JP5014705B2 - Organic electroluminescence device using phosphorescent compound - Google Patents

Description

  The present invention relates to an organic electroluminescence device using a phosphorescent compound. More specifically, the present invention includes an organic layer containing a phosphorescent compound and a polymer compound, the manufacturing process is simplified, a large area can be realized, and high luminous efficiency and high durability can be obtained. The present invention relates to an organic electroluminescence element.

  In recent years, in order to expand the use of organic electroluminescence elements (also referred to as organic EL elements in this specification), material development using phosphorescent compounds having high emission efficiency has been actively performed.

  Further, the organic EL element generally has a configuration including one or more organic layers sandwiched between an anode and a cathode. When a polymer compound is used as a material for forming these layers, a solution in which the polymer compound is dissolved can be applied to easily form a film, and the device can be increased in area and mass-produced.

  For example, Patent Document 1 discloses an organic EL element having a layer composed of a polymer compound having a structural unit derived from a hole-transporting carbazole derivative and an electron-transporting oxadiazole derivative, and a phosphorescent compound. Has been.

However, when the polymer compound contains a structural unit derived from a carbazole derivative, there is a problem that high luminous efficiency cannot be obtained and the durability of the device is low.
On the other hand, Patent Document 2 attempts to use a triphenylamine derivative instead of a carbazole derivative as a hole transporting compound in order to obtain high luminous efficiency. Specifically, a polymer compound having a structural unit derived from a triphenylamine derivative, an oxadiazole derivative, and a phosphorescent compound is disclosed.

  However, depending on the combination of monomers used, there are cases where the distribution of structural units derived from each monomer in the polymer compound becomes non-uniform due to differences in the polymerizability of the individual compounds. In the organic EL device using a polymer compound having a non-uniform distribution, there is a problem that high luminous efficiency cannot be obtained and the durability of the device is low.

For this reason, it has been desired to develop a material that is suitable for large area and mass production, and that can obtain high luminous efficiency and high durability.
JP 2002-363227 A JP-A-2005-97589

  An object of the present invention is to provide an organic EL device that simplifies the manufacturing process, achieves a large area, and provides high luminous efficiency and high durability.

As a result of earnest research to solve the above problems, the present inventors,
It has been found that the above problems can be solved by using a phosphorescent compound and a polymer compound containing a structural unit derived from a specific triphenylamine derivative and a structural unit derived from a specific heterocyclic derivative. The invention has been completed.

That is, the present invention is summarized as follows.
[1] In an organic electroluminescence device including one or more organic layers sandwiched between an anode and a cathode,
At least one of the organic layers includes a phosphorescent compound and a polymer compound,
The polymer compound includes a structural unit derived from a monomer represented by the following formula (1) and a structural unit derived from a monomer having a heterocycle containing two or more heteroatoms. An organic electroluminescence device characterized by the above.

(Wherein R ^{1 to} R ²⁷ each independently represents a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R ¹ In each of ˜R ⁴ , R ⁵ ˜R ⁹ , R ¹⁰ ˜R ¹⁴ , and R ¹⁵ ˜R ¹⁹ , two groups bonded to adjacent carbon atoms on the benzene ring are bonded to each other and condensed. A ring may be formed X ¹
Is a single bond, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, —SO ₂ —, —NR
-(R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group), -CO-, or a divalent organic group having 1 to 20 carbon atoms (the organic group is an oxygen atom ( -O-), a sulfur atom (-S -), - SO - , - SO 2 -, -. NR- (R is a hydrogen atom, an alkyl group or a phenyl group, 1 to 4 carbon atoms) and - Y ¹ represents a polymerizable functional group, which may be substituted with an atom or group selected from the group consisting of CO—. p is 0
Or 1 is shown. )
[2] The organic electroluminescence device as described in [1] above, wherein the monomer having a heterocycle is an oxadiazole derivative or a triazole derivative.

  [3] The organic electro according to [2], wherein the monomer having a heterocycle is selected from the group consisting of monomers represented by the following formulas (2) to (5): Luminescence element.

(In the formulas (2) to (5), R ^{28 to} R ⁷¹ are respectively synonymous with R ¹ in the above formula (1).
^{R 28 ~R 31, R 32 ~R} 36, R 37 ~R 40, R 42 ~R 44, R 45 ~R 49, R 50 ~R 54, R 58 ~R 62, R 63 ~R 66, and R ^In each of ^{67 to} R ⁷¹ , two groups bonded to adjacent carbon atoms on the benzene ring may be bonded to each other to form a condensed ring, and X ^{2 to} X ⁵ are has the same meaning as X ¹ in the formula (1), Y ² to Y ⁵ are each the same meaning as Y ¹ in the formula (1). In said formula (5), Ar represents a phenyl group or a naphthyl group. )
[4] The organic electroluminescent element according to any one of [1] to [3], wherein the phosphorescent compound is an iridium complex.

[5] An image display device using the organic EL element according to any one of [1] to [4].
[6] A surface-emitting light source using the organic EL device according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, while a manufacturing process is simplified and a large area can be implement | achieved, the organic EL element which can obtain high luminous efficiency and high durability can be provided.

Hereinafter, the present invention will be specifically described.
The organic EL device according to the present invention includes one or more organic layers sandwiched between an anode and a cathode, and at least one of the organic layers contains a phosphorescent compound and a specific polymer compound. Including.

1. Polymer Compound The polymer compound used in the present invention is obtained by copolymerizing the monomer represented by the above formula (1) and a monomer having a specific heterocycle. In the polymerization of the polymer compound, one or more monomers represented by the formula (1) are combined with one or more monomers having the heterocycle. May be used.

  Since the monomer represented by the above formula (1) is a hole transporting compound, and the monomer having a heterocycle is an electron transporting compound, the polymer compound used in the present invention is a hole transporting compound. It has a transporting site and an electron transporting site. For this reason, in the organic EL device according to the present invention, holes and electrons are efficiently recombined on the phosphorescent compound contained in the same organic layer as the polymer compound, and high luminous efficiency is obtained.

  The monomer represented by the above formula (1) is a triphenylamine derivative. When a polymer compound containing a structural unit derived from this monomer is used, an organic layer is formed together with a phosphorescent compound. In addition, high luminous efficiency and high durability can be obtained.

In formula (1), R ^{1 to} R ²⁷ each independently represent a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. .

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, and a hexyl group.

  Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an isobutoxy group, and a tertiary butoxy group.

