JP2009043896A - Organic light-emitting element and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic light-emitting element which has high light emission efficiency, high luminance, and extremely long-life optical output. <P>SOLUTION: The organic light emitting element comprises a positive electrode and a negative electrode, and a layer formed of an organic compound sandwiched between the positive electrode and negative electrode, and is characterized in that the layer formed of the organic compound contains at least one of aryl amine polymer expressed by general formula (1). In formula (1), Ar<SB>1</SB>and Ar<SB>2</SB>each represents a substituted or unsubstituted aryl group or substituted or unsubstituted condensed polycyclic aromatic group, wherein, one of Ar<SB>1</SB>and Ar<SB>2</SB>represents a substituted or unsubstituted fluorenyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic light emitting device and a display.

  The manufacturing process of the organic light emitting device is classified into a dry method and a wet method. Here, the dry method is a method of forming a thin film using a gas phase process such as a vacuum vapor deposition method mainly using a low molecular weight material in the film forming process. On the other hand, the wet method mainly uses a polymer material in the film forming process, and forms a thin film by using a spin coating method, an ink jet coating method, a dispenser coating method, a spray coating method, a dip coating method, or the like. How to do it.

  In dry methods such as vacuum deposition, the production apparatus is a batch type, and a material film may be formed on a portion that is not necessary for light emission of the device. For this reason, much more material than necessary is consumed wastefully, and it can be said that this method has a problem in productivity.

  On the other hand, production by a wet method can be produced by continuous processing. For example, the application can be selected by a droplet discharge method such as an inkjet application method or a dispenser application method. In these methods, since the patterning and coating can be simultaneously performed by coating the material only on the necessary portion of the element, the productivity can be greatly improved.

  Therefore, recently, organic layers such as a charge injection layer, a charge transport layer, and a light emitting layer of an organic light emitting device are required to be formed by a coating process with high productivity.

  Here, it is known that a coating-type hole injection material uses a thin film composed of a mixture of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid in order to improve charge injection properties. (See Non-Patent Document 1). However, an organic light emitting device using this hole injection material is excellent in initial characteristics, but has a problem that luminance deterioration is remarkable when it is used for a long time. Therefore, a material that is excellent in charge injection property and charge transport property and more chemically stable is desired.

  However, at present, charge injection materials and charge transport materials that can be used in these coating processes are limited, and initial characteristics such as light emission efficiency and durability characteristics such as luminance deterioration due to long-time light emission are not sufficient. was there.

Appl. Phys. Lett. , 75, 1679 (1999)

  An object of the present invention is to provide an organic light emitting device having high light emission efficiency, high luminance, and extremely long life light output. Another object of the present invention is to provide an organic light emitting device that is easy to manufacture and can be produced by a relatively inexpensive coating method.

  The organic light-emitting device of the present invention comprises an anode, a cathode, and a layer made of an organic compound sandwiched between the anode and the cathode. The layer made of the organic compound has the following general formula (1) At least one kind of arylamine polymer represented by the formula:

（式（１）において、Ｒ₁及びＲ₂は、それぞれ水素原子、置換あるいは無置換のアルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基、ハロゲン原子又はアルコキシ基を表す。Ａｒ₁及びＡｒ₂は、それぞれ置換あるいは無置換のアリール基又は置換あるいは無置換の縮合多環芳香族基を表す。但し、Ａｒ₁及びＡｒ₂のうちいずれかは、置換あるいは無置換のフルオレニル基を表す。Ａｒ₃は、置換あるいは無置換の２個以上のベンゼン環からなるアリーレン基又は置換あるいは無置換の２価の縮合多環芳香族基を表す。Ａｒ₄は、置換あるいは無置換のアリーレン基又は置換あるいは無置換の２価の縮合多環芳香族基を表す。ｍは１０以上２００以下の整数を表す。ｎは０以上２００以下の整数を表す。）

(In the formula (1), R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a halogen atom or an alkoxy group. Ar ₁ and Ar ₂ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted condensed polycyclic aromatic group, provided that either Ar ₁ or Ar ₂ is a substituted or unsubstituted fluorenyl group. Ar ₃ represents an arylene group composed of two or more substituted or unsubstituted benzene rings or a substituted or unsubstituted divalent condensed polycyclic aromatic group, and Ar ₄ represents a substituted or unsubstituted arylene. Represents a group or a substituted or unsubstituted divalent condensed polycyclic aromatic group, m represents an integer of 10 or more and 200 or less, and n represents an integer of 0 or more and 200 or less.)

  ADVANTAGE OF THE INVENTION According to this invention, the organic light emitting element which has the light output of high luminous efficiency, high-intensity, and a very long lifetime can be provided. Moreover, according to this invention, the organic light emitting element which is easy to manufacture and can be produced with the comparatively cheap coating method can be provided.

  Hereinafter, the present invention will be described in detail. First, the organic light emitting device of the present invention will be described.

  The organic light emitting device of the present invention includes an anode, a cathode, and a layer made of an organic compound sandwiched between the anode and the cathode.

