. The roll diameter was 1000 mm. On the other hand, the square electrode of the second electrode is a hollow square tube type titanium alloy T64 covered with lmm of the same dielectric material as the above under the same conditions, and is opposed to the opposing square tube type fixed electrode group. did.

[0164] Ten rectangular tube electrodes were arranged around the roll rotating electrode with the counter electrode gap being lmm. The total discharge area of the rectangular tube type fixed electrode group is 150cm (length in the width direction) X 4cm (carrying) Length in the feed direction) X 10 (number of electrodes) = 6000 cm ² . In all cases, appropriate filters were installed.

[0165] During plasma discharge, the first electrode (roll rotating electrode) is adjusted to 120 ° C and the second electrode (square tube fixed electrode group) is adjusted to 80 ° C, and the roll rotating electrode is rotated by the drive. A thin film was formed. Of the 10 rectangular tube-type fixed electrodes, 2 from the upstream side are used for the first layer (adhesion layer), and the next 6 are used for the second layer (ceramic layer). The following two were used for film formation of the third layer (protective layer), and three layers were laminated in one pass by setting each condition.

[0166] (First layer: Adhesion layer)

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

[0167] <Gas conditions>

 Discharge gas: Nitrogen gas 94.5% by volume

 Thin-film forming gas: Hexamethinoresinsiloxane (vaporized by mixing with nitrogen gas in a vaporizer manufactured by Lintec) 0.5% by volume

Additive gas: Oxygen gas 5.0 volume ^_0/0

 <Power supply conditions: Only the power supply on the first electrode side was used>

 1st electrode side Power supply type

 Frequency 80kHz

Output density lOWZcm 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 Mac Science Co., Ltd. described above.

[0168] (Second layer: Ceramic layer)

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

[0169] <Gas conditions>

 Discharge gas: Nitrogen gas 94.9% by volume

 Thin-film forming gas: hexamethinoresisiloxane (vaporized by mixing with nitrogen gas using a vaporizer manufactured by Lintec) 0.1% by volume

Additive gas: Oxygen gas 5.0 volume ^_0/0

<Power supply conditions> 1st electrode side Power supply type

 Frequency 80kHz

Output density lOWZcm ²

 Second electrode side power supply type High frequency power supply by Pearl Industries

 Frequency 13. 56MHz

Output density lOWZcm 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 MacScience.

[0170] (3rd layer: protective layer)

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

[0171] <Gas conditions>

Discharge gas: nitrogen gas 93.0 volume ^_0/0

 Thin-film forming gas: Hexamethinoresinsiloxane (vaporized by mixing with nitrogen gas in a Lintec vaporizer) 2.0 vol%

Additive gas: Oxygen gas 5.0 volume ^_0/0

 <Power supply conditions: Only the power supply on the first electrode side was used>

 1st electrode side Power supply type

 Frequency 80kHz

Output density lOWZcm ²

 The density of the third layer (protective layer) formed was 1.95 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science Co., Ltd. described above.

[0172] Results of measuring the water vapor permeability by a method according to ^{JIS K 7129B, 10- 3 g /} m 2 - was day or less. JIS-K-results of measurement of the oxygen transmission rate by a method according to 7126B, was less than 10- ² mlZm ² 'date' Mpa.

[0173] Next, after patterning was performed on a substrate on which ITO (indium tin oxide) was deposited to 120 nm on the base material 1, the substrate with the ITO transparent electrode was ultrasonically washed with isopropyl alcohol and dried. After drying with nitrogen gas, UV ozone cleaning was performed for 5 minutes. Was fixed on a substrate holder of a vacuum deposition apparatus available on the market, the pressure was reduced to a vacuum degree 4 X 10- ⁴ Pa, prepared ITO substrate 100 did.

 [0174] Next, the organic EL element OL EDI-1 of the present invention was produced using an ink jet recording method as shown in FIG. Hereinafter, the process will be described with reference to FIG.