Among these, R < ¹ > -R < ²⁷ > is respectively independently a hydrogen atom, a fluorine atom, C1-C1.
8 linear alkyl groups are preferred.
In R ^{1 to} R ⁴ , two groups bonded to adjacent carbon atoms on the benzene ring may be bonded to each other to form a condensed ring. R ^{5 to} R ⁹ , R ^{10 to} R ¹⁴ , and R ^{15 to} R ¹⁹ are the same as R ^{1 to} R ⁴ . Of these, monomers in which R ¹⁰ and R ¹¹ and R ⁸ and R ⁹ are bonded to each other to form a condensed ring are preferable.

X ¹ is a linking group, and is a single bond, an oxygen atom (—O—), a sulfur atom (—S—), —SO—.
, —SO ₂ —, —NR— (R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group), —CO—, or a divalent organic group having 1 to 20 carbon atoms ( The organic group includes an oxygen atom (—O—), a sulfur atom (—S—), —SO—, —SO ₂ —, —NR— (R represents a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms or a phenyl group is represented. And an atom or group selected from the group consisting of —CO—. ). One or two or more oxygen atoms (—O—) may be contained, and the same applies to sulfur atoms (—S—), —SO—, —SO ₂ —, —NR—, and —CO—. is there. In addition, it contains two or more atoms or groups selected from the group consisting of oxygen atom (—O—), sulfur atom (—S—), —SO—, —SO ₂ —, —NR— and —CO—. You may go out.

Among these, X ¹ is preferably a single bond, an oxygen atom (—O—), or a linking group represented by the following formulas (S1) to (S3). In the following formula (S1), n represents an integer of 0 to 5.

X ¹ is preferably bonded to the para position with respect to the nitrogen atom N bonded to the phenyl group.
Y ¹ represents a polymerizable functional group, and the functional group may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable functional groups. Of these, the radical polymerizable functional group is preferable because the copolymer can be easily produced.

Examples of Y ¹ include urethane (meth) acrylate groups such as allyl group, alkenyl group, acrylate group, methacrylate group, methacryloyloxyethyl carbamate group, vinylamide group, and derivatives thereof. Of these, alkenyl groups are preferred.

Specifically, the partial structure formed by X ¹ and Y ¹ is preferably a partial structure represented by the following formulas (A1) to (A12). Among these, the partial structures represented by the following formulas (A1), (A5), (A8), and (A12) are more preferable because functional groups can be easily introduced.

p represents 0 or 1.
Specific examples of the monomer represented by the above formula (1) include monomers represented by the following formulas (B1) to (B6) from the viewpoint of carrier mobility in the polymer compound. The monomers represented by the following formulas (B1), (B2), and (B5) are more preferably used.

  In the monomer having a heterocycle used in the present invention, the heterocycle contains two or more heteroatoms. The monomer may contain one or more such heterocycles. A polymer compound containing a structural unit derived from the monomer can have high luminous efficiency and high durability when an organic layer is formed together with a phosphorescent compound.

  Examples of the heterocycle include imidazole, pyrazole, pyridazine, pyrimidine, pyrazine, oxadiazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, oxadiazole, thiadiazole, and condensed rings thereof. Of these, oxadiazole and triazole are preferable. That is, as the monomer having a heterocycle, an oxadiazole derivative and a triazole derivative are preferable.

As the monomer having a heterocyclic ring, monomers represented by the above formulas (2) to (5) are more preferable.
In said formula (2)-(5), R < ²⁸ > -R < ⁷¹ > is synonymous with R < ¹ > in said Formula (1), respectively. Among these, R ^{28 to} R ⁷¹ are preferably each independently a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 8 carbon atoms, or a tertiary butyl group. In the above formula (2), R ³⁴ is more preferably a tertiary butyl group, and in the above formula (3), R ⁴⁷ is more preferably a tertiary butyl group.

In R ^{28 to} R ³¹ , two groups bonded to adjacent carbon atoms on the benzene ring may be bonded to each other to form a condensed ring, and R ^{32 to} R ³⁶ , R ^{37 to} R ⁴⁰ , R ^{42 to} R ⁴⁴ , R ^{45 to} R ⁴⁹ , R ^{50 to} R ⁵⁴ , R ^{58 to} R ⁶² , R ^{63 to} R ⁶⁶ , and R ^{67 to} R ⁷¹ are the same as R ^{28 to} R ³¹ . is there. In the above formula (2), a monomer in which R ²⁸ and R ²⁹ and R ³² and R ³³ are bonded to each other to form a condensed ring is preferable.

In the above formula (5), Ar represents a phenyl group or a naphthyl group.
X ² has the same meaning as X ¹ in formula (1), and the preferred range is also the same. X ^{3 to} X ⁵ are also the same as X ² .

Y ² has the same meaning as Y ¹ in the above formula (1), and the preferred range is also the same. Y ^{3 to} Y ⁵ are also the same as Y ² .
Specific examples of the partial structure formed by X ² and Y ² , X ³ and Y ³ , X ⁴ and Y ⁴ , and X ⁵ and Y ⁵ include the above formulas ( A partial structure represented by A1) to (A12) is preferable. Among these, the partial structures represented by the above formulas (A1), (A5), (A8), and (A12) are more preferable because a functional group can be easily introduced into a monomer having a heterocycle.

  As the monomer having a heterocyclic ring, from the viewpoint of carrier mobility in the polymer compound, specifically, monomers represented by the following formulas (C1) to (C4) are preferably used. The monomers represented by the following formulas (C1) to (C3) are more preferably used.

  Specifically, the polymer compound used in the present invention includes a polymer compound containing a structural unit derived from the above formula (B2) and the above formula (C1), the above formula (B5) and the above formula (C2). A polymer compound containing a structural unit derived and a polymer compound containing a structural unit derived from the above formulas (B1) and (C3) are preferably used. When these polymer compounds are used, holes and electrons recombine more efficiently on the phosphorescent compound, and higher luminous efficiency can be obtained. In addition, an organic layer having a uniform distribution can be formed together with the phosphorescent compound, and an organic EL element having excellent durability can be obtained.

  The polymer compound may further contain a structural unit derived from another polymerizable compound as long as it does not contradict the purpose of the present application. Examples of such polymerizable compounds include (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate, and compounds having no carrier transport properties such as styrene and derivatives thereof, but are not limited thereto. Is not to be done.

  In addition, the weight average molecular weight of the polymer compound used in the present invention is preferably 1,000 to 2,000,000, and more preferably 5,000 to 1,000,000. The molecular weight in this specification means the polystyrene conversion molecular weight measured using GPC (gel permeation chromatography) method. It is preferable for the molecular weight to be in this range since the polymer is soluble in an organic solvent and a uniform thin film can be obtained.