  Hereinafter, the organic light emitting device of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view showing a first embodiment of the organic light-emitting device of the present invention. In the organic light emitting device 10 of FIG. 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially provided on a substrate 1. The organic light emitting device 10 of FIG. 1 is useful when the light emitting layer 3 has all the hole transporting ability, electron transporting ability, and light emitting performance. Further, it is also useful when an organic compound having any one of the characteristics of hole transport ability, electron transport ability and light emitting performance is mixed.

  FIG. 2 is a cross-sectional view showing a second embodiment of the organic light emitting device of the present invention. In the organic light emitting device 20 of FIG. 2, an anode 2, a hole transport layer 5, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This organic light emitting device 20 is useful when a light emitting organic compound having either a hole transporting property or an electron transporting property and an organic compound having only an electron transporting property or only a hole transporting property are used in combination. is there. In the organic light emitting device 20, the hole transport layer 5 or the electron transport layer 6 also serves as a light emitting layer.

  FIG. 3 is a cross-sectional view showing a third embodiment of the organic light-emitting device of the present invention. An organic light emitting device 30 in FIG. 3 is obtained by providing the light emitting layer 3 between the hole transport layer 5 and the electron transport layer 6 in the organic light emitting device 20 in FIG. The organic light emitting device 30 is a device in which the function of transporting carriers and the function of emitting light are separated, and compounds having hole transporting properties, electron transporting properties, and light emitting properties can be used in appropriate combinations. . For this reason, the degree of freedom in material selection is increased, and various compounds having different emission wavelengths can be used, so that the emission hue can be diversified. Furthermore, it is possible to effectively confine each carrier or exciton in the central light emitting layer 3 to improve the light emission efficiency of the organic light emitting device 30.

  FIG. 4 is a cross-sectional view showing a fourth embodiment of the organic light emitting device of the present invention. An organic light emitting device 40 in FIG. 4 is obtained by providing a hole injection layer 7 between the anode 2 and the hole transport layer 5 in the organic light emitting device 30 in FIG. 3. By providing the hole injection layer 7, the adhesion between the anode 2 and the hole transport layer 5 or the hole injection property is improved, which is effective for lowering the voltage. Further, a buffer layer may be provided in place of the hole injection layer 7, but the function is the same as that of the hole injection layer.

  FIG. 5 is a cross-sectional view showing a fifth embodiment of the organic light-emitting device of the present invention. The organic light emitting device of FIG. 5 is obtained by providing an electron injection layer 8 between the electron transport layer 6 and the cathode 4 in the organic light emitting device 40 of FIG. By providing the electron injection layer 8, the adhesion or electron injection between the cathode 4 and the electron transport layer 6 is improved, which is effective for lowering the voltage.

  FIG. 6 is a cross-sectional view showing a sixth embodiment of the organic light emitting device of the present invention. The organic light emitting device 60 of FIG. 6 is obtained by providing the hole / exciton blocking layer 9 between the light emitting layer 3 and the electron transport layer 6 in the organic light emitting device 30 of FIG. By providing the hole / exciton blocking layer 9, holes or excitons are prevented from being released from the light emitting layer 3 to the cathode 4 side, which is effective in improving luminous efficiency.

  FIG. 7 is a cross-sectional view showing a seventh embodiment of the organic light-emitting device of the present invention. In the organic light emitting device 70 of FIG. 7, an anode 2, a hole injection layer 7, a light emitting layer 3, an electron injection layer 8, and a cathode 4 are sequentially provided on a substrate 1.

  However, FIG. 1 to FIG. 7 are very basic device configurations, and the organic light-emitting device of the present invention is not limited to these. For example, an insulating layer, an adhesive layer or an interference layer is provided at the interface between the electrode and the organic layer, and the hole injection layer or the hole transport layer is composed of two layers having different ionization potentials. it can.

  As an embodiment of the organic light emitting device of the present invention, preferably, a layer made of an organic compound includes the hole injection layer 7 and the light emitting layer 3, and the hole injection layer 7 is in contact with the light emitting layer 3. Is.

  The organic light-emitting device of the present invention is characterized in that at least one kind of arylamine polymer represented by the following general formula (1) is contained in a layer made of an organic compound.

In the formula (1), R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a halogen atom or an alkoxy group.

Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the aralkyl group represented by R ₁ and R ₂ include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group, a biphenyl group, and a terphenyl group.

Examples of the halogen atom represented by R ₁ and R ₂ include fluorine, chlorine, bromine and the like.

Examples of the alkoxy group represented by R ₁ and R ₂ include a methoxy group, an ethoxy group, and a propoxy group.

  As the substituents that the alkyl group, aralkyl group and aryl group may further have, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aralkyl group such as a benzyl group, a phenethyl group and a naphthylmethyl group, Aryl group such as phenyl group, biphenyl group, condensed polycyclic aromatic group such as naphthyl group, fluorenyl group, anthryl group, pyrenyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, phenoxy group, naphthoxy group, etc. Examples include aryloxy groups, halogen atoms such as fluorine, chlorine, bromine and iodine, nitro groups, and cyano groups.

