JP5857724B2 - ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE, LIGHTING DEVICE, AND ORGANIC ELECTROLUMINESCENT ELEMENT MANUFACTURING METHOD - Google Patents

Description

The present invention relates to an organic electroluminescent element material, an organic electroluminescent element, a display device , a lighting device, and an organic electroluminescent manufacturing method , and in particular, excellent in luminous efficiency, luminous lifetime, and color purity, and further excellent in driving voltage. the organic electroluminescence device and a material, a method of manufacturing a display device and an illumination apparatus and such organic electroluminescent device using such an organic electroluminescence element.

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

  On the other hand, an organic EL element has a structure in which a light emitting layer containing a compound that emits light 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 by utilizing the emission of light (fluorescence, phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Furthermore, since the organic EL element is a self-luminous type, the viewing angle is wide, the visibility is high, and the thin film type solid-state element has attracted attention from the viewpoints of space saving and portability. For future practical use, it is desired to develop an organic EL device that emits light with high power, high efficiency and low power consumption.

  As such an organic electroluminescence element, a fluorescent emission type using light emission from an excited singlet, a phosphorescent type using light emission from an excitation triplet, and the like are known as a light emitter.

  In the case of using light emission from an excited singlet, the generation ratio of singlet excitons and triplet excitons is 1: 3. Therefore, the generation probability of luminescent excited species is 25%, and the light extraction efficiency is about Since it is 20%, the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  On the other hand, the organic EL device using phosphorescence emission from the excited triplet has an upper limit of 100% on the internal quantum efficiency, so that in principle the emission efficiency is four times that of the excited singlet, Since there is a possibility that a performance almost equal to that of a cathode tube may be obtained, it is also attracting attention as a lighting application. Such phosphorescent emitters have been studied mainly with transition metal complexes such as iridium complexes or platinum, and typical examples include orthometalated iridium complexes.

  These complexes are referred to as phosphorescent dopants because they are used by being dispersed and added in a light emitting layer together with a light emitting host material (or simply referred to as a host).

Since the performance (emission efficiency, emission lifetime, emission color, etc.) of the organic EL element varies greatly depending not only on the dopant but also on the host, the development of both has been conducted vigorously.
For example, in order to obtain high luminous efficiency, in the 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. In Thompson et al., Various electron transport materials are used as phosphorescent compound hosts, and they are doped with a novel iridium complex.

In any method, by appropriately selecting and using a dopant and a host, the light emission luminance and light emission efficiency of the light emitting device are greatly improved as compared with the conventional device. There was a problem that it was shorter than the fluorescent element.
In particular, in the case of a blue light emitting device, the emission lifetime is extremely shortened, and a combination of a blue dopant and a host that satisfies all of high emission efficiency, short wavelength, and long lifetime has not yet been found, and its creation is an urgent need. is there.

  In addition, development of a blue host that greatly affects the performance of an organic EL element has been actively conducted, and a host material using a dibenzofuran derivative has been studied (for example, see Patent Document 1). Furthermore, a host in which a phenylene group is combined with a dibenzofuran derivative has been studied (for example, see Patent Documents 1 to 3).

International Publication No. 2006/128800 International Publication No. 2008/072596 International Publication No. 2009/008099

  However, even if any of the above-described compounds is used, the light emission efficiency and the light emission lifetime of the organic EL device are insufficient, and further improvement in device performance is desired.

Accordingly, an object of the present invention is to provide an organic EL element having high light emission efficiency and a long lifetime, a display device and an illumination device using the element, and a method for manufacturing the element . It is another object of the present invention to provide an organic EL element with high emission efficiency, a display device and an illumination device including the element, and a method for manufacturing the element, regardless of the type of the luminescent dopant.

In order to achieve the above object of the present invention, according to one aspect of the present invention,
Following general formula (2-1 -1) or (2 1 2) A material for an organic electroluminescence device characterized by being represented by is provided.

In the general formula (2-1 -1) and (2-1-2), A represents a heteroaromatic ring group, or aromatic hydrocarbon groups as the bound heteroaromatic radical, B is a hydrocarbon aromatic to display the ring group or heteroaromatic ring group. X and Y represent an oxygen atom or a sulfur atom, Z represents a monocyclic arylene group, a combination of monocyclic arylene groups, a monocyclic heteroarylene group, a combination of monocyclic heteroarylene groups, or a monocyclic arylene group And a monocyclic heteroarylene group .

According to another aspect of the invention,
A pair of electrodes;
An organic layer provided between the pair of electrodes and including a light-emitting layer,
An organic electroluminescent device is provided, wherein the organic electroluminescent device material is contained in at least one of the organic layers.

According to yet another aspect of the invention,
A display device comprising the organic electroluminescence element is provided.

According to yet another aspect of the invention,
Provided is a lighting device comprising the organic electroluminescence element.
According to yet another aspect of the invention,
In the method for producing an organic electroluminescence element for producing the organic electroluminescence element,
There is provided a method of manufacturing an organic electroluminescence element, wherein at least one of the organic layers is formed by a wet process.

According to the present invention, it is possible to provide an organic EL element having high luminous efficiency and a long lifetime, a display device and an illumination device including the element, and a method for manufacturing the element . Furthermore, it is possible to provide an organic EL element with high emission efficiency, a display device and an illumination device including the element, and a method for manufacturing the element regardless of the type of the luminescent dopant.

It is the schematic perspective view which showed an example of the structure of the display apparatus of this invention. It is the schematic perspective view which showed an example of the structure of the display part shown in FIG. It is a schematic perspective view which shows an example of the illuminating device using the organic EL element of this invention. It is a schematic perspective view which shows an example of the illuminating device using the organic EL element of this invention.

  Hereinafter, preferred embodiments of the present invention will be described.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described.
In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode // hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode Buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode

The light emitting layer may form a unit to form a light emitting layer unit. Further, a non-light emitting intermediate layer may be provided between the light emitting layers, and the intermediate layer may include a charge generation layer.
The organic EL element of the present invention preferably emits white light and is preferably a lighting device using these.

  Hereinafter, each layer which comprises the organic EL element of this invention is demonstrated.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided with a single layer or a plurality of layers.

  An electron transport material (including a hole blocking material and an electron injection material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer. Can be selected from any conventionally known compounds.

Examples of conventionally known materials used for the 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, And azacarbazole derivatives including carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives, and the like. Here, the azacarbazole derivative refers to one in which one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom.
In the oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.
Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.

In addition, metal-free or metal phthalocyanine, or those having the terminal substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material.
Further, similarly to the hole injection layer and the hole transport layer, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.

  The electron transport layer is made of an electron transport material such as a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an ink jet method, a printing method, or a spraying method. The film can be formed by a known thinning method such as a coating method, a curtain coating method, or an LB method (Langmuir Brodgett method).

  Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. This electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. For example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  Hereinafter, although the specific example of the conventionally well-known compound (electron transport material) preferably used for formation of the electron carrying layer of the organic EL element of this invention is given, this invention is not limited to these.