The polymer compound may be a random copolymer, a block copolymer, or an alternating copolymer.
In the polymer compound, the content of the structural unit derived from the monomer represented by the formula (1) is preferably 5 to 95 mol%, more preferably 20 to 80 mol%. The content of the structural unit derived from the monomer having is preferably 5 to 95 mol%, more preferably 20 to 80 mol% (wherein the structure derived from the monomer represented by the formula (1) above) The total of the content of the unit and the content of the structural unit derived from the monomer having a hetero ring is 100 mol%.)

  The polymer compound may be polymerized by radical polymerization, cationic polymerization, anionic polymerization, or addition polymerization, but radical polymerization is preferred. It is desirable to polymerize the polymer compound using the monomer so that the content of the structural unit falls within the above range.

2. Phosphorescent compound The phosphorescent compound used in the present invention is not particularly limited as long as it is a low-molecular compound that emits phosphorescence at room temperature. In the present invention, the phosphorescent compounds may be used alone or in combination of two or more.

  In the organic layer containing the phosphorescent compound and the polymer compound used for the organic EL device according to the present invention, the phosphorescent compound is contained in a state dispersed in a matrix formed of the polymer compound. Yes. For this reason, it is possible to obtain light emission that is usually difficult to use, that is, light emission via the triplet excited state of the phosphorescent compound. Therefore, when using the organic layer, high luminous efficiency can be obtained.

  As the phosphorescent compound, a transition metal complex is preferably used. The transition metal used in this transition metal complex is the first transition element series of the periodic table, that is, Sc of atomic number 21 to Zn of 30, the second transition element series, that is, Y of atomic number 39 to Cd of 48, The third transition element series, that is, any metal atom from Hf of atomic number 72 to Hg of 80. Among these, as the transition metal complex, a palladium complex, an osmium complex, an iridium complex, a platinum complex, and a gold complex are preferable, an iridium complex and a platinum complex are more preferable, and an iridium complex is most preferable.

  As the iridium complex, specifically, a complex represented by the following formulas (E-1) to (E-34) is preferable because a long-life organic EL device is obtained with high luminous efficiency. Complexes represented by (E-1), (E-2), (E-17), and (E-32) to (E-34) are more preferable.

The iridium complexes represented by the above formulas (E-1) to (E-34) are obtained by a known method.
3. Organic EL device <organic layer containing phosphorescent compound and polymer compound>
The organic EL device according to the present invention includes one or more organic layers sandwiched between an anode and a cathode, and the phosphorescent compound and the polymer compound are contained in at least one of the organic layers. Including.

  An example of the configuration of the organic EL element according to the present invention is shown in FIG. 1, but the configuration of the organic EL element according to the present invention is not limited to this. In FIG. 1, a hole transport layer (3), a light emitting layer (4) and an electron transport layer (5) are arranged in this order between an anode (2) and a cathode (6) provided on a transparent substrate (1). Provided. In the organic EL element, for example, between the anode (2) and the cathode (6), either 1) a hole transport layer / light emitting layer, 2) a light emitting layer / electron transport layer, or 3) only a light emitting layer is provided. Also good. Two or more light emitting layers may be stacked.

  In the above, the organic layer containing the phosphorescent compound and the polymer compound can be used as a light emitting layer having both hole transport properties and electron transport properties. For this reason, even if it does not provide the layer which consists of another organic material, there exists an advantage which can produce the organic EL element which has high luminous efficiency.

  As a combination of the compounds contained in the organic layer, specifically, a polymer compound containing a structural unit derived from the above formula (B2) and the above formula (C1) and the above formula (E-2) are used. A combination of a polymer compound containing a structural unit derived from the above formula (B5) and the above formula (C2) and an iridium complex represented by the above formula (E-33), A combination of a polymer compound containing a structural unit derived from B1) and the above formula (C3) and an iridium complex represented by the above formula (E-17), and from the above formula (B1) and the above formula (C3) A combination of the polymer compound containing the derived structural unit and the iridium complex represented by the above formula (E-34) is particularly preferable. By combining these, an organic layer having a more uniform distribution can be obtained, and an element exhibiting higher luminous efficiency as well as excellent durability can be obtained.

  The organic layer containing the phosphorescent compound and the polymer compound is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight of the phosphorescent compound with respect to 100 parts by weight of the polymer compound. It is desirable to include parts by weight.

Although it does not specifically limit as a manufacturing method of the said organic layer, For example, it can manufacture as follows. First, a solution in which the phosphorescent compound and the polymer compound are dissolved is prepared. The solution is preferably prepared using the phosphorescent compound and the polymer compound so that the content of the phosphorescent compound is in the above range. The solvent used for the preparation of the solution is not particularly limited. For example, a chlorine solvent such as chloroform, methylene chloride, dichloroethane, an ether solvent such as tetrahydrofuran and anisole, an aromatic hydrocarbon solvent such as toluene and xylene, Ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate are used. Next, the solution prepared in this manner is formed on a substrate using an inkjet method, a spin coating method, a dip coating method, a printing method, or the like. The total concentration of the phosphorescent compound and the polymer compound in the solution depends on the compound used and the film formation conditions. For example, in the case of a spin coating method or a dip coating method, It is preferable that it is 10 wt%. As described above, since the organic layer is easily formed, the manufacturing process can be simplified and the area of the device can be increased.
<Other materials>
Each of the above layers may be formed by mixing a polymer material as a binder. Examples of the polymer material include polymethyl methacrylate, polycarbonate, polyester, polysulfone, and polyphenylene oxide.

  In addition, the materials used for each of the layers may be formed by mixing materials having different functions, for example, a light emitting material, a hole transport material, an electron transport material, and the like. The organic layer containing the phosphorescent compound and the polymer compound may further contain other hole transport materials and / or electron transport materials for the purpose of supplementing carrier transport properties. Such a transport material may be a low molecular compound or a high molecular compound.

  As the hole transport material for forming the hole transport layer or the hole transport material mixed in the light emitting layer, for example, TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1 '-Biphenyl-4,4'diamine); α-NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl); m-MTDATA (4,4', 4 '' -Low molecular triphenylamine derivatives such as tris (3-methylphenylphenylamino) triphenylamine); polyvinylcarbazole; a polymer compound obtained by polymerizing by introducing a polymerizable substituent into the triphenylamine derivative; polyparaphenylene vinylene And fluorescent light-emitting polymer compounds such as polydialkylfluorene. Examples of the polymer compound include a polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575. The hole transport materials may be used singly or in combination of two or more, or different hole transport materials may be laminated and used. The thickness of the hole transport layer depends on the conductivity of the hole transport layer and cannot be generally limited, but is preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm. .