In the formula (1), Ar ₁ and Ar ₂ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted condensed polycyclic aromatic group.

Examples of the aryl group represented by Ar ₁ and Ar ₂ include a phenyl group, a biphenyl group, and a terphenyl group.

Examples of the condensed polycyclic heterocyclic group represented by Ar ₁ and Ar ₂ include a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, and a pyrenyl group.

  Examples of the substituent that the aryl group and the condensed polycyclic heterocyclic group may further have include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a tert-butyl group, a benzyl group, a phenethyl group, and a naphthylmethyl group. Aryl groups such as aralkyl groups, phenyl groups, biphenyl groups, condensed polycyclic aromatic groups such as naphthyl groups, fluorenyl groups, anthryl groups, pyrenyl groups, alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, phenoxy groups, naphthoxy groups And aryloxy groups such as a group, halogen atoms such as fluorine, chlorine, bromine and iodine, nitro groups, cyano groups and the like.

However, either Ar ₁ or Ar ₂ represents a substituted or unsubstituted fluorenyl group. If either Ar ₁ or Ar ₂ is a fluorenyl group, the polymer has high charge transport properties and excellent film properties. From the viewpoint of improving the film property, Ar ₁ and Ar ₂ are preferably a substituted or unsubstituted fluorenyl group.

In the formula (1), Ar ₃ represents an arylene group composed of two or more substituted or unsubstituted benzene rings or a substituted or unsubstituted divalent condensed polycyclic aromatic group.

The arylene group composed of two or more benzene rings represented by Ar ₃ refers to a substituent constituted by connecting two or more, preferably two to four benzene rings, with a single bond. Specific examples of the arylene group include a biphenylene group and a terphenylene group.

Examples of the divalent condensed polycyclic aromatic group represented by Ar ₃ include a naphthylene group, a fluorenylene group, an anthrylene group, a phenanthrylene group, and a pyrenylene group.

  Examples of the substituent that the arylene group and the divalent condensed polycyclic aromatic group may have include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a benzyl group, a phenethyl group, and a naphthylmethyl group. Aryl groups such as aralkyl groups, phenyl groups, biphenyl groups, condensed polycyclic aromatic groups such as naphthyl groups, fluorenyl groups, anthryl groups, pyrenyl groups, alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, phenoxy groups, naphthoxy groups And aryloxy groups such as a group, halogen atoms such as fluorine, chlorine, bromine and iodine, nitro groups, cyano groups and the like.

In the formula (1), Ar ₄ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent condensed polycyclic aromatic group.

Examples of the arylene group represented by Ar ₄ include a phenylene group, a biphenylene group, and a terphenylene group.

Examples of the divalent condensed polycyclic aromatic group represented by Ar ₄ include a naphthylene group, a fluorenylene group, an anthrylene group, a phenanthrylene group, and a pyrenylene group.

  Examples of the substituent that the arylene group and the divalent condensed polycyclic aromatic group may have include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 3-methylbutyl group, 2-ethylhexyl group, and octyl group. Group, benzyl group, phenethyl group, aralkyl group such as naphthylmethyl group, aryl group such as phenyl group and biphenyl group, condensed polycyclic aromatic group such as naphthyl group, fluorenyl group, anthryl group, pyrenyl group, methoxy group, ethoxy Groups, alkoxy groups such as propoxy group, aryloxy groups such as phenoxy group and naphthoxy group, halogen atoms such as fluorine, chlorine, bromine and iodine, nitro group, cyano group and the like.

  In Formula (1), m represents an integer of 10 or more and 200 or less.

  In the formula (1), n represents an integer of 0 or more and 200 or less.

  In the arylamine polymer contained in the organic light-emitting device of the present invention, the solubility of the polymer itself can be adjusted by the repeating numbers m and n. The number of repetitions m is not particularly specified, but is preferably 10 or more and 100 or less in that the solubility in a solvent can be sufficiently increased. The repeating number n is preferably 0 or more and 100 or less for the same reason. Further, the molecular weight of the polymer is determined by various factors such as the reaction temperature, the reaction solvent, the amount of the reaction solvent, and the catalyst when the polymer is synthesized.

  By the way, in the organic light emitting device of the present invention, the layer made of an organic compound may contain at least one kind of arylamine polymer represented by the following general formula (2) instead of the arylamine polymer of the formula (1). Good.

In the formula (2), R ₃ and R ₄ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a halogen atom or an alkoxy group.

Specific examples of the alkyl group, the aralkyl group, the aryl group, the halogen atom and the alkoxy group represented by R ₃ and R ₄ , and the substituent that the alkyl group, the aralkyl group and the aryl group may further have are represented by the formula (1 It is the same as R ₁ and R ₂ in).

In the formula (2), Ar ₅ and Ar ₆ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted condensed polycyclic aromatic group.