  In addition, a compound represented by the following general formula (R-1) is more preferably used for forming the electron transport layer of the organic EL device of the present invention.

In the general formula (R-1), G _{1 to} G ₈ represent a nitrogen atom or —C (Rs) ═, and at least one of the G _{1 to} G ₈ represents a nitrogen atom. Rr is a substituent, and is preferably an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group. Rs represents a hydrogen atom or a substituent, and the substituent represented by Rs is preferably an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group, and an aromatic hydrocarbon group or It is more preferably an aromatic heterocyclic group.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferably adjusted to a range of 2 nm to 5 μm, more preferably adjusted to a range of 2 nm to 200 nm, and particularly preferably adjusted to a range of 5 nm to 100 nm.

  For the formation of the light-emitting layer, a light-emitting dopant or a host compound, which will be described later, is used, for example, a vacuum deposition method, a wet coating method (also referred to as a wet process, for example, a spin coating method, a casting method, a die coating method, a blade coating method, , An inkjet method, a printing method, a spray coating method, a curtain coating method, an LB method (Langmuir Brodgett method) and the like.

  The light emitting layer of the organic EL device of the present invention contains a light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant, phosphorescent dopant group) or fluorescent dopant) compound and a light emitting host compound. Is preferred.

(1) Luminescent dopant compound A luminescent dopant compound (also referred to as a luminescent dopant) will be described.
As the light-emitting dopant, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used.

(1.1) Phosphorescent dopant (also called phosphorescent dopant)
The phosphorescent dopant according to the present invention will be described.
The phosphorescent dopant compound according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

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

There are two types of light emission of the phosphorescent dopant in principle.
One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the luminescent host compound, and this energy is transferred to the phosphorescent dopant to obtain light emission from the phosphorescent dopant. Energy transfer type.
The other is a carrier trap type in which a phosphorescent dopant serves as a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant compound is obtained.
In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

In the range which does not impair the objective effect of this invention, you may use together the compound etc. which are described in the following patent gazettes in the light emitting layer which concerns on the organic EL element of this invention.
For example, International Publication No. 00/70655, JP 2002-280178, JP 2001-181616, JP 2002-280179, JP 2001-181617, JP 2002-280180, JP 2001-247859 A, JP 2002-299060 A, JP 2001-313178 A, JP 2002-302671 A, JP 2001-345183 A, JP 2002-324679 A, International Publication. No. 02/15645, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-2002 A. No. 117978, Japanese Patent Application Laid-Open No. 2002-33858 JP, JP-A-2002-170684, JP-A-2002-352960, WO01 / 93642, JP-A-2002-50483, JP-A-2002-1000047, JP-A-2002-173684. JP-A-2002-359082, JP-A-2002-175484, JP-A-2002-363552, JP-A-2002-184582, JP-A-2003-7469, JP-A-2002-525808, JP 2003-7471, JP 2002-525833, JP 2003-31366, JP 2002-226495, JP 2002-234894, JP 2002-2335076, JP 2002 No. 2411751, JP 2001-319779 A. JP, 2001-319780, 2002-62824, 2002-100474, 2002-203679, 2002-343572, 2002-203678, etc. It is.

(1.2) Fluorescent dopants Fluorescent dopants (also referred to as fluorescent compounds) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamines. And dyes having a high fluorescence quantum yield, such as laser dyes, and the like, dyes based on dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

(1.3) Combined use with conventionally known light-emitting dopants The light-emitting dopants may be used in combination of a plurality of compounds, and combinations of phosphorescent dopants having different structures or phosphorescent dopants and fluorescent dopants. You may use it in combination.

  Here, specific examples of usable luminescent dopants are given as the luminescent dopant, but the present invention is not limited thereto.

(2) Host compound The host compound contained in the light emitting layer of the organic EL device of the present invention is preferably a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C) of less than 0.1, More preferred is a compound having a phosphorescence quantum yield of less than 0.01.

  As the host compound, one type of compound may be used alone, or a plurality of types of compounds may be used in combination.

  The light-emitting host compound used in the present invention is not particularly limited in terms of structure, but typically, a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, Those having a basic skeleton such as an oligoarylene compound, or a carboline derivative or a diazacarbazole derivative (here, a diazacarbazole derivative is a compound in which at least one carbon atom of a hydrocarbon ring constituting a carboline ring of a carboline derivative is nitrogen Represents an atom substituted with an atom.) And the like.

  The host compound used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). Good.

  As the host compound, a compound having a hole transporting ability and an electron transporting ability, which prevents emission of longer wavelengths and has a high Tg (glass transition temperature) is preferable.

  In the present invention, the light emitting layer may have three layers. In that case, the host compound may be different for each light emitting layer, but when the same compound is used, excellent driving life characteristics and chromaticity are obtained. It is preferable because stability can be obtained.

  In addition, the host compound preferably has a lowest excited triplet energy (T1) larger than 2.7 eV because higher luminous efficiency can be obtained. The lowest excited triplet energy as used in the present invention refers to the peak energy of the emission band corresponding to the transition between the lowest vibrational bands of the phosphorescence emission spectrum observed at a liquid nitrogen temperature after dissolving the host compound in a solvent.

In the present invention, a compound having a glass transition point of 90 ° C. or higher is preferable, and a compound having a glass transition temperature of 130 ° C. or higher is preferable because excellent driving life characteristics can be obtained.
Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

  In the organic EL device of the present invention, since the host material is responsible for carrier transport, a material having carrier transport capability is preferable. Carrier mobility is used as a physical property representing carrier transport ability, but the carrier mobility of an organic material generally depends on the electric field strength. Since a material having a high electric field strength dependency easily breaks the balance of hole and electron injection / transport, it is preferable to use a material having a low electric field strength dependency of mobility for the intermediate layer material and the host material.

Here, the present inventors considered the factors that hinder the improvement of the luminous efficiency and the durability with respect to the above-described problems of the present invention.
In the study by the present inventors, when various host compounds and various dopant compounds are used in the light emitting layer, the emission characteristics (emission efficiency, drive voltage and emission spectrum) and durability of the organic EL element change, and the host It was found that the compound and the dopant compound include a combination having a good compatibility and a combination having a poor compatibility. Although the cause is still unknown, various interactions such as host compounds (H-H), host compound and dopant compound (HD), and dopant compounds (DD) occur in the light emitting layer. It is speculated that these interactions cause differences in the transport properties of carriers such as anions and cations and the stability of excitons generated by the binding of each carrier, resulting in changes in emission characteristics and durability. ing.

  In response to the above considerations, the present inventors have focused on various host compounds having dibenzofuran and dibenzothiophene as partial structures, and represented by the general formula (1) having a specific partial structure containing dibenzofuran and dibenzothiophene. When the compound to be used is used as a host compound, it has been found that good light emission characteristics are exhibited, and the present invention has been achieved.