  Examples of the electron transport material for forming the electron transport layer or the electron transport material mixed in the light emitting layer include quinolinol derivative metal complexes such as Alq3 (aluminum trisquinolinolate), oxadiazole derivatives, triazole derivatives, imidazole. Low molecular compounds such as derivatives, triazine derivatives, and triarylborane derivatives; high molecular compounds obtained by polymerizing a low molecular compound by introducing a polymerizable substituent. Examples of the polymer compound include poly PBD disclosed in JP-A-10-1665. The electron transport materials may be used singly or in combination of two or more, or different electron transport materials may be laminated and used. The thickness of the electron transport layer depends on the conductivity of the electron transport layer and cannot be generally limited, but is preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm. .

  Further, a hole block layer may be provided adjacent to the cathode side of the light emitting layer for the purpose of suppressing holes from passing through the light emitting layer and efficiently recombining holes and electrons in the light emitting layer. Good. In order to form the hole block layer, known materials such as triazole derivatives, oxadiazole derivatives, and phenanthroline derivatives are used.

  A buffer layer may be provided between the anode and the hole transport layer or between the anode and the organic layer stacked adjacent to the anode in order to relax the injection barrier in hole injection. In order to form the buffer layer, a known material such as copper phthalocyanine, a mixture of polyethylenedioxythiophene and polystyrenesulfonic acid (PEDOT: PSS) is used.

  An insulating layer having a thickness of 0.1 to 10 nm is provided between the cathode and the electron transport layer or between the cathode and the organic layer laminated adjacent to the cathode in order to improve the electron injection efficiency. May be. In order to form the insulating layer, known materials such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina are used.

  As the anode material, for example, a known transparent conductive material such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, polyaniline or other conductive polymer is used. The surface resistance of the electrode formed of the transparent conductive material is preferably 1 to 50Ω / □ (ohm / square). The thickness of the anode is preferably 50 to 300 nm.

Examples of the cathode material include alkali metals such as Li, Na, K, and Cs; Mg, Ca
Al, MgAg alloys; Al and alkaline earth metals or alloys of alkali metals such as AlLi, AlCa and the like, and known cathode materials are used. The thickness of the cathode is preferably 10 nm to 1 μm, more preferably 50 to 500 nm. When a highly active metal such as an alkali metal or alkaline earth metal is used as the cathode, the thickness of the cathode is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm. In this case, a metal layer that is stable to the atmosphere is laminated on the cathode for the purpose of protecting the cathode metal. Examples of the metal forming the metal layer include Al, Ag, Au, Pt, Cu, Ni, and Cr. The thickness of the metal layer is preferably 10 nm to 1 μm, more preferably 50 to 500 nm.

  As the substrate of the organic EL device according to the present invention, an insulating substrate transparent to the emission wavelength of the light emitting material is used, and transparent plastics such as PET (polyethylene terephthalate) and polycarbonate are used in addition to glass.

  Examples of the film formation method of the hole transport layer, the light emitting layer, and the electron transport layer include a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ink jet method, a spin coating method, a printing method, a spray method, and a dispenser method. Is used. In the case of a low molecular compound, resistance heating vapor deposition or electron beam vapor deposition is preferably used, and in the case of a polymer material, an ink jet method, a spin coating method, or a printing method is suitably used.

  In addition, as a method for forming the anode material, for example, an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like is used. As a method for forming the cathode material, for example, a resistance heating evaporation method, An electron beam evaporation method, a sputtering method, an ion plating method, or the like is used.

4). Use The organic EL device according to the present invention is suitably used in an image display device as a pixel by a matrix method or a segment method by a known method. The organic EL element is also suitably used as a surface light source without forming pixels.

  Specifically, the organic EL device according to the present invention includes a display device such as a computer, a television, a mobile terminal, a mobile phone, a car navigation, a viewfinder of a video camera, a backlight, an electrophotography, an illumination light source, a recording light source, and an exposure. It is suitably used for light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Example]
[Synthesis Example 1] Synthesis of polymer compound (I) In a sealed container, 500 mg of the compound represented by the above formula (B2) (synthesized according to the method described in Patent Document 2) and the above formula (C1) 500 mg of a compound (synthesized according to the method described in JP-A-10-1665) was added, and dehydrated toluene (9.9 mL) was added. Subsequently, a toluene solution (0.1 M, 198 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the freeze degassing operation was repeated 5 times. It sealed in vacuum and stirred at 60 ° C. for 60 hours. After the reaction, the reaction solution was dropped into 500 mL of acetone to obtain a precipitate. Further, reprecipitation purification with toluene-acetone was repeated twice, followed by vacuum drying at 50 ° C. overnight to obtain a polymer compound (I).

The weight average molecular weight (Mw) of the polymer compound (I) is 68100, and the molecular weight distribution index (Mw /
Mn) was 1.96. The number of structural units derived from the compound represented by the above formula (B2) in the polymer compound (I) estimated from the result of ¹³ C-NMR measurement and the structure derived from the compound represented by the above formula (C1) The ratio (X: Y) with the number y of units was 40:60.
[Synthesis Example 2] Synthesis of polymer compound (II) (2-1) Synthesis of compound represented by formula (C2)

  Synthesized as in scheme (1). 30 mL of thionyl chloride was added to 5.0 g (28 mmol) of 4-tert-butylbenzoic acid and 4.2 g (28 mmol) of 4-vinylbenzoic acid, and the mixture was heated to reflux for 3 hours. The obtained solution was dried under reduced pressure, 20 mL of N, N-dimethylformamide (DMF) and 4.5 g (57 mmol) of pyridine were dissolved in the residue, and 5.4 g (28 mmol) of isophthalic acid dihydrazide was added at room temperature. Stir for 5 hours. The reaction solution was poured into 500 mL of water, and the resulting precipitate was collected by filtration and dried. To the obtained solid, 15 g of phosphorus oxychloride and 30 mL of chloroform were added and heated under reflux for 3 hours. The reaction solution was poured into 500 mL of saturated aqueous sodium carbonate solution, 100 mL of chloroform was added, and the organic layer was concentrated under reduced pressure. Methanol was added to this and cooled to −50 ° C., and the resulting solid was collected by filtration and dried. The product was further purified by silica gel column chromatography to obtain 1.1 g (2.5 mmol) of the compound represented by the above formula (C2).