The aryl group and condensed polycyclic aromatic group represented by Ar ₅ and Ar ₆ are the same as Ar ₁ and Ar ₂ in formula (1).

  As the substituent that the aryl group and the condensed polycyclic aromatic group may further have, an alkyl group such as a methyl group, an ethyl group, a propyl group, a tert-butyl group, and a 3-methylbutyl group, a benzyl group, a phenethyl group, Aralkyl groups such as naphthylmethyl groups, aryl groups such as phenyl groups and biphenyl groups, condensed polycyclic aromatic groups such as naphthyl groups, fluorenyl groups, anthryl groups and pyrenyl groups, alkoxy groups such as methoxy groups, ethoxy groups and propoxy groups Aryloxy groups such as phenoxy group and naphthoxy group, halogen atoms such as fluorine, chlorine, bromine and iodine, nitro group and cyano group.

However, either Ar ₅ or Ar ₆ represents a substituted or unsubstituted fluorenyl group. If either Ar ₅ or Ar ₆ is a fluorenyl group, the polymer has high charge transporting properties and excellent film properties. From the viewpoint of further improving the film property, Ar ₅ and Ar ₆ are preferably a substituted or unsubstituted fluorenyl group.

In the formula (2), Ar ₇ represents an arylene group composed of two or more substituted or unsubstituted benzene rings or a substituted or unsubstituted divalent condensed polycyclic aromatic group.

An arylene group composed of two or more benzene rings and a divalent condensed polycyclic aromatic group represented by Ar ₇ , and an arylene group composed of two or more benzene rings and a condensed polycyclic aromatic group Optional substituents are the same as those for Ar ₃ .

In the formula (2), Ar ₈ represents a substituted or unsubstituted arylene group or a substituted or unsubstituted divalent condensed polycyclic aromatic group.

The arylene group and divalent condensed polycyclic aromatic group represented by Ar ₈ and the substituent that the arylene group and condensed polycyclic aromatic group may further have are the same as those for Ar ₄ .

  In the formula (2), o represents an integer of 10 or more and 200 or less.

  The solubility of the polymer itself can also be adjusted by the number of repetitions of the arylamine polymer of the formula (2). The number of repetitions o does not particularly define the range, but is preferably 10 or more and 100 or less because the film stability is improved as the molecular weight is increased. Further, the molecular weight of the polymer is determined by various factors such as the reaction temperature, the reaction solvent, the amount of the reaction solvent, and the catalyst when the polymer is synthesized.

  Next, specific examples of the arylamine polymer contained in the organic light-emitting device of the present invention are shown below. However, the present invention is not limited to these.

  As described above, the organic light-emitting device of the present invention includes an arylamine polymer represented by the formula (1) or (2) in a layer made of an organic compound. Here, the layer made of an organic compound specifically refers to the light emitting layer 3, the hole transport layer 5, the electron transport layer 6, the hole injection layer 7, the electron injection layer 8 and the like shown in FIGS. It refers to any of the hole / exciton blocking layer 9. The arylamine polymer of the formula (1) or (2) is preferably included in the hole injection layer 7 or the light emitting layer 3.

  When the arylamine polymer of the formula (1) or (2) is included in the light emitting layer 3, the light emitting layer 3 may be composed only of the arylamine polymer of the formula (1) or (2), and It may consist of guests.

  When the light emitting layer 3 is comprised with a host and a guest, the arylamine polymer of Formula (1) or (2) may be a host or a guest.

  When the arylamine polymer of the formula (1) or (2) is used as a guest of the light emitting layer 3, generally known hole transporting compounds, light emitting compounds and electron transporting compounds are used as the corresponding hosts. Can be used. For example, a triarylamine derivative, a phenylenediamine derivative, a triazole derivative, an oxadiazol derivative, an imidazole derivative, a phthalocyanine derivative, poly (vinylcarbazole), poly (thiophene), and the like can be given.

  In such a case, the content of the arylamine polymer of the formula (1) or (2) is preferably 0.1 wt% or more and 50 wt% or less with respect to the total weight of the material constituting the light emitting layer 3. More preferably, it is 0.5 wt% or more and 30 wt% or less.

  When the arylamine polymer of the formula (1) or (2) is used as the host of the light emitting layer 3, generally known fluorescent light emitting compounds and phosphorescent light emitting compounds can be used as the corresponding guests. .

  Examples of fluorescent light-emitting compounds include benzoxazole and derivatives thereof, benzimidazole and derivatives thereof, benzothiazole and derivatives thereof, styrylbenzene and derivatives thereof, polyphenyl and derivatives thereof, diphenylbutadiene and derivatives thereof, and tetraphenylbutadiene and derivatives thereof. , Naphthalimide and derivatives thereof, coumarin and derivatives thereof, condensed ring aromatic compounds, perinone and derivatives thereof, oxadiazole and derivatives thereof, oxazine and derivatives thereof, aldazine and derivatives thereof, pyraridine and derivatives thereof, cyclopentadiene and derivatives thereof Bisstyrylanthracene and derivatives thereof, quinacridone and derivatives thereof, pyrrolopyridine and derivatives thereof, thiadiazolopyridine and derivatives thereof, cyclopentadiene and Derivatives, styrylamine and derivatives thereof, diketopyrrolopyrrole and derivatives thereof, aromatic dimethylidin compounds, metal complexes having 8-quinolinol or derivatives thereof as ligands, metal complexes having pyromethene or derivatives thereof as ligands, Examples thereof include various metal complexes represented by rare earth complexes and transition metal complexes, polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene, organic silanes, and derivatives thereof.