 [0175] First, using a commercially available inkjet head 10 (KM 512S non-aqueous head manufactured by Co-Caminolta), fluid D containing the polymer of Exemplified Compound A7 and THF was discharged onto the ITO substrate 100, and 100 ° C. A hole transport layer 111 having a thickness of 50 nm was formed under the conditions of 60 minutes.

 [0176] Next, a polymer of Exemplified Compound A15 shown below as a host, Exemplified Compound 1-1 (mass ratio 100: 5) as a phosphorescent compound, and Fluid D2 containing THF are converted into holes. A light-emitting layer 112 having a thickness of 50 nm was formed on the transport layer 111 by discharging at 100 ° C. for 60 minutes.

 [0177] Next, using the inkjet head 10, a fluid D3 containing a polymer of the following exemplary compound A28 and ethyl acetate is discharged onto the light emitting layer 112, and the conditions are 100 ° C and 60 minutes. Thus, an electron transport layer 113 having a thickness of 50 nm was formed. Next, an aluminum layer 114 (cathode) having a thickness of 200 nm was formed on the electron transport layer 113 by vapor deposition.

 Further, the organic solvent content in the hole transport layer 111, the light emitting layer 112, and the electron transport layer 113 was adjusted as shown in Table 1. Further, a base material 115 having a gas nolia layer was pasted thereon to produce an organic EL element OLED1-1.

 [0179] (Synthesis of Polymer of Exemplary Compound A15)

 Example Reaction Compound A15 1.34 g (2.5 mmol), 2,2'-azobis (isobutyronitryl) (AIBN) O. 010 g (0.06 lmmol) and 30 ml of butyl acetate were placed in a reaction vessel, and the nitrogen was replaced. Thereafter, the mixture was reacted at 80 ° C for 10 hours. After the reaction, it was poured into acetone for reprecipitation, and the polymer was recovered by filtration. Purified by adding the recovered polymer chloroform solution into methanol and reprecipitating it twice, and after recovery, vacuum-dried to give the desired Exemplified Compound A15 polymer 1.20 g Got as.

 [0180] The weight average molecular weight of the obtained polymer was 10,000 in terms of polystyrene (according to GPC (gel permeation chromatography) measurement using HFIP (hexafluoroisopropanol) as an eluent).

[0181] By a similar method, a polymer of Exemplified Compound A7 (weight average molecular weight 36000) and a polymer of Exemplified Compound A 28 were synthesized. (Weight average molecular weight 26000) 《Preparation of organic EL element OLED1-2-1-13》

 In the manufacturing method of the organic EL element OLED1-1, the organic EL element OL ED 1-2-1 is the same as the manufacturing method of the organic EL element OLED1-1 except that the material of each layer is changed to the material shown in Table 1. — 13 was made.

 [0182] << Production of organic EL elements OLED1-14, 1 15 >>

 After depositing A37 as a hole transport layer with a thickness of 50 nm on a glass substrate having an indium tin oxide transparent electrode (ITO electrode) according to a conventional method, A31 as a light emitting layer, phosphorescent compound 1-60 (mass) The ratio 100: 5) is deposited with a thickness of 50 nm, and then A34 is deposited with a thickness of 50 nm as an electron transport layer. Formed. Furthermore, the organic EL elements OLED1-14 and 1-15 were fabricated by laminating the base material 1 having a gas noria layer.

 [0183] <Production of organic EL element OLED1-16>

 In the manufacturing method of the organic EL element OLED 11, the materials of each layer are changed to the materials shown in Table 1 below, and the organic EL element is replaced with a glass substrate having an indium tin oxide transparent electrode (ITO electrode). The organic EL device OLED1-16 was manufactured by the same manufacturing method as the EL device OLED1-1.

 [0184] Table 1 shows the organic solvent contents of the organic layers of organic ELOLED1-1 to 1-16. The measurement method was the method described above.