Identification data of the compound (C2) are as follows.
Calcd _{(C 28 H 24 N 4 O} 2) C, 74.98; H, 5.39; N, 12.49. Measurement C, 75.30; H, 5.18; N, 12.26.
Mass spectrometry (EI): 448 (M ⁺ ).
(2-2) Synthesis of polymer compound (II) Instead of the compound represented by the above formula (B2) and the compound represented by the above formula (C1), a compound represented by the above formula (B5) (patent) Polymer compound (II) was obtained in the same manner as in Synthesis Example 1, except that the compound represented by the above formula (C2) and the compound represented by the above formula (C2) were used.

The weight average molecular weight (Mw) of the polymer compound (II) was 100500, and the molecular weight distribution index (Mw / Mn) was 2.33. The number of structural units derived from the compound represented by the above formula (B5) in the polymer compound (II) estimated from the result of ¹³ C-NMR measurement and the structure derived from the compound represented by the above formula (C2) The ratio (X: Y) to the number y of units was 48:52.
[Synthesis Example 3] Synthesis of Polymer Compound (III) (3-1) Synthesis of Compound Represented by Formula (C3) above

Synthesized as in scheme (2). Methyl 4-tert-butylbenzoate (3.5 g, 18 mmol) was dissolved in ethanol (50 mL), and hydrazine monohydrate (2.0 g, 40 mmol) was dissolved.
l) was added and heated to reflux for 10 hours. The obtained reaction mixture was poured into 300 mL of water, and the solid was collected by filtration and dried. To this solid, 20 mL of pyridine and 4.4 g (20 mmol) of 4-bromobenzoyl chloride were added and stirred at room temperature for 5 hours. The resulting solution was poured into 300 mL of water, and the solid was collected by filtration and dried. To this solid, 20 mL of o-dichlorobenzene, 1.8 g (19 mmol) of aniline and 6.5 g (47 mmol) of phosphorus trichloride were added and heated to reflux for 3 hours. The reaction solution was poured into 300 mL of water, and organic substances were extracted with chloroform. After concentration of the extract under reduced pressure, 50 mL of 1,2-dimethoxyethane, 3.0 g (20 mmol) of 4-vinylphenylboronic acid, 0.23 g (0.20 mmol) of tetrakis (triphenylphosphine) palladium and 6.3 g of sodium carbonate ( 59 mL of an aqueous solution containing 59 mmol) was added, and the mixture was heated to reflux for 3 hours. After cooling the reaction solution to room temperature, the organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 2.8 g (6.1 mmol) of the compound represented by the above formula (C3).

Identification data of the compound (C3) are as follows.
Calcd _{(C 32 H 29 N 3)} C, 84.36; H, 6.42; N, 9.22.
Measurement C, 84.57; H, 6.33; N, 9.04.
Mass spectrometry (EI): 455 (M ⁺ ).
(3-2) Synthesis of polymer compound (III) Instead of the compound represented by the above formula (B2) and the compound represented by the above formula (C1), a compound represented by the above formula (B1) (patent) A polymer compound (III) was obtained in the same manner as in Synthesis Example 1 except that the compound represented by the above formula (C3) was used and the compound represented by the above formula (C3) was used.

The weight average molecular weight (Mw) of the polymer compound (III) was 55900, and the molecular weight distribution index (Mw / Mn) was 2.04. The number of structural units derived from the compound represented by the formula (B1) in the polymer compound (III) estimated from the result of ¹³ C-NMR measurement and the structure derived from the compound represented by the formula (C3) The ratio (X: Y) with the number y of units was 45:55.
[Synthesis Example 4] Synthesis of iridium complex (E-2)

(4-1) Synthesis of Compound (a) The compound (a) was synthesized as shown in Scheme (3). Contains 6.0 g (38 mmol) of 2-bromopyridine, 6.8 g (38 mmol) of 4-tert-butylphenylboronic acid, 0.50 g (0.43 mmol) of tetrakis (triphenylphosphine) palladium, and 14 g (100 mmol) of potassium carbonate. 50 mL of an aqueous solution and 50 mL of 1,2-dimethoxyethane were mixed and heated to reflux for 3 hours. After cooling the reaction solution to room temperature, ethyl acetate was added, the organic layer was separated, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 7.5 g (35 mmol) of compound (a).
(4-2) Synthesis of iridium complex (b) To a mixture of 4.9 g (23 mmol) of compound (a) and 4.0 g (11 mmol) of iridium trichloride trihydrate, 75 mL of 2-ethoxyethanol and 25 mL of water were added. , And refluxed for 24 hours. The resulting precipitate was collected by filtration, washed with cold methanol, and then dried to obtain 7.0 g (5.4 mmol) of an iridium complex (b).
(4-3) Synthesis of iridium complex (E-2) 20 mL of glycerin was added to a mixture of 3.0 g (2.3 mmol) of iridium complex (b) and 3.0 g (14 mmol) of compound (a), Stir for hours. After cooling the reaction solution to room temperature, 200 mL of water was added, and the precipitate was collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography to obtain 1.6 g (1.9 mmol) of an iridium complex (E-2).

Identification data of the iridium complex (E-2) is as follows.
Calcd _{(C 45 H 48 IrN 3)} C, 65.66; H, 5.88; N, 5.1
1. Measurement C, 65.73; H, 5.82; N, 5.06.
Mass spectrometry (FAB): 823 (M ⁺ ).
[Synthesis Example 5] Synthesis of iridium complex (E-17)

  Synthesized as in scheme (4). Compound (c) was synthesized by the same method as the synthesis of compound (a) except that 1-chloroisoquinoline was used instead of 2-bromopyridine. Next, an iridium complex (d) was synthesized by the same method as the synthesis of the iridium complex (b) except that the compound (c) was used instead of the compound (a). 20 mL of glycerol was added to a mixture of 1.2 g (0.80 mmol) of the iridium complex (d) and 1.0 g (3.8 mmol) of the compound (c), and the mixture was heated and stirred at 200 ° C. for 24 hours. After cooling the reaction solution to room temperature, 200 mL of water was added, and the precipitate was collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography to obtain 0.30 g (0.31 mmol) of an iridium complex (E-17).