  Furthermore, when the compound of this invention was used as a host compound, even if it changed the kind of dopant, it discovered that the light emission characteristic and durability maintained a favorable value, and the value did not change a lot. On the other hand, when the existing host compound is applied to a plurality of types of dopants, it has been observed that the luminous efficiency fluctuates and shows low performance depending on the type of dopant, and the host compound of the present invention exhibits specific performance. You can see that Although the details are not yet clear, it is assumed that the above interaction was appropriately adjusted.

  Moreover, it became clear by using the compound of this invention for another layer, especially a positive hole transport layer with a light emitting layer, that the performance of this organic EL element further improved. Regarding the above factors, it is presumed that the carrier injectability, transportability, etc. were appropriately adjusted, but details are unknown.

(2.1) Compound represented by general formula (1) The material for an organic EL device of the present invention will be described below.
The organic EL device material of the present invention is represented by the following general formula (1).

In the general formula (1), A represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group in which an aromatic hydrocarbon group and an aromatic heterocyclic group are bonded.
In the general formula (1), examples of the aromatic hydrocarbon group (also referred to as an aryl group) represented by A include a phenyl group, a xylyl group, a naphthyl group, an anthryl group, a fluorenyl group, a phenanthryl group, and a biphenylyl group. A phenyl group, a biphenyl group or a naphthyl group, and more preferably a phenyl group or a biphenyl group.
In the general formula (1), examples of the aromatic heterocyclic group represented by A (also referred to as a heteroaryl group) include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzoimidazolyl group, a pyrazolyl group, Pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group , Isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (carboline ring of the above carbolinyl group) One of the carbon atoms constituting the is replaced by a nitrogen atom Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group and the like, and more preferably a pyridyl group, a pyrimidyl group, a quinolyl group, a carbazolyl group, a carbolinyl group, or a diazacarbazolyl group, A carbazolyl group is more preferable.
In the general formula (1), the group in which the aromatic hydrocarbon group represented by A and the aromatic heterocyclic group are bonded is a group in which the aromatic hydrocarbon group and the aromatic heterocyclic group described above are linked. Although it will not specifically limit if it exists, it is preferable to have a silyl group, an arylphosphoryl group, or a carbazolyl group as a partial structure, and it is more preferable to have a carbazolyl group as a partial structure.

  In the general formula (1), an aromatic hydrocarbon group represented by A, an aromatic heterocyclic group, or a group in which an aromatic hydrocarbon group and an aromatic heterocyclic group are bonded is represented by the following general formula (A-1 ) To (A-6), preferably (A-1) to (A-4), more preferably (A-1) to (A-). More preferably, it is represented by any one of 3).

In the general formula (1), B represents a substituent.
In the general formula (1), examples of the substituent represented by B include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group (also referred to as an aryl group, such as a phenyl group, a xylyl group, and a naphthyl group). Group, anthryl group, fluorenyl group, phenanthryl group, biphenylyl group, etc.), non-aromatic heterocyclic group, aromatic heterocyclic group (also called heteroaryl group, 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-triazol-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, quino Group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is a nitrogen atom) Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), halogen atom, alkoxyl group, cycloalkoxyl group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxy Carbonyl group, aryloxycarbonyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, nitro group, Ano group, alkylphosphino group, arylphosphino group, alkylphosphoryl group, arylphosphoryl group, alkylthiophosphoryl group or arylthiophosphoryl group, silyl group, etc., alkyl group, cycloalkyl group, aromatic hydrocarbon group, It is preferably an aromatic heterocyclic group, an alkoxyl group, a cycloalkoxyl group, an aryloxy group, an amino group, a nitro group or a cyano group, more preferably an aromatic hydrocarbon group, an aromatic heterocyclic group or an amino group. A phenyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group or a diarylamino group is more preferred, and a phenyl group or a carbazolyl group is most preferred.
These groups may be further substituted with the above-mentioned substituents, or they may be bonded to each other to form a ring.

  In General formula (1), n represents the integer of 0-2.

In General formula (1), X and Y represent an oxygen atom or a sulfur atom.
In the general formula (1), X and Y may be the same or different from each other, but X is preferably an oxygen atom. X or Y is preferably a sulfur atom.

In the general formula (1), Z is a monocyclic arylene group, a combination of a monocyclic arylene group, a monocyclic heteroarylene group, a combination of a monocyclic heteroarylene group, or a monocyclic arylene group and a monocyclic heterocycle. Represents a combination with an arylene group.
Here, monocyclic means a 6-membered ring or a 5-membered ring and does not have a condensed ring structure. An arylene group and a heteroarylene group are a hydrogen atom from an aryl group and a heteroaryl group, respectively. Represents a divalent linking group in which one is removed.
In the general formula (1), examples of the aryl group corresponding to the monocyclic arylene group represented by Z include a phenyl group and a biphenyl group, and the hetero group corresponding to the monocyclic heteroarylene group represented by Z. Examples of the aryl group include pyridyl group, pyrimidine group, triazine group, thienyl group, furyl group, pyrazolyl group, imidazolyl group, triazolyl group, oxazolyl group, thiazolyl group, diazaoxazolyl group, diazathiazolyl group and the like. Group, biphenyl group, pyridyl group or pyrimidine group, more preferably phenyl group or biphenyl group, and 1,3-phenylene, 3,3′-biphenyl as the bonding mode of the phenyl group or biphenyl group Most preferably.

(2.2) Compound represented by general formula (2-1) or (2-2) General formula (1) may be represented by the following general formula (2-1) or (2-2). preferable.

  In the general formulas (2-1) and (2-2), A, B, X, Y and Z have the same meanings as A, B, X, Y and Z in the general formula (1), respectively.

  The general formula (2-1) is preferably represented by the following general formula (2-1-1) or (2-1-2).

  In the general formulas (2-1-1) and (2-1-2), A, B, X, Y and Z have the same meanings as A, B, X, Y and Z in the general formula (2-1), respectively. It is.

  The general formula (2-1) is more preferably represented by the general formula (2-1-1).

  In the general formula, (2-2) is preferably represented by the following general formula (2-2-1) or (2-2-2).

  In the general formulas (2-2-1) and (2-2-2), A, B, X, Y and Z have the same meanings as A, B, X, Y and Z in the general formula (2-2), respectively. It is.

  The general formula (2-2) is more preferably represented by the general formula (2-2-2).

(2.3) Compounds represented by general formula (3-1), (3-2), (3-3) or (3-4) General formula (1) is represented by the following general formula (3-1) , (3-2), (3-3) or (3-4).

  In the general formulas (3-1), (3-2), (3-3) and (3-4), A, B, X and Y are the same as those in the general formulas (2-1) and (2-2). It is synonymous with A, B, X, and Y, respectively.

  The general formula (1) is more preferably represented by the general formula (3-1) or (3-3).

  The organic EL device material of the present invention described above may be used in any layer in the organic layer of the organic EL device, but is preferably used in the light emitting layer, the electron transport layer, and the hole transport layer. More preferably, it is used for a light emitting layer and a positive hole transport layer, and it is still more preferable that it is used for a light emitting layer. Furthermore, the organic EL device material of the present invention is most preferably used together with a phosphorescent dopant as a host material in the light emitting layer. Further, as a more preferred embodiment, it is preferably used for both the hole transport layer and the light emitting layer.