  Examples of the phosphorescent light emitting compound include transition metal complexes. The transition metal complex is not particularly limited, but is preferably an iridium complex, a platinum complex, a rhenium complex, a copper complex, a ruthenium complex, or the like, and more preferably an iridium complex.

  In such a case, the content of the arylamine polymer of the formula (1) or (2) is preferably 50% by weight or more and 99.9% by weight or less with respect to the total weight of the material constituting the light emitting layer 3. More preferably, it is 70 weight% or more and 99.5 weight% or less.

  The organic light emitting device of the present invention can be used together with a known hole transporting compound, light emitting compound, electron transporting compound or the like.

  Examples of these known compounds are given below.

  The material constituting the anode should have a work function as large as possible. For example, a simple metal such as gold, silver, platinum, nickel, palladium, cobalt, selenium, vanadium or an alloy obtained by combining a plurality of these metals, a metal oxide such as tin oxide, zinc oxide, indium tin oxide (ITO), and indium zinc oxide Can be used. In addition, conductive polymers such as polyaniline, polypyrrole, polythiophene, and polyphenylene sulfide can also be used. These electrode materials may be used alone or in combination of two or more.

  On the other hand, the material constituting the cathode is preferably a material having a small work function. For example, a single metal such as lithium, sodium, potassium, cesium, calcium, magnesium, aluminum, indium, silver, lead, tin, chromium, an alloy in which a plurality of these metals are combined, or a salt thereof can be used. A metal oxide such as indium tin oxide (ITO) can also be used. Moreover, the cathode may be composed of a single layer or a plurality of layers.

  Although it does not specifically limit as a board | substrate used with the organic light emitting element of this invention, Transparent substrates, such as opaque board | substrates, such as a metal board | substrate and a ceramic board | substrate, glass, quartz, a plastic sheet, are used. It is also possible to control the color light by using a color filter film, a fluorescent color conversion filter film, a dielectric reflection film or the like on the substrate.

  Note that a protective layer or a sealing layer can be provided for the manufactured element in order to prevent contact with oxygen, moisture, or the like. As the protective layer, diamond thin films, inorganic material films such as metal oxides and metal nitrides, polymer films such as fluorine resin, polyparaxylene, polyethylene, silicone resin, polystyrene resin, epoxy resin, phenol resin, urea resin, or the like Examples thereof include a photocurable resin. Further, it is possible to cover glass, a gas-impermeable film, a metal, etc., and to package the element itself with an appropriate sealing resin.

  Next, the manufacturing method of the organic light emitting element of this invention is demonstrated. In the organic light-emitting device of the present invention, in particular, a layer containing the arylamine polymer of the formula (1) or (2) is formed by a coating method. This is because the arylamine polymer of the formula (1) or (2) is a high molecular weight compound and has no sublimation property, so that layer formation by vapor deposition cannot be performed. In addition, since the arylamine polymer of the formula (1) or (2) has this feature, it is possible to prepare a coating solution without crystallization and to perform coating easily like a normal polymer material.

  Specific examples of the coating method include a casting method, a spin coating method, a slit coater method, a printing method, an ink jet method, a dispensing method, a spray method, a dip method, and an LB film method.

  The film thickness of the layer containing the arylamine polymer of the formula (1) or (2) is less than 10 μm, preferably 0.5 μm or less, more preferably 0.005 μm to 0.5 μm.

  The organic light emitting device of the present invention may have a plurality of organic layers in addition to the light emitting layer. For example, the hole transport layer 5, the electron transport layer 6, the hole injection layer 7, the electron injection layer 8, the hole / exciton blocking layer 9 and the like shown in FIGS. These layers can be formed by any method such as a vacuum deposition method or a solution coating method.

  The layer containing an organic compound other than the arylamine polymer of the formula (1) or (2) can be formed into a thin film by a dry method such as a general vacuum deposition method, and a suitable solvent can be used. It is also possible to form a thin film by a coating method or the like performed by dissolving.

  In the case of forming a thin film by a coating method, specific coating methods include a casting method, a spin coating method, a slit coater method, a printing method, an ink jet method, a dispense method, a spray method, a dip method, and an LB film method.

  The film thickness of the organic layer other than the light emitting layer is thinner than 5 μm, preferably 1 μm or less, and more preferably 5 nm or more and 500 nm or less.

  As described above, the layer containing the arylamine polymer of the formula (1) or (2) is formed by a coating method. In such a case, preferably, a coating liquid composition described later is prepared prior to the formation of the layer.