Identification data of the iridium complex (E-17) is as follows.
Calcd _{(C 57 H 54 IrN 3)} C, 70.34; H, 5.59; N, 4.3
2. Measurement C, 70.51; H, 5.50; N, 4.19.
Mass spectrometry (FAB): 973 (M ⁺ ).
[Synthesis Example 6] Synthesis of polymer compound (IV) Polymer compound (IV) was synthesized in the same manner as in Synthesis Example 1 except that N-vinylcarbazole was used instead of the compound represented by formula (B2). )

The weight average molecular weight (Mw) of the polymer compound (IV) was 51000, and the molecular weight distribution index (Mw / Mn) was 2.31. The number x of structural units derived from N-vinylcarbazole in the polymer compound (IV) estimated from the result of ¹³ C-NMR measurement and the number y of structural units derived from the compound represented by the above formula (C1) The ratio (X: Y) was 67:33.
[Synthesis Example 7] Synthesis of polymer compound (V) (7-1) Synthesis of compound (f)

Synthesized as in scheme (5). Compound (e) was synthesized by the same method as the synthesis of compound (a) except that 4-bromophenylboronic acid was used instead of 4-tert-butylphenylboronic acid. To 0.48 g (20 mmol) of magnesium was added 10 mL of tetrahydrofuran (THF), and 40 mL of a THF solution of 4.0 g (17 mmol) of compound (e) was added dropwise thereto over 1 hour. After dropping, the mixture was further stirred at room temperature for 1 hour, and 20 mL of a THF solution of 3.0 g (52 mmol) of acetone was added dropwise while cooling with ice. After stirring at room temperature for 1 hour, 500 mL of water was added to the resulting reaction solution. The organic matter was extracted with ethyl acetate, washed with water and saturated brine, and dried by adding magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2.1 g (9.8 mmol) of compound (f).
(7-2) Synthesis of iridium complex (g)

  Synthesized as in scheme (6). To a mixture of iridium complex (b) 0.50 g (0.30 mmol) and compound (f) 0.15 g (0.70 mmol), 10 mL of glycerin was added, and the mixture was heated and stirred at 200 ° C. for 12 hours. After cooling the reaction solution to room temperature, 100 mL of water was added, and the precipitate was collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography to obtain 0.22 g (0.27 mmol) of an iridium complex (g).

Identification data of the iridium complex (g) is as follows.
Calcd _{(C 44 H 44 IrN 3)} C, 65.48; H, 5.50; N, 5.2
1. Measurement C, 65.77; H, 5.36; N, 5.04.
Mass spectrometry (FAB): 807 (M ⁺ ).
(7-3) Synthesis of polymer compound (V) In a sealed container, put 80 mg of the iridium complex (g), 460 mg of the compound represented by the above formula (B2), and 460 mg of the compound represented by the above formula (C1). , Dehydrated toluene (9.9 mL) was added. Subsequently, a toluene solution (0.1 M, 198 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the freeze degassing operation was repeated 5 times. It sealed in vacuum and stirred at 60 ° C. for 60 hours. After the reaction, the reaction solution was dropped into 500 mL of acetone to obtain a precipitate. Further, reprecipitation purification with toluene-acetone was repeated twice, followed by vacuum drying at 50 ° C. overnight to obtain a polymer compound (V).

The weight average molecular weight (Mw) of the polymer compound (V) was 70500, and the molecular weight distribution index (Mw / Mn) was 1.86. Number z of structural units derived from the iridium complex (g) in the polymer compound (V) estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement, structural units derived from the compound represented by the above formula (B2) And the ratio (Z: X: Y) of the number y of structural units derived from the compound represented by the formula (C1) was 5:38:57.
[Synthesis Example 8] Synthesis of polymer compound (VI) Instead of the compound represented by the above formula (B2) and the compound represented by the above formula (C1), 9-ethyl-3-vinylcarbazole (Patent Document 1) The polymer compound (VI) was obtained in the same manner as in Synthesis Example 1, except that the compound represented by the above formula (C2) was used.

The polymer compound (VI) had a weight average molecular weight (Mw) of 81500 and a molecular weight distribution index (Mw / Mn) of 2.31. The number x of structural units derived from 9-ethyl-3-vinylcarbazole in the polymer compound (VI) estimated from the results of ¹³ C-NMR measurement and the structural units derived from the compound represented by the above formula (C2) The ratio (X: Y) with the number y was 70:30.
[Synthesis Example 9] Synthesis of polymer compound (VII) Instead of the iridium complex (g), the compound represented by the above formula (B2), and the compound represented by the above formula (C1), Iridium complex (h) (synthesized according to the method described in JP-A-2003-206320), a compound represented by the above formula (B5), and a compound represented by the above formula (C2) The polymer compound (VII) was obtained in the same manner as in Synthesis Example 7 (7-3).

The polymer compound (VII) had a weight average molecular weight (Mw) of 94500 and a molecular weight distribution index (Mw / Mn) of 2.55. Number z of structural units derived from the iridium complex (h) in the polymer compound (VII) estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement, structural units derived from the compound represented by the above formula (B5) And the ratio (Z: X: Y) of the number y of structural units derived from the compound represented by the above formula (C2) was 6:47:47.

[Synthesis Example 10] Synthesis of polymer compound (VIII) In place of the compound represented by the above formula (B2) and the compound represented by the above formula (C1), N-vinylcarbazole and the above formula (C3) are used. A polymer compound (VIII) was obtained in the same manner as in Synthesis Example 1 except that the above compound was used.

The weight average molecular weight (Mw) of the high molecular compound (VIII) was 51000, and the molecular weight distribution index (Mw / Mn) was 2.25. Polymer compounds estimated from the results of ¹³ C-NMR measurement (
The ratio (X: Y) of the number x of structural units derived from N-vinylcarbazole and the number y of structural units derived from the compound represented by the above formula (C3) in VIII) was 68:32.
Synthesis Example 11 Synthesis of Polymer Compound (IX) (11-1) Synthesis of Compound (i)

Synthesized as in scheme (7). Dissolve 5.0 g (33 mmol) of 1-chloroisoquinoline, 5.5 g (34 mmol) of 4-acetylphenylboronic acid and 0.35 g (0.30 mmol) of tetrakis (triphenylphosphine) palladium in 50 mL of 1,2-dimethoxyethane. Then, 50 mL of an aqueous solution of 12.3 g (89 mmol) of potassium carbonate was added and heated to reflux for 3 hours. The resulting reaction solution was allowed to cool to room temperature, 100 mL of water and 100 mL of ethyl acetate were added, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, 50 mL of diethyl ether and 35 mL (35 mmol) of diethyl ether solution of methyllithium (1.0 mol / l) were added to the residue, and the mixture was stirred at room temperature for 2 hours. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 4.8 g (19 mmol) of compound (i).
(11-2) Synthesis of iridium complex (j)

  Synthesized as in scheme (8). 10 mL of glycerol was added to a mixture of 0.61 g (0.41 mmol) of the iridium complex (d) and 0.22 g (0.88 mmol) of the compound (i), and the mixture was heated and stirred at 200 ° C. for 12 hours. After cooling the reaction solution to room temperature, 100 mL of water was added, and the precipitate was collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography to obtain 0.16 g (0.17 mmol) of an iridium complex (j).