(2.4) Specific examples Hereinafter, although the example of the organic EL element material which concerns on this invention is given, this invention is not limited to these.

(2.5) Synthesis Example Hereinafter, a synthesis example of the organic EL element material of the present invention will be described, but the present invention is not limited thereto. The synthesis method of the above compounds (25) and (46) will be described as an example.

(2.5.1) Synthesis of Intermediate 3- (8-Bromodibenzothiophenyl) -9-phenyl-9H-carbazole

Under a nitrogen stream, 300 ml of dehydrated tetrahydrofuran (THF) and 50 ml of degassed water were added to a 500 ml four-headed flask, followed by 7.0 g of 2,8-dibromodibenzothiophene, 9-phenyl-3- (4,4,5 , 5-tetramethyl-1,3,2-dioxoboranyl) -9H-carbazole (6.9 g), sodium carbonate (2.5 g) and tetrakis (triphenylphosphine) palladium (0) (1.0 g) were added, and the mixture was heated to reflux for 6 hours.
After allowing to cool, ethyl acetate was further added, followed by liquid separation. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain 4.0 g of the desired 3- (8-bromodibenzothiophenyl) -9-phenyl-9H-carbazole (43% yield). The structure of the obtained compound was confirmed by Mass and NMR.

(2.5.2) Intermediate Synthesis of (8- (9-phenyl-9H-carbazolyl)) dibenzothiophenyl) boronic acid

  Under a nitrogen stream, 4.0 g of 3- (8-bromodibenzothiophenyl) -9-phenyl-9H-carbazole, 200 ml of dehydrated THF were added to a 300 ml four-headed flask and cooled in a dry ice / acetone bath. To this solution, 5.5 ml of n-BuLi (1.63 Min Hexane) was added dropwise, and after completion of the addition, the solution was stirred for 1 hour. Further, a solution prepared by mixing 1.0 g of trimethoxyborane with 15 ml of dehydrated THF was added dropwise to this solution. After stirring for 30 minutes as it was, the dry ice / acetone bath was removed and the mixture was warmed, and quenched at -10 ° C by adding 50 ml of water. After returning to room temperature, 30 ml of 1N hydrochloric acid was added. After standing overnight, ethyl acetate was added, and the organic layer was separated, washed with water until neutral, added with magnesium sulfate, dried, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography to obtain 2.3 g of the desired (8- (9-phenyl-9H-carbazolyl)) dibenzothiophenyl) boronic acid (yield 62%). The structure of the compound was confirmed by Mass and NMR.

(2.5.3) Synthesis of Intermediate A

Under a nitrogen stream, 200 ml of dehydrated tetrahydrofuran (THF) and 25 ml of degassed water were added to a 300 ml four-head flask, followed by 2.3 g of (8- (9-phenyl-9H-carbazolyl)) dibenzothiophenyl) boronic acid, 1.4 g of 4,4′-biphenyl, 0.8 g of sodium carbonate and 0.3 g of tetrakis (triphenylphosphine) palladium (0) were added, and the mixture was heated to reflux for 8 hours.
After allowing to cool, ethyl acetate was further added, followed by liquid separation. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain a crude product. This crude product was purified by GPC to obtain 1.2 g of the desired intermediate A (yield 40%). The structure of the obtained compound was confirmed by Mass and NMR.

(2.5.4) Intermediate 9- (6-Bromodibenzofuranyl) -9H-carbazole synthesis

Under a nitrogen stream, 12.0 g of 2-iodo-6-bromodibenzofuran, 5.9 g of 9H-carbazole, and 300 ml of dimethyl sulfoxide (DMSO) were added to a 500 ml four-head flask, and nitrogen bubbling was performed for 15 minutes while stirring. To this solution, 6.7 g of potassium carbonate and 2.0 g of metallic copper were added and reacted at 140 ° C. for 8 hours.
After allowing to cool, the reaction solution is added to 1 L of water, and the precipitated solid is collected by filtration, dried and recrystallized with toluene to obtain 9- (6-bromodibenzofuranyl) -9H-carbazole as the target intermediate. 9.6 g was obtained (yield 72%). The structure of the obtained compound was confirmed by Mass measurement and NMR measurement.

(2.5.5) Intermediate Synthesis of (8- (9H-carbazolyl) dibenzofuranyl) boronic acid

  Under a nitrogen stream, 4.1 g of 9- (6-bromodibenzofuranyl) -9H-carbazole and 150 ml of dehydrated THF were added to a 300 ml four-head flask and cooled in a dry ice / acetone bath. To this solution, 6.8 ml of n-BuLi (1.63 Min Hexane) was added dropwise, and after completion of the addition, the solution was stirred for 1 hour. Further, a solution prepared by mixing 1.3 g of trimethoxyborane with 15 ml of dehydrated THF was added dropwise to this solution. After stirring at low temperature for 30 minutes, the temperature was returned to room temperature, 30 ml of 1N hydrochloric acid was added, and the mixture was allowed to stand overnight. Ethyl acetate was added to this solution, and the organic layer was separated and washed with water until neutral. After adding magnesium sulfate and drying, this was filtered off and the filtrate was concentrated under reduced pressure to obtain a crude product. Further, this crude product was recrystallized with THF / MeOH to obtain 1.6 g of the desired (8- (9H-carbazolyl) dibenzofuranyl) boronic acid (yield 42%). The structure of the obtained compound was confirmed by Mass and NMR.

(2.5.6) Synthesis of compound (25) of the present invention

After adding 100 ml of DMSO to a 300 ml four-head flask and degassing by nitrogen bubbling, intermediate A, 9- (6-bromodibenzofuranyl) -9H-carbazole 1.2 g, (8- (9H-carbazolyl) dibenzofura Nyl) boronic acid 0.9 g, potassium carbonate 0.6 g, 1,1′-bis (diphenylphosphino) ferrocene-palladium (II) dichloride · dichloromethane complex 115 mg were added and reacted at 140 ° C. for 10 hours.
After allowing to cool, the reaction solution was added to 400 ml of water, and the precipitated solid was collected by filtration and washed with water to obtain a crude product. Furthermore, this crude product was purified by column chromatography and GPC to obtain 0.9 g of the desired compound (25) of the present invention (yield 54%). The structure of the obtained compound was confirmed by Mass and NMR.
In the preparation of the organic EL device described later, a sample obtained by subjecting the compound (25) of the present invention to GPC purification again and then sublimation purification was used.