  The coating liquid composition refers to a solution-like mixture containing at least one arylamine polymer represented by the formula (1) or (2) and a solvent. When this coating liquid composition is used, a layer made of an organic compound constituting an organic light emitting device, particularly a charge injection layer or a charge transport layer can be formed by a coating method. Further, by using this coating liquid composition, an organic light emitting device having a relatively low cost and a large area can be easily produced.

  Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, n-dodecylbenzene, and methylnaphthalene, ether solvents such as tetrahydrofuran, dioxane, and diglyme, chloroform, monochlorobenzene, and 1,2-dichlorobenzene. Halogen solvents such as acetone, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate and n-butyl acetate, alcohol solvents such as methanol, ethanol and n-propanol, etc. It is done. These solvents may be used alone or in combination of two or more. Moreover, the film thickness of the thin film formed can be adjusted by adjusting the viscosity of these solvents or adjusting the concentration of the solvent in the solution.

  Moreover, in this coating liquid composition, in addition to the arylamine polymer of the formula (1) or (2), as the additive, for example, the above-mentioned known hole transporting compound, luminescent compound, electron transporting compound, etc. It may be included.

  Furthermore, in this coating solution composition, the content of the arylamine polymer of the formula (1) or (2) is preferably 0.05% by weight or more and 20% by weight or less, more preferably with respect to the entire composition. Is 0.1 wt% or more and 5 wt% or less.

  The organic light emitting device of the present invention can constitute a display by being appropriately combined. Specifically, the display of the present invention includes a plurality of the organic light-emitting elements of the present invention and a drive circuit for the organic light-emitting elements, and is driven by a passive matrix system or an active matrix system. Hereinafter, a display in which the organic light emitting device of the present invention is combined with an active matrix system will be described with reference to the drawings.

  FIG. 8 is a schematic cross-sectional view showing the arrangement of the organic light emitting elements on the substrate, the circuits arranged outside thereof, and the data lines. Here, the circuit is composed of a thin film transistor TFT and a storage capacitor Ch.

  In FIG. 8, only one organic light emitting element is shown, but when a display is configured, a plurality of organic light emitting elements are arranged two-dimensionally as shown in FIG. In the present embodiment, the arylamine polymer of the formula (1) or (2) is included in the organic compound layer in FIG.

  FIG. 9 is a diagram showing details of the configuration of the circuit shown in FIG. The circuit shown in FIG. 9 has a typical circuit configuration called a current programming method. The circuit that can be employed in the display of the present invention is not limited to this. The circuit shown in FIG. 9 includes a drive transistor T1, a switching transistor T2, a storage capacitor Ch, and an organic light emitting element. Since the circuit configuration is well known, detailed description of the operation is omitted.

  The organic light-emitting device of the present invention can be used as an exposure light source of a display, an illumination device, or an electrophotographic image forming apparatus by being used as one light emitting point.

  The case where the organic light emitting device of the present invention is used for a display will be described below.

  FIG. 10 is a schematic diagram showing a state in which a plurality of organic light emitting elements and circuits shown in FIGS. 8 and 9 are arranged in a two-dimensional manner on the same plane as one pixel, that is, a state in which a display is configured in a matrix. It is.

  The pixel in FIG. 10 is connected to a gate driver and a source driver through a wiring, and enters a light emitting state or a non-light emitting state when a driving pulse is supplied.

  Thus, the area | region where the organic light emitting element of this invention is multiply arranged by the in-plane direction in the same surface as a pixel is a display area of a display. That is, the organic light emitting device of the present invention can be used as a display area of a display.

  The display of the present invention may be any embodiment as long as it is a display device for a television or a PC, or a device having a part for displaying an image. For example, a portable display device on which the display of the present invention is mounted may be used. Alternatively, the display of the present invention can be used in an electronic imaging device such as a digital camera or a display unit of a mobile phone.

  FIG. 11 is a schematic diagram showing a configuration in which the display shown in FIG. 10 is made into a panel module. The panel module shown in FIG. 11 has a configuration in which components (interfaces) necessary for connection with external devices such as interface drivers and connection terminals are integrated in a housing in addition to the display (display device) shown in FIG. I'm taking it.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

  <Synthesis Example 1> [Exemplary Compound No. 1] 1-1 Synthesis]

(I) The following reagents and solvent were charged into a 500 ml three-necked flask.
2-Iodofluorene derivative (compound [1]): 30 g (93.7 mmol)
Acetamide (compound [2]): 5.5 g (93.7 mmol)
Copper powder: 11.9 g (187.4 mmol)
Potassium carbonate: 25.9 g (187.4 mmol)
1,2-dichlorobenzene: 250 ml

  Next, the reaction solution was heated to 180 ° C. and stirred for 16 hours. After completion of the reaction, the reaction solution was filtered, and the organic layer was extracted with chloroform. Next, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 20.0 g (yield 85%) of Compound [3] as white crystals.