Identification data of the iridium complex (j) is as follows.
Calcd _{(C 56 H 50 IrN 3)} C, 70.26; H, 5.26; N, 4.3
9. Measurement C, 69.90; H, 5.38; N, 4.61.
Mass spectrometry (FAB): 957 (M ⁺ ).
(11-3) Synthesis of polymer compound (IX) Instead of the iridium complex (g), the compound represented by the above formula (B2), and the compound represented by the above formula (C1), an iridium complex (j) A polymer compound (IX) was obtained in the same manner as in Synthesis Example 7 (7-3) except that the compound represented by the above formula (B1) and the compound represented by the above formula (C3) were used. It was.

The polymer compound (IX) had a weight average molecular weight (Mw) of 61900 and a molecular weight distribution index (Mw / Mn) of 2.18. Number z of structural units derived from the iridium complex (j) in the polymer compound (IX) estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement, structural units derived from the compound represented by the above formula (B1) And the ratio (Z: X: Y) of the number y of structural units derived from the compound represented by the formula (C3) was 5:43:52. [Synthesis Example 12] Synthesis of iridium complex (E-34)

  Synthesized as in scheme (9). Compound (k) was synthesized by the same method as the synthesis of compound (c) except that 4-n-butylphenylboronic acid was used instead of 4-tert-butylphenylboronic acid. Next, an iridium complex (l) was synthesized by the same method as the synthesis of the iridium complex (b) except that the compound (k) was used instead of the compound (a). 20 ml of glycerin was added to a mixture of 2.4 g (1.6 mmol) of iridium complex (l) and 2.0 g (7.6 mmol) of compound (k), and the mixture was heated and stirred at 200 ° C. for 24 hours. After cooling the reaction solution to room temperature, 200 mL of water was added, and the precipitate was collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography to obtain 0.60 g (0.62 mmol) of an iridium complex (E-34).

Identification data of the iridium complex (E-34) is as follows.
Calcd _{(C 57 H 54 IrN 3)} C, 70.34; H, 5.59; N, 4.3
2. Measurement C, 70.38; H, 5.61; N, 4.19.
Mass spectrometry (FAB): 973 (M ⁺ ).
[Synthesis Example 13] Synthesis of polymer compound (X) (13-1) Synthesis of compound (n)

Synthesized as in scheme (10). The compound (m) was synthesized by the same method as the synthesis of the compound (e) except that 1-chloroisoquinoline was used instead of 2-bromopyridine. Compound (m) (1.5 g, 5.3 mmol) and dichloro (bis (diphenylphosphino) propane) nickel (0.10 g, 0.18 mmol) were dissolved in 20 ml of THF. To this solution, 15 ml (7.5 mmol) of 5-hexenylmagnesium bromide in THF (0.50 M) was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 5 hours. After adding 5 ml of methanol to the obtained reaction solution, the solvent was distilled off under reduced pressure and purified by silica gel column chromatography to obtain 0.90 g (3.1 mmol) of compound (n).
(13-2) Synthesis of iridium complex (o)

  Synthesized as in scheme (11). 10 ml of glycerol was added to a mixture of 0.50 g (0.33 mmol) of the iridium complex (l) and 0.20 g (0.70 mmol) of the compound (n), and the mixture was heated and stirred at 180 ° C. for 48 hours. The reaction solution was cooled to room temperature, 100 ml of water was added, and the precipitate was collected by filtration and dried. The obtained crude product was purified by silica gel column chromatography to obtain 0.10 g (0.10 mmol) of an iridium complex (o).

Identification data of the iridium complex (o) is as follows.
Calcd _{(C 59 H 56 IrN 3)} C, 70.91; H, 5.65; N, 4.2
0. Measurement C, 70.65; H, 5.82; N, 4.44.
Mass spectrometry (FAB): 999 (M ⁺ ).
(13-3) Synthesis of polymer compound (X) Instead of the iridium complex (g), the compound represented by the above formula (B2), and the compound represented by the above formula (C1), an iridium complex (o) A polymer compound (X) was obtained in the same manner as in Synthesis Example 7 (7-3) except that the compound represented by the above formula (B1) and the compound represented by the above formula (C3) were used. It was.