(2.5.7) Synthesis of compound (46) of the present invention

After adding 100 ml of DMSO to a 300 ml four-head flask and degassing by nitrogen bubbling, 3.3 g of 9- (6-bromodibenzofuranyl) -9H-carbazole, 0.6 g of 1,3-phenylenediboronic acid, potassium carbonate 1.1 g of 1,1′-bis (diphenylphosphino) ferrocene-palladium (II) dichloride · dichloromethane complex 450 mg was added and reacted at 140 ° C. for 8 hours. After allowing to cool, the reaction solution was added to 300 ml of water, and the precipitated solid was collected by filtration and washed with water to obtain a crude product. Further, this crude product was dissolved in THF, MeOH was gradually added, and the precipitated solid was collected by filtration to obtain 1.4 g of the desired compound (46) of the present invention (yield 48%). The structure of the obtained compound was confirmed by Mass and NMR.
In the production of the organic EL device described later, a sample obtained by further purifying the compound (46) of the present invention after GPC purification and sublimation was used.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

Inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.
In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can do.
Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

Further, a hole transport layer having a high p property doped with impurities can be used. For example, JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

  Although the specific example of the compound preferably used for formation of the positive hole transport layer of the organic EL element of this invention below is given, this invention is not limited to these. Note that n represents an integer of 2 or more. The number average molecular weight of the polymer used in the organic EL device of the present invention is preferably 1000 to 100,000, and more preferably 2000 to 50000. By setting it as this range, when forming the organic layer of an organic EL element by the apply | coating method, the solubility to a solvent and viscosity become suitable for organic layer formation, and an organic layer can be formed easily.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and a very small ability to transport holes. By blocking the holes, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the said electron carrying layer can be used as a hole-blocking layer as needed.

  The hole blocking layer in the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  The hole blocking layer preferably contains a carbazole derivative or an azacarbazole derivative (wherein the azacarbazole derivative indicates that one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom). .

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the shortest wave layer.

  Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.
(1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA As a value (eV unit converted value) calculated by performing structure optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
(2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports holes. By blocking electrons, the recombination probability of electrons and holes can be improved.

  Moreover, the structure of the said positive hole transport layer can be used as an electron blocking layer as needed. In the present invention, the thickness of the hole blocking layer and the electron blocking layer is preferably 3 nm to 100 nm, and more preferably 3 nm to 30 nm.

<< Injection layer: hole injection layer (anode buffer layer), electron injection layer (cathode buffer layer) >>
The injection layer includes a hole injection layer and an electron injection layer.
The injection layer is provided as necessary between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer.

  The injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998, NT. The details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of “S.

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

  The details of the electron injection layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically, metals represented by strontium, aluminum and the like. Buffer layer, alkali metal compound buffer layer typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide Etc.

  The injection layer is preferably a very thin film, and depending on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

  In addition, the materials used for the hole injection layer and the electron injection layer can be used in combination with other materials. For example, the materials can be mixed and used in the hole transport layer or the electron transport layer. is there.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) that can form a transparent conductive film may be used.

  The anode may be formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a desired shape pattern may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. In the case of using a coatable material such as an organic conductive compound, a wet film forming method such as a printing method or a coating method can be used.

  When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance of 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.

"cathode"
On the other hand, a metal having a small work function (4 eV or less) (electron-injecting metal), an alloy, an electrically conductive compound, and a mixture thereof can be used as an electrode material for the cathode.
Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance of the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually preferably in the range of 10 nm to 5 μm, and more preferably in the range of 50 nm to 200 nm.

In order to transmit the emitted light, it is advantageous that either the anode or the cathode of the organic EL element is transparent or translucent, so that the emission luminance is improved.
Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
The support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention is not particularly limited in type, such as glass, plastic, etc., and is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent.
Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability measured by a method in accordance with JIS K 7129-1992 (25 ± 0.5 ° C., It is preferably a barrier film having a relative humidity (90 ± 2)% RH) of 0.01 g / (m ² · 24 h) or less, and further, oxygen permeation measured by a method according to JIS K 7126-1987. A high barrier film having a degree of 10 ⁻³ ml / (m ² · 24 h · MPa) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

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

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

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

  The external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, external extraction quantum efficiency (%) = number of photons emitted to the outside of the organic EL element / number of electrons flowed to the organic EL element × 100.

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

<< Method for Manufacturing Organic EL Element >>
As an example of a method for producing an organic EL device, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode explain.

  First, a thin film made of a desired electrode material, for example, an anode material, is formed on a suitable substrate so as to have a thickness of 1.0 μm or less, preferably 10 nm to 200 nm, to produce an anode.

  Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer is sequentially formed on the anode.

  In the organic EL device of the present invention, the light emitting layer when the compound represented by the general formula (1) according to the present invention is used for the light emitting layer, and the cathode and the electron transport layer adjacent to the cathode are applied by a wet method. -It is preferable to form a film.

  Examples of wet coating methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but a precise thin film is formed. From the viewpoint of possible and high productivity, a method with high roll-to-roll method suitability such as a die coating method, a roll coating method, an ink jet method, and a spray coating method is preferable. Different film forming methods may be applied for each layer.

  Examples of the liquid medium for dissolving or dispersing the organic EL device material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO) can be used. As a dispersion method, it is possible to disperse by a dispersion method such as ultrasonic wave, high shearing force dispersion or media dispersion.

  After sequentially forming these layers, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm, and a desired organic EL element is obtained by providing a cathode. can get.

  Alternatively, the cathode, electron injection layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order in the reverse order.

  When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-polarity. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.

<Sealing>
In the organic EL device of the present invention, the anode, the cathode, and each layer provided between the anode and the cathode are preferably sealed from the outside air by a sealing member.

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

  The sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Further, transparency and electrical insulation are not particularly limited.

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

In the present invention, since the organic EL element can be thinned, a polymer film,
It is preferable to use a metal film.
Furthermore, the polymer film has a oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · MPa) or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

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

As the adhesive, specifically, photo-curing and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers, methacrylic acid oligomers, moisture-curing adhesives such as 2-cyanoacrylates, Examples thereof include epoxy-based heat and chemical curing type (two-component mixing), hot melt type polyamide, polyester, polyolefin, and cationic curing type ultraviolet curing epoxy resin adhesive.
In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive.

  Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

It is also possible to suitably form an inorganic or organic layer as a sealing film by coating the electrode and the organic layer on the outer side of the electrode facing the support substrate with the organic layer interposed therebetween, and in contact with the support substrate. In this case, the material for forming the sealing film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. Can do.
Furthermore, in order to improve the brittleness of the sealing film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials.

  The method for forming these sealing films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma treatment method, atmospheric pressure A plasma treatment method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

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

  Examples of hygroscopic compounds include metal oxides (sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.), sulfates (sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.), metals Halides (calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (barium perchlorate, magnesium perchlorate, etc.) Among them, anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

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

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (transparent substrate-air interface) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the organic EL element, or is transparent to the transparent electrode or light-emitting layer. This is because light undergoes total reflection with the substrate, and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the side direction of the organic EL element.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), substrate A method of improving efficiency by imparting light condensing properties (Japanese Patent Laid-Open No. Sho 63-314795), a method of forming a reflective surface on the side surface of an organic EL element (Japanese Patent Laid-Open No. 1-220394), a substrate, A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the light emitters (Japanese Patent Laid-Open No. 62-172691), and having a lower refractive index than the substrate between the substrate and the light emitter. A method of introducing a flat layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of the substrate, the transparent electrode layer and the light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Etc.)