[0185] [Table 1]

Light emitting layer (50nm)

 Organic EL device hole transport layer Electron transport layer Organic layer

 Host Host dopant Remarks No. (50nm) (50nm) Organic solvent content

 No. Molecular weight (5% by mass)

 OLED 1-1 A 7 A 15 10000 1-1 A 28 22ppm The present invention

OLED 1-2 A 7 A 15 10000 1 1 2 A 27 lOppm The present invention

OLED 1-3 A 16 A15 250000 1 31 A 28 15ppm The present invention

OLED 1-4 A 38 A43 512.6 1 1 2 A 32 llppm The present invention

OLED 1-5 A 37 A 40 408.5 1 1 17 A 30 15 ppm The present invention

OLED 1-6 A 36 A 46 498.6 1 1 20 A35 18ppi The present invention

OLED 1-7 A37 A 47 498.6 1 32 A 32 lOppra

OLED 1-8 A 38 A 40 408.5 1 -14 A 32 15ppm The present invention

OLED 1 9 A 37 A 46 498.6 1 -60 A 35 68 ppm The present invention

OLED 1 1 10 A 36 A 47 498.6 1 -72 A 30 lOppm The present invention

OLED 1 11 A 36 A31 484.6 Ir-12 A35 130ppm Comparative example

OLED 1 -12 A 37 A31 484.6 1 -60 A 34 120ppm

OLED 1 -13 A 37 A 31 484.6 1 -60 A 34 0.06ppm The present invention

OLED 1 14 A 37 A 31 484.6 1 -60 A 34 1500ppm Comparative example

OLED 1 -15 A37 A31 484.6 1 -60 A 34 0.003ppm Comparative example

OLED 1 -16 A 37 A31 484.6 1 60 A 34 22ppm

[0186] << Evaluation of organic EL elements >>

 The organic EL devices obtained as described below were evaluated and the results are shown in Table 1.

 [0187] (Light emission brightness)

To measure the light emission luminance (cdXm ² ) when an organic EL device temperature is 23 ° C and a 10V DC voltage is applied. Luminance was expressed as a relative value when OLED1-11 is set to 100. The emission luminance was measured using CS-1000 (manufactured by Co-Camino Norta Sensing).

[0188] (Dark spot)

In addition, after driving at a constant current of 15 mAZcm ² for 30 hours, the number of non-luminous spots (dark spots) that can be visually confirmed in a 2 mm × ² mm square range was measured.

[0189] (Voltage increase rate)

 When driving at a constant current of lOmA / cm, 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.

[0190] (Stability over time)

The organic EL device was stored for one month at 60 ° C and 70% Rh. cd / m ² ) was measured. The stability over time was expressed as a relative value with respect to the measured emission luminance before storage.

 [0191] The results obtained are shown in Table 2.

[0192] [Table 2]

[0193] From Table 2, compared to the comparison, in the organic EL device of the present invention, the dark spot and the voltage increase rate were significantly reduced, the temporal stability was improved, and the emission luminance was also improved. In addition, the improvement effect was more noticeable when using a substrate with one gas layer than a glass substrate.

 [0194] Example 2

A green light-emitting organic EL device prepared in the same manner as in Example 1 except that the phosphorescent compound of the organic EL device OLED1-1 of the present invention prepared in Example 1 was replaced with Ir 1, and the organic EL device of the present invention. A red light-emitting organic EL device fabricated in the same way except that the phosphorescent compound of the element OLED1-1 was replaced by Ir-9 was placed side by side on the same substrate to produce the active matrix type full-color display device shown in Fig. 4. did. FIG. 5 shows only a schematic diagram of the display portion A of the produced full-color display device. That is, a plurality of scanning lines 5 and data lines 6 are included on the same substrate. It has a wiring section and a plurality of juxtaposed pixels 3 (light emission color is a red area pixel, a green area pixel, a blue area pixel, etc.), and the scanning line 5 and the plurality of data lines 6 of the wiring section are Each of them is made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are not shown).

 The plurality of pixels 3 are driven by an active matrix system in which an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor are provided, and scanning from a scanning line 5 When a signal is applied, it receives an image data signal from the data line 6 and emits light according to the received image data. In this way, full-color display is possible by appropriately juxtaposing the red, green, and blue pixels.