(Ii) The following reagents and solvent were charged into a 300 ml three-necked flask.
4,4′-Diiodobiphenyl (Compound [4]): 10.1 g (24.9 mmol)
Compound [3]: 15.0 g (59.7 mmol)
Copper powder: 6.3 g (99.6 mmol)
Potassium carbonate: 13.8 g (99.6 mmol)
1,2-dichlorobenzene: 150 ml

  Next, the reaction solution was heated to 180 ° C. and stirred for 24 hours. After completion of the reaction, the reaction solution was filtered, and the organic layer was extracted with chloroform. Next, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 11.7 g (yield 72%) of intermediate compound [5] as white crystals.

(Iii) The following reagents and solvent were charged into a 300 ml three-necked flask.
Intermediate compound [5]: 10.0 g (15.3 mmol)
2-methoxyethanol: 50 ml
Toluene: 50ml

  Next, 2.1 g (38.3 mmol) of sodium methoxide was further added at room temperature under a nitrogen atmosphere, and then the reaction solution was heated to 60 ° C. and stirred for 3 hours. After completion of the reaction, water was added, and the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, after concentrating the organic layer under reduced pressure, the concentrate is purified by silica gel column chromatography (developing solvent: mixed solvent of hexane and toluene), whereby intermediate compound [6], which is an arylamine compound, is obtained as white crystals. As a result, 8.3 g (yield 95%) was obtained.

(Iv) The following reagents and solvents were charged into a 100 ml three-necked flask.
Intermediate compound [6]: 1.5 g (2.64 mmol)
4,4′-Dibromobiphenyl (compound [7]): 0.82 g (2.64 mmol)
Xylene: 50ml

  Next, 0.25 g (2.64 mmol) of sodium tert-butoxide was added at room temperature under a nitrogen atmosphere. Next, 0.03 g (0.13 mmol) of palladium acetate and 0.025 g (0.13 mmol) of tri-tert-butylphosphine were added, and then the reaction solution was heated to 130 ° C. and stirred for 12 hours. After completion of the reaction, water was added and the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, after the organic layer was concentrated under reduced pressure, the concentrate was purified by silica gel column chromatography (developing solvent: toluene). Next, reprecipitation is carried out with methanol, and the precipitate is collected by filtration to give Exemplified Compound Nos. 1-1 was obtained as yellow amorphous in 0.91 g (yield 48%).

  <Synthesis Example 2> [Exemplary Compound No. 2] Synthesis of 2-1]

(I) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [6]: 3.0 g (5.27 mmol)
4-bromoiodobenzene (compound [8]): 3.6 g (12.7 mmol)
Copper powder: 1.0 g (15.8 mmol)
Potassium carbonate: 2.2 g (15.8 mmol)
1,2-dichlorobenzene: 100 ml

  Next, the reaction solution was heated to 180 ° C. and stirred for 24 hours. After completion of the reaction, the reaction solution was filtered, the organic layer was extracted with chloroform and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The crude product thus obtained is purified by silica gel column column chromatography (developing solvent: a mixed solvent of hexane and toluene) to give 2.41 g of intermediate compound [9], which is an arylamine compound, as yellow crystals. (Yield 52%).

(Ii) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [9]: 1.5 g (1.71 mmol)
Dipinacol borane compound (compound [10]): 0.76 g (1.71 mmol)
Toluene: 50ml
Ethanol: 20ml

Next, while stirring the reaction solution at room temperature under a nitrogen atmosphere, an aqueous solution prepared by mixing 3.2 g of sodium carbonate and 15 ml of water was added dropwise, and then 0.10 g of tetrakis (triphenylphosphine) palladium (0). (0.09 mmol) was added. Next, the reaction solution was stirred for 10 hours while refluxing. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. After the organic layer was concentrated under reduced pressure, the resulting concentrate was purified by silica gel column chromatography (developing solvent: toluene). Next, by reprecipitating with methanol and collecting the precipitate by filtration, Exemplified Compound No. 0.90 g (yield 58%) of 2-1 was obtained as yellow amorphous.

  <Synthesis Example 3> [Exemplary Compound No. Synthesis of 2-2]

(I) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [6]: 3.0 g (5.27 mmol)
3-bromoiodobenzene (compound [11]): 3.6 g (12.7 mmol)
Copper powder: 1.0 g (15.8 mmol)
Potassium carbonate: 2.2 g (15.8 mmol)
1,2-dichlorobenzene: 100 ml

  Next, the reaction solution was heated to 180 ° C. and stirred for 24 hours. After completion of the reaction, the reaction solution was filtered, the organic layer was extracted with chloroform and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product thus obtained is purified by silica gel column chromatography (developing solvent: mixed solvent of hexane and toluene) to obtain 2.87 g of intermediate compound [12], which is an arylamine compound, as white crystals. (Yield 62%).