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

  In the present invention, by combining these means, it is possible to obtain an organic EL device having further high luminance or durability.

When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less, and more 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.

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

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

As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

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

<Condenser sheet>
The organic EL element of the present invention is processed in a microlens array-like structure on the light extraction side of the substrate, or combined with a condensing sheet, for example, in a specific direction, for example, an organic EL element light emitting surface. On the other hand, the brightness | luminance in a specific direction can be raised by condensing in a front direction.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.

  As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources.

  For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Examples include, but are not limited to, the light source of the sensor. In particular, it can be effectively used as a backlight of a liquid crystal display device and a light source for illumination.

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

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

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE 1931 color system at 1000 cd / m ² is X = 0 when the 2 ° viewing angle front luminance is measured by the above method. .33 ± 0.07, Y = 0.33 ± 0.1.

<Display device>
The display device of the present invention will be described. The display device of the present invention comprises the organic EL element of the present invention. Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here.

  In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like. In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.

  The configuration of the organic EL element included in the display device is selected from the organic EL elements of the present invention as necessary. Moreover, the manufacturing method of an organic EL element is as having shown in the one aspect | mode of the manufacturing method of the organic EL element of the above-mentioned this invention.

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

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

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

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

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

FIG. 1 is a schematic perspective view showing an example of the configuration of a display device composed of the organic EL element of the present invention, which displays image information by light emission of the organic EL element, for example, a display such as a mobile phone FIG.
As shown in FIG. 1, the display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
The control unit B is electrically connected to the display unit A.
The control unit B sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. As a result, each pixel sequentially emits light according to the image data signal for each scanning line by the scanning signal, and the image information is displayed on the display unit A.

FIG. 2 is a schematic diagram of the display unit A shown in FIG.
The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate.
The main members of the display unit A will be described below.
FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material. 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).
When a scanning signal is transmitted from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region in the same substrate on the same substrate.

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

The organic EL element of the present invention may be used as an organic EL element having a resonator structure, and the purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However, It is not limited to these.
Moreover, you may use for the said use by making a laser oscillation. Furthermore, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).

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

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

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

It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. Since other layers are common, patterning of the mask or the like is not necessary. In addition, an electrode film or the like can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is improved.
According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

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

<< One Embodiment of Lighting Device of the Present Invention >>
One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.
The non-light emitting surface of the organic EL device of the present invention is covered with a glass case, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX TRACK manufactured by Toagosei Co., Ltd.) is used as a sealing material. LC0629B) is applied, and this is overlaid on the cathode to be in close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed, and as shown in FIG. 3 and FIG. Can be formed.

FIG. 3 shows a schematic diagram of the illumination device.
As shown in FIG. 3, the organic EL element 101 is covered with a glass cover 102. The sealing operation with the glass cover 102 is performed in a glove box (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere.

FIG. 4 shows a cross-sectional view of the lighting device.
As shown in FIG. 4, the cathode 105 and the organic EL layer 106 are formed on a glass substrate 107 with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
Moreover, the structure of the compound used by the following Example is represented by a following formula.

<< Production of Organic EL Element 1-1 >>
An ITO film having a film thickness of 100 nm was formed on a glass substrate of 100 mm × 100 mm × 1.1 mm, patterned, and this ITO transparent electrode substrate was ultrasonically cleaned with isopropyl alcohol and dried with dry nitrogen gas. UV ozone cleaning was performed for 5 minutes.

  This transparent electrode substrate was fixed to a substrate holder of a vacuum deposition apparatus, and a resistance heating boat containing separately prepared compounds for each constituent layer was attached to the vacuum deposition apparatus.

Next, after depressurizing the vacuum chamber to 4 × 10 ⁻⁴ Pa, α-NPD was deposited on the transparent support substrate at a deposition rate of 0.1 nm / second to provide a 40 nm-thick hole transport layer.

  Further, Comparative 1 as the host compound and D-50 as the dopant compound were co-deposited on the hole transport layer at a deposition rate of 0.1 nm / second and 0.010 nm / second, respectively, to emit light having a thickness of 60 nm. A layer was provided.

Subsequently, Alq ₃ 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 60 nm. The substrate temperature during vapor deposition was room temperature.

  Subsequently, lithium fluoride was vapor-deposited to provide a cathode buffer layer with a thickness of 0.5 nm, aluminum was vapor-deposited to provide a cathode with a thickness of 150 nm, and an organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-12 >>
In the production of the organic EL device 1-1, the host compound was changed to the compounds shown in Table 1.
Other than that produced the organic EL element 1-2 to 1-12 similarly.

<< Evaluation of Organic EL Elements 1-1 to 1-12 >>
After the device is fabricated, the non-light emitting surfaces of the organic EL devices 1-1 to 1-12 are each covered with a glass case, and a glass substrate having a thickness of 1.1 mm is used as a sealing substrate, and an epoxy photocuring material is used as a sealing material around A mold adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied, and this is overlaid on the cathode and brought into intimate contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured and sealed. A lighting device having the structure shown in FIGS. 3 and 4 was produced and used as a sample.
The following evaluation was performed on each sample thus produced. The evaluation results are shown in Table 1.

(1) Luminous efficiency (measurement of external extraction quantum efficiency)
The organic EL element is allowed to emit light at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² and light emission luminance (L) [cd / m ² ] immediately after the start of light emission is measured. Thus, the external extraction quantum efficiency (η) was calculated. CS-2000 (manufactured by Konica Minolta Sensing) was used for measuring the emission luminance.
The light emission efficiency (external extraction quantum efficiency) was expressed as a relative value with the light emission luminance of the organic EL element 1-1 as 100.

(2) Luminous life The organic EL device emits light continuously at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and the light emission luminance is half the initial luminance. The time required to become (half-life τ1 / 2) was measured, and this was used as a measure of the emission lifetime.
Since the organic EL element 1-1 had a short lifetime, the light emission lifetime was expressed as a relative value with the half-life of the organic EL element 1-2 as 100.

(3) Summary As shown in Table 1, the organic EL elements 1-5 , 1-9 and 1-12 of the present invention have a luminous efficiency higher than that of the organic EL elements 1-1 to 1-3 of the comparative example. It is equivalent or better and has a long light emission life.
From the above, it can be seen that it is effective to use the organic EL device material of the present invention as the host compound of the light emitting layer for improving the light emission efficiency and the light emission lifetime of the organic EL device.

<< Preparation of Organic EL Element 2-1 >>
On a transparent electrode substrate prepared in the same manner as in Example 1, poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) was diluted to 70% with pure water. Using this solution, a thin film was formed by spin coating under conditions of 3000 rpm and 30 seconds, and then dried at 200 ° C. for 1 hour to provide a 20 nm-thick hole transport layer.

  Using a solution of 3 mg of hole transport material HT-1 (TPD) and 40 mg of hole transport material HT-2 (α-NPD) dissolved in toluene on a hole transport layer under a nitrogen atmosphere, 1500 rpm A thin film was formed by spin coating under conditions of 30 seconds, and further irradiated with ultraviolet light for 180 seconds to carry out photopolymerization and crosslinking, thereby providing a second hole transport layer having a thickness of about 20 nm.