 [0196] By driving the full-color display device, a clear full-color moving image display was obtained.

 [0197] Example 3

 <Production of lighting device>

 The non-light emitting surface of each of the organic EL elements emitting blue light, green light and red light produced in Example 2 was covered with a glass case to obtain a lighting device.

[0198] Example 4

 <Production of organic EL element OLED4-1>

 An organic EL element OLED4-1 was produced in the same manner as in the production of the organic EL element OLED1-1 of Example 1, except that the materials and film thicknesses shown in Table 3 were changed. In Table 3, “%” represents mass ratio (%).

[0199] [Table 3] Organic EL element Organic layer Material Film thickness (rrm)

 Hole injection layer A 39 40

 Hole Transport Exhibition A 36 10

 A 43 (97%)

 Light emitting layer 1 15

 1 1 1 (3%)

 Intermediate eyebrow 1 A 40 5

 A 43 (92%)

 0LE04 1 1 9

 I r-9 (8%)

 Middle layer 2 A 43 5

 A 43 (95%)

 Light emitting layer 3 5

 I r-1 (5%)

 Hole blocking layer A 33 10

Electron transport layer A 35 50 [0200] The drying conditions were adjusted so that the solvent content of the organic layer was 25 ppm. Next, aluminum having a thickness of 200 nm was deposited thereon. For sealing, the substrate 1 was attached in the same manner as the organic EL element OLED1-1.

 [0201] The produced organic EL element OLED4-1 was provided with a glass case with a reflective coating on the non-light-emitting surface side in the same manner as in Example 3 to provide an illumination device. The obtained illuminating device was able to be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

 [0202] Next, the color reproduction range when combined with a color filter commercially available for display was evaluated. It was confirmed that the combination of the organic EL element 41 and the color filter has excellent performance in color reproducibility with a wide color gamut.

Claims

An organic electoluminescence device having at least one organic layer between an anode and a cathode on a substrate, wherein at least one layer of the organic layer is phosphorescence represented by the following general formula (1) An organic electoluminescence device comprising a light-emitting layer containing an organic compound, wherein the organic layer contains 10-pm to 103 ppm of an organic solvent.

 [Chemical formula 1] General formula (1)

[Wherein, R represents a substituent. Z is a group of nonmetallic atoms necessary to form a 5- to 7-membered ring

 1

 Represents. nl represents an integer of 0 to 5. B to B are carbon atom, nitrogen atom and oxygen atom, respectively.

 1 5

 Alternatively, it represents a sulfur atom, and at least one of B to B represents a nitrogen atom. M is the element circumference

 1 5 1 Represents Group 8 to Group 10 metals in the Periodic Table. X and X are carbon atoms and nitrogen atoms, respectively.

 1 2

 Or an oxygen atom, and L represents a group of atoms that form a bidentate ligand with X and X.

 1 1 2

 The ml represents an integer of 1, 2 or 3, m2 represents a force of 0, 1 or 2 and ml + m2 represents 2 or 3. ]

 [2] The organic electroluminescent device according to claim 1, wherein the organic layer contains an organic solvent in an amount of 0.1 ppm to LOOppm.

[3] The organic electroluminescent device according to claim 1 or 2, wherein the light emitting layer contains a polymer compound having a weight average molecular weight of 5000 or more as a host compound.

 [4] The organic electoluminescence device according to any one of [1] to [3], wherein a gas barrier layer is provided on the substrate.

[5] According to any one of claims 1 to 4, wherein the light emission is blue. The organic-elect mouth luminescence element of description.

 [6] The organic electoluminescence device according to any one of [1] to [4], wherein the light emission is white.

[7] A display device comprising the organic electoluminescence device according to any one of [1] to [6].

[8] An illuminating device comprising the organic electoluminescence device according to any one of [1] to [6].

[9] A display device comprising the illumination device according to claim 8 and a liquid crystal element as display means.