The weight average molecular weight (Mw) of the polymer compound (X) was 61900, and the molecular weight distribution index (Mw / Mn) was 2.50. Number z of structural units derived from the iridium complex (j) in the polymer compound (IX) estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement, structural units derived from the compound represented by the above formula (B1) And the ratio (Z: X: Y) of the number y of structural units derived from the compound represented by the above formula (C3) was 4:45:51.
[Synthesis Example 14] Coating solution (I)
92 mg of the polymer compound (I) and 8 mg of the iridium complex (E-2) were dissolved in 2900 mg of toluene, and this solution was filtered with a filter having a pore size of 0.2 μm to prepare a coating solution (I).
[Synthesis Example 15] Coating solution (II)
Instead of polymer compound (I) and iridium complex (E-2), polymer compound (II) and iridium complex (E-33) (synthesized according to the method described in JP-T-2004-506305) are used. The coating solution (II) was prepared in the same manner as in Synthesis Example 14, except that
[Synthesis Example 16] Coating solution (III)
A coating solution (III) was prepared in the same manner as in Synthesis Example 14 except that the polymer compound (III) and the iridium complex (E-17) were used instead of the polymer compound (I) and the iridium complex (E-2). ) Was prepared.
[Synthesis Example 17] Coating solution (IV)
A coating solution (IV) was prepared in the same manner as in Synthesis Example 14 except that the polymer compound (IV) and the iridium complex (E-2) were used instead of the polymer compound (I) and the iridium complex (E-2). ) Was prepared.
[Synthesis Example 18] Coating solution (V)
100 mg of the polymer compound (V) was dissolved in 2900 mg of toluene, and this solution was filtered with a filter having a pore size of 0.2 μm to prepare a coating solution (V).
[Synthesis Example 19] Coating solution (VI)
A coating solution (VI) was prepared in the same manner as in Synthesis Example 14 except that the polymer compound (VI) and the iridium complex (E-33) were used instead of the polymer compound (I) and the iridium complex (E-2). ) Was prepared.
[Synthesis Example 20] Coating solution (VII)
A coating solution (VII) was prepared in the same manner as in Synthesis Example 18, except that the polymer compound (VII) was used instead of the polymer compound (V).
[Synthesis Example 21] Coating solution (VIII)
A coating solution (VIII) was prepared in the same manner as in Synthesis Example 14 except that the polymer compound (VIII) and the iridium complex (E-17) were used instead of the polymer compound (I) and the iridium complex (E-2). ) Was prepared.
[Synthesis Example 22] Coating solution (IX)
A coating solution (IX) was prepared in the same manner as in Synthesis Example 18, except that the polymer compound (IX) was used instead of the polymer compound (V).
[Synthesis Example 23] Coating solution (X)
A coating solution (X) was prepared in the same manner as in Synthesis Example 14 except that the polymer compound (III) and the iridium complex (E-34) were used instead of the polymer compound (I) and the iridium complex (E-2). ) Was prepared.
[Synthesis Example 24] Coating solution (XI)
A coating solution (XI) was prepared in the same manner as in Synthesis Example 14 except that the polymer compound (VIII) and the iridium complex (E-34) were used instead of the polymer compound (I) and the iridium complex (E-2). ) Was prepared.
[Synthesis Example 25] Coating solution (XII)
A coating solution (XII) was prepared in the same manner as in Synthesis Example 18, except that the polymer compound (X) was used instead of the polymer compound (V).
[Example 1] Preparation of organic EL element and evaluation of light emission characteristics A substrate with ITO (manufactured by Nippon Electric Co., Ltd.) was used. This was a substrate in which two ITO (indium tin oxide) electrodes (anodes) having a width of 4 mm were formed in one stripe on one surface of a 25 mm square glass substrate.

  First, poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid (manufactured by Bayer Co., Ltd., trade name “BYTRON P”) on the above-mentioned ITO-attached substrate under conditions of a rotation speed of 3500 rpm and a coating time of 40 seconds. Then, it was applied by spin coating. Then, it dried for 2 hours at 60 degreeC under pressure reduction with the vacuum dryer, and formed the anode buffer layer. The film thickness of the obtained anode buffer layer was about 50 nm.

  Next, the coating solution (I) was coated on the anode buffer layer by a spin coating method under the conditions of a rotation speed of 3000 rpm and a coating time of 30 seconds. After the application, it was dried at room temperature (25 ° C.) for 30 minutes to form a light emitting layer. The film thickness of the obtained light emitting layer was about 100 nm.

  Next, the substrate on which the light emitting layer was formed was placed in a vapor deposition apparatus. Next, calcium and aluminum were co-evaporated at a weight ratio of 1:10, and two cathodes having a width of 3 mm were formed in a stripe shape so as to be orthogonal to the extending direction of the anode. The film thickness of the obtained cathode was about 50 nm.

Finally, lead wires (wirings) were attached to the anode and the cathode in an argon atmosphere, and four organic EL elements measuring 4 mm in length and 3 mm in width were produced. A voltage was applied to the organic EL element to emit light using a programmable DC voltage / current source (TR6143, manufactured by Advantest Corporation). The emission luminance was measured using a luminance meter (BM-8, manufactured by Topcon Corporation). Table 1 shows the emission color, the maximum emission external quantum efficiency, and the luminance half-life at 100 cd / m ² lighting of the produced organic EL element.
[Examples 2 to 4 and Comparative Examples 1 to 8] Preparation of organic EL elements and evaluation of light emission characteristics Organic EL elements were prepared in the same manner as in Example 1 except that the coating solution was changed to the solution shown in Table 1. And measured. Table 1 shows the emission color, the maximum emission external quantum efficiency, and the luminance half-life at 100 cd / m ² lighting of the produced organic EL element.

FIG. 1 is a cross-sectional view of an example of an organic EL element according to the present invention.

Explanation of symbols

1: Glass substrate 2: Anode 3: Hole transport layer 4: Light emitting layer 5: Electron transport layer 6: Cathode

Claims (7)

In an organic electroluminescence device including one or more organic layers sandwiched between an anode and a cathode,
At least one of the organic layers includes a phosphorescent compound and a polymer compound,
The polymer compound is derived from a structural unit derived from a monomer represented by any of the following formulas (B1) to (B6) and a monomer having a heterocycle containing two or more heteroatoms. An organic electroluminescence device comprising a structural unit to be cut.

  The organic electroluminescence device according to claim 1, wherein the monomer having a heterocycle is an oxadiazole derivative or a triazole derivative. The organic electroluminescence device according to claim 2, wherein the monomer having a heterocycle is selected from the group consisting of monomers represented by the following formulas (2) to (5).

(In formulas (2) to (5), R ^{28 to} R ⁷¹ are each a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. the ^{stands, R 28 ~R 31, R 32} ~R 36, R 37 ~R 40, R 42 ~R 44, R 45 ~R 49, R 50 ~R 54, R 58 ~R 62, R 63 ~R 66 , And R ^{67 to} R ⁷¹ , two groups bonded to adjacent carbon atoms on the benzene ring may be bonded to each other to form a condensed ring, and X ^{2 to} X ⁵ are Single bond, oxygen atom (—O—), sulfur atom (—S—), —SO—, —SO ₂ —, —NR— (R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or Represents a phenyl group), -CO-, or a divalent organic group having 1 to 20 carbon atoms (the organic group includes an oxygen atom (-O-), a sulfur atom (-S ), - SO -, - SO 2 -, - NR- (R is a hydrogen atom, or atoms selected from the group consisting of) and -CO- represents an alkyl group or a phenyl group, having 1 to 4 carbon atoms. And Y ^{2 to} Y ⁵ each represents a polymerizable functional group . In the formula (5), Ar represents a phenyl group or a naphthyl group.) The organic electroluminescence device according to claim 3, wherein the monomer having a heterocycle is represented by any of the following formulas (C1) to (C4).

The phosphorescence-emitting compound, an organic electroluminescent device according to any one of claims 1 to 4, characterized in that an iridium complex. The image display apparatus using the organic electroluminescent element in any one of Claims 1-5 . The surface emitting light source using the organic electroluminescent element in any one of Claims 1-5 .

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