  On this second hole transport layer, using a solution prepared by dissolving 100 mg of Comparative 2 as a host compound and 10 mg of D-50 as a luminescent dopant compound in 10 ml of toluene and 2 ml of THF, respectively, at 600 rpm, 30 A thin film was formed by spin coating under the conditions of seconds. It vacuum-dried at 80 degreeC for 1 hour, and provided the light emitting layer with a film thickness of about 50 nm.

Further, a thin film was formed on this light emitting layer by spin coating under conditions of 1000 rpm and 30 seconds using a solution of 50 mg of ET-40 dissolved in 10 ml of butanol, followed by vacuum drying at 60 ° C. for 1 hour. An electron transport layer having a thickness of about 30 nm was provided. Thus, the organic EL element 2-1 was produced.
The cathode buffer layer and the cathode were formed by the same method as in Example 1.

<< Production of Organic EL Elements 2-2 to 2-11 >>
In the production of the organic EL element 2-1, the host compound was changed to the compounds shown in Table 2.
Other than that produced the organic EL element 2-2 to 2-11 similarly.
In Comparative Example 1 as the host compound, sufficient solubility in the solvent was not obtained, and the device could not be produced by the same method as the production of the organic EL device 2-1.

<< Evaluation of Organic EL Elements 2-1 to 2-11 >>
When evaluating the produced organic EL elements 2-1 to 2-11, these organic EL elements were sealed in the same manner as the organic EL elements 1-1 to 1-12 of Example 1, and FIGS. A lighting device as shown in FIG.
Each sample thus produced was evaluated for light emission efficiency and light emission lifetime in the same manner as in Example 1. The luminous efficiency and the luminous lifetime were expressed as relative values with each characteristic value of the organic EL element 2-1 being 100.
The evaluation results are shown in Table 2.

As shown in Table 2, the organic EL element 2-11 of the present invention forming each organic layer by a wet coating method, as compared with the organic EL element 2-1 and 2-2 of the Comparative Example, the luminous efficiency equivalent That is all and the light emission life is long. This is presumably because the interaction between molecules was moderately adjusted even in the light emitting layer formed by coating.
From the above, it can be seen that it is effective to use the organic EL device material of the present invention as the host compound of the light emitting layer for improving the light emission efficiency and the light emission lifetime of the organic EL device.

<< Production of Organic EL Element 3-1 >>
In the production of the organic EL device 1-1, the host compound was changed to Comparison 2, the luminescent dopant was changed to D-26, and the BCP was deposited on the luminescent layer after the luminescent layer was formed and before the electron transport layer was formed. A 5 nm hole blocking layer was provided by vapor deposition at 0.1 nm / second. Other than that produced the organic EL element 3-1.

<< Production of Organic EL Elements 3-2 to 3-15 >>
In preparation of the organic EL element 3-1, the host compound and the dopant were changed to the compounds shown in Table 3. Other than that produced the organic EL element 3-2-3-15 similarly.

<< Evaluation of Organic EL Elements 3-1 to 3-15 >>
When evaluating the produced organic EL elements 3-1 to 3-15, these organic EL elements were sealed in the same manner as the organic EL elements 1-1 to 1-12 of Example 1, and FIGS. A lighting device as shown in FIG.
The luminous efficiency of each sample thus produced was evaluated in the same manner as in Example 1. The luminous efficiency was expressed as a relative value with the luminous luminance of the organic EL element 3-1 as 100.
The evaluation results are shown in Table 3.

As shown in Table 3, the organic EL elements 3-7 to 3-10 using the organic EL element material of the present invention as a host compound emit light in comparison with the organic EL elements 3-1 to 3-6 of the comparative example. It can be seen that the luminous efficiency change when the dopant is changed is small, and that even when combined with dopants of various structures, light is emitted efficiently.
From the above, it can be seen that it is effective to use the organic EL element material of the present invention as a host material for the luminous efficiency of the organic EL element.

<< Preparation of Organic EL Element 4-1 >>
In the production of the organic EL element 1-1, a second hole transport layer was provided between the hole transport layer and the light emitting layer. The second hole transport layer was formed by depositing Comparative 1 on the hole transport layer at a deposition rate of 0.2 nm / sec. The film thickness of the second hole transport layer was 10 nm.
Other than that produced the organic EL element 3-1.

<< Production of Organic EL Elements 3-2 to 3-9 >>
In preparation of the organic EL element 3-1, the hole transport material and the host compound of the second hole transport layer were changed to the compounds shown in Table 4.
Other than that produced the organic EL element 3-2-3-10 similarly.

<< Evaluation of Organic EL Elements 3-1 to 3-10 >>
When evaluating the produced organic EL elements 3-1 to 3-10, these organic EL elements were sealed in the same manner as the organic EL elements 1-1 to 1-12 of Example 1, and FIGS. A lighting device as shown in FIG.
Each sample thus produced was evaluated for light emission efficiency and light emission lifetime in the same manner as in Example 1, and the following evaluation was performed. The luminous efficiency and the luminous lifetime were expressed as relative values with each characteristic value of the organic EL element 3-1 being 100.

The organic EL element is caused to emit light under a constant current condition of ^2.5 mA / cm ² , and the drive voltage (initial drive voltage) at that time and the drive voltage when the light emission luminance reaches 50% are measured, and ΔV = ( (Driving voltage at 50% luminance) − (initial driving voltage) was calculated.
ΔV was expressed as a relative value where ΔV of the organic EL element 3-1 was 100. The smaller the numerical value, the smaller the drive voltage change.
The evaluation results are shown in Table 4.

As shown in Table 4, the organic EL element 4-8 using the organic EL element material of the present invention as a host compound was compared with the organic EL elements 4-1 and 4-2 of the comparative example, and its luminous efficiency and lifetime. It can be seen that the voltage rise when the element is driven is further suppressed. Furthermore, the organic EL elements 4-5 and 4-10 using the organic EL element material of the present invention as the second hole transporting material have luminous efficiency, emission lifetime and It can be seen that the driving voltage is excellent.
From the above, it is effective to use the organic EL device material of the present invention as a hole transport material or a host compound for improving the light emission efficiency and lifetime of the organic EL device and suppressing the voltage rise during device driving. I know that there is. Furthermore, it turns out that it is especially effective to use the organic electroluminescent element material of this invention for both a positive hole transport material and a host compound.

<Production of full-color display device>

(1) Production of Blue Light-Emitting Element The organic EL element 1-12 of Example 1 was a blue light-emitting element.

(2) Production of Green Light-Emitting Element In production of the organic EL element 1-6 of Example 1, D-50 was changed to D-4.
Other than that produced the green light emitting element similarly.

(3) Production of red light emitting device In production of the organic EL device 1-5 of Example 1, D-50 was changed to D-7.
Otherwise, a red light emitting device was produced in the same manner.

(4) Production of Display Device The red, green, and blue light emitting organic EL elements produced above were arranged in parallel on the same substrate, and an active matrix type full color display device having a form as shown in FIG. 1 was produced.
In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown.
As shown in FIG. 2, the display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of pixels 3 arranged in parallel (light emission color of red region pixels, green region pixels). Pixel, blue region pixel, etc.). Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material. 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 a scanning signal is transmitted from the scanning line 5. The image data signal is received from the data line 6 and light is emitted according to the received image data. In this manner, a full color display device was manufactured by appropriately arranging the red, green, and blue pixels 3 in parallel.
It was confirmed that when the obtained full-color display device was driven, high brightness, high durability, and clear full-color moving image display were obtained.

<< Preparation of white light emitting element and white lighting device >>
The electrode of the transparent electrode substrate described in Example 1 was patterned to 20 mm × 20 mm, and each layer was formed in the same manner as in Example 1 thereon.

  First, α-NPD was deposited on a transparent substrate to provide a hole transport layer having a thickness of 25 nm.

Then, by energizing the entered was molybdenum resistance heating boat of host compound to reduction compound (45), D-50 and D-6, each containing a molybdenum resistance heating boat independently as dopant compound, host compound der Ru of compound (45), the deposition rate of the D-50, D-6 which is a light-emitting dopant is 100: 6: adjusted to 0.4, provided the light-emitting layer having a thickness of 40nm .

Next, an electron transporting layer having a thickness of 40nm using Alq _3.

In addition, a stainless steel square hole mask with the same shape as the transparent electrode is placed on the electron transport layer, lithium fluoride is deposited to provide a 0.5 nm thick cathode buffer layer, and aluminum is deposited. Thus, a cathode having a thickness of 150 nm was provided.
In this way, an organic EL element was produced.

  The produced organic EL element was sealed in the same manner as in Example 1 to produce an illumination device as shown in FIGS.

  When the manufactured lighting device was energized, almost white light was obtained, confirming that it could be used as a lighting device.

<< Preparation of white light emitting element and white lighting device >>
A transparent substrate provided with this ITO transparent electrode after patterning on a substrate (NA45 manufactured by NH Techno Glass Co., Ltd.) on which a 100 nm ITO (indium tin oxide) film was formed as an anode on a 100 mm × 100 mm × 1.1 mm glass substrate The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

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

  The substrate was transferred to a nitrogen atmosphere, and a spin coating method was performed using a solution of 50 mg of commercially available ADS254BE (American Dye Source, Inc.) dissolved in 10 ml of toluene on the hole transport layer at 2500 rpm for 30 seconds. A thin film was formed. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and provided the 2nd positive hole transport layer.

The host compound to reduction compound a (43) 110 mg, using a solution obtained by dissolving D-6 0.2 mg, the D-4,0.5mg and D-50 20 mg, butyl acetate 10 ml, 1000 rpm, A thin film was formed by spin coating under conditions of 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and provided the light emitting layer with a film thickness of 70 nm. Further, a thin film was formed by spin coating at 2000 rpm for 30 seconds using a solution of 25 mg of ET-10 dissolved in 5 ml of hexafluoroisopropanol (HFIP), followed by vacuum drying at 60 ° C. for 1 hour. A first electron transport layer was provided.

  Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of ET-7 was put in a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus.

After depressurizing the vacuum tank to 4 × 10 ⁻⁴ Pa, the molybdenum resistance heating boat containing ET-7 was energized and heated, and deposited on the first electron transport layer at a deposition rate of 0.1 nm / second. Thus, a second electron transport layer having a thickness of 20 nm was provided. The substrate temperature during vapor deposition was room temperature.
Subsequently, lithium fluoride was vapor-deposited to provide a cathode buffer layer having a thickness of 0.5 nm, and aluminum was vapor-deposited to provide a cathode having a thickness of 110 nm to produce an organic EL device.

The produced organic EL device was sealed in the same manner as in Example 1. Further, when the deviation in chromaticity was confirmed using a spectral radiance meter CS-2000 (manufactured by Konica Minolta Sensing), it was 0.018. . Incidentally, the deviation of the chromaticity using the CIE chromaticity represents the deviation of the chromaticity coordinates at 1000 cd / ^{m 2} brightness chromaticity coordinates at the time of 100 cd / ^{m 2} brightness.
Further, an illumination device as shown in FIGS. 3 and 4 was produced using this organic EL element.
When the manufactured lighting device was energized, almost white light was obtained, confirming that it could be used as a lighting device.

Further in the fabrication of a white light-emitting device of Example 6, the host compound of compound (43) from the comparison 2, and Comparative 3 are white light emitting device of Comparative similarly -1 was changed to, to prepare -2.
The produced organic EL device was sealed in the same manner as in Example 1, and when the chromaticity shift was confirmed, the chromaticity shift of the white light emitting device-1 using Comparative 2 was 0.042, and Comparative 3 was used. The deviation of chromaticity of the white light emitting element-2 was 0.030.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 101 Organic EL element 102 Glass cover 105 Cathode 106 Organic EL layer 107 Transparent electrode exhausted glass substrate 108 Nitrogen gas 109 Water trapping agent A Display part B Control part

Claims (9)

It represents with the following general formula (2-1-1) or (2-1-2), The organic electroluminescent element material characterized by the above-mentioned.

[In General Formulas (2-1-1) and (2-1-2), A represents a heteroaromatic ring group or a group in which a hydrocarbon aromatic ring group and a heteroaromatic ring group are bonded, and B represents a hydrocarbon. An aromatic ring group or a heteroaromatic ring group is represented. X and Y represent an oxygen atom or a sulfur atom, Z represents a monocyclic arylene group, a combination of monocyclic arylene groups, a monocyclic heteroarylene group, a combination of monocyclic heteroarylene groups, or a monocyclic arylene group And a monocyclic heteroarylene group. ] In the said general formula (2-1-1) and (2-1-2), A is represented by the following general formula (A-3) or (A-4), It is characterized by the above-mentioned. Material for organic electroluminescence element.

  In the said General formula (2-1-1) and (2-1-2), X or Y is a sulfur atom, The organic electroluminescent element material of Claim 1 or 2 characterized by the above-mentioned.   In any one of the general formulas (2-1-1) and (2-1-2), Z is 1,3-phenylene or 3,3′-biphenyl. The material for an organic electroluminescent element according to the item. A pair of electrodes;
An organic layer comprising a plurality of layers including a light-emitting layer provided between the pair of electrodes,
The organic electroluminescent element in which the organic electroluminescent element material of any one of Claims 1-4 is contained in at least 1 layer among the said organic layers.   6. The organic electroluminescent element according to claim 5, wherein the layer containing the organic electroluminescent element material is the light emitting layer. Display apparatus comprising the organic electroluminescence device according to claim 5 or 6. Lighting apparatus comprising the organic electroluminescence device according to claim 5 or 6. In the manufacturing method of the organic electroluminescent element which manufactures the organic electroluminescent element of Claim 5 or 6,
Method for producing organic electroluminescent device you characterized that you formed by a wet process at least one layer of the organic layer.

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