(Ii) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [12]: 1.5 g (1.71 mmol)
Dipinacol borane compound (compound [10]): 0.76 g (1.71 mmol)
Toluene: 50ml
Ethanol: 20ml

  Next, stirring the reaction solution at room temperature under a nitrogen atmosphere, an aqueous solution prepared by mixing 3.2 g of sodium carbonate and 15 ml of water was dropped, and then 0.10 g of tetrakis (triphenylphosphine) palladium (0) ( 0.09 mmol) was added. Next, the reaction solution was stirred for 10 hours while refluxing. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: toluene), then reprecipitated with methanol, and the precipitate was collected by filtration. As a white amorphous, 2-2 was obtained in an amount of 0.65 g (42% yield).

  <Synthesis Example 4> [Exemplary Compound No. Synthesis of 2-3]

(I) In Synthesis Example 1 (i), 2-iodo-9,9-di- (3-methylbutyl) fluorene was used in place of the compound [1]. Other than this, an intermediate compound [13], which is an arylamine compound, was obtained in the same manner as in Synthesis Examples 1 (i) to (iii) and Synthesis Example 2 (i).

(Ii) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [13]: 1.6 g (1.45 mmol)
Dipinacol borane compound (compound [14]): 0.81 g (1.45 mmol)
Toluene: 50ml
Ethanol: 20ml

  Next, stirring the reaction solution at room temperature under a nitrogen atmosphere, an aqueous solution prepared by mixing 3.0 g of sodium carbonate and 15 ml of water was dropped, and then 0.10 g of tetrakis (triphenylphosphine) palladium (0) ( 0.09 mmol) was added. Next, the reaction solution was stirred for 10 hours while refluxing. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: toluene), then reprecipitated with methanol, and the precipitate was collected by filtration. Obtained 0.81 g (yield 46%) of 2-3 as yellow amorphous.

  <Synthesis Example 5> [Exemplary Compound No. Synthesis of 2-4]

(I) The following reagents and solvent were charged into a 200 ml three-necked flask.
N, N′-diphenylbenzidine (compound [15]): 5.0 g (14.9 mmol)
Iodofluorene compound (compound [16]): 13.4 g (35.7 mmol)
Copper powder: 3.8 g (59.6 mmol)
Potassium carbonate: 8.2 g (59.6 mmol)
1,2-dichlorobenzene: 100 ml

  Next, the reaction solution was heated to 180 ° C. and stirred for 20 hours. After completion of the reaction, the reaction solution was filtered, the organic layer was extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. By purifying the crude product thus obtained by silica gel column chromatography (developing solvent: mixed solvent of hexane and toluene), 11.4 g of intermediate compound [17], which is an arylamine compound, as yellow crystals ( Yield 92%).

(Ii) Into a 100 ml three-necked flask, 5.0 g (6.0 mmol) of the intermediate compound [17] and 50 ml of chloroform were charged. Next, after adding 0.10 g (0.6 mmol) of iron (III) chloride at room temperature, a solution prepared by mixing 1.92 g (12.0 mmol) of bromine and 5 ml of carbon tetrachloride was added dropwise. Next, the reaction solution was stirred at room temperature for 10 hours. After completion of the reaction, water was added to the reaction solution, and the organic layer was extracted with chloroform and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure. By purifying the crude product thus obtained by silica gel column chromatography (developing solvent: mixed solvent of hexane and toluene), 3.7 g of the intermediate compound [18] as an arylamine compound as yellow crystals ( Yield 62%).

(Iii) The following reagents and solvents were charged into a 200 ml three-necked flask.
Intermediate compound [18]: 1.50 g (1.51 mmol)
Dipinacol borane compound (compound [14]): 0.85 g (1.51 mmol)
Toluene: 50ml
Ethanol: 20ml

  Next, stirring the reaction solution at room temperature under a nitrogen atmosphere, an aqueous solution prepared by mixing 3.0 g of sodium carbonate and 15 ml of water was dropped, and then 0.10 g of tetrakis (triphenylphosphine) palladium (0) ( 0.09 mmol) was added. Next, the reaction solution was stirred for 10 hours while refluxing. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: toluene), then reprecipitated with methanol, and the precipitate was collected by filtration. 0.54g (yield 32%) of 2-4 was obtained as yellow amorphous.

  <Synthesis Example 6> [Exemplary Compound No. Synthesis of 1-2]

(I) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [9]: 1.0 g (1.14 mmol)
Dibromofluorene: 0.2 g (0.57 mmol)
Nickel (II) cyclooctadiene complex: 1.25 g (4.56 mmol)
2,2-bipyridyl: 0.71 g (4.56 mmol)
Cyclooctadiene: 0.49 g (4.56 mmol)
Toluene: 50ml

  Next, the reaction solution was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: toluene), then reprecipitated with methanol, and the precipitate was collected by filtration. 0.51 g (yield 55%) of 2-3 was obtained as yellow amorphous.

  <Synthesis Example 7> [Exemplary Compound No. Synthesis of 1-7]

(I) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [19]: 1.0 g (0.91 mmol)
Dibromofluorene compound: 0.064 g (0.18 mmol)
Nickel (II) cyclooctadiene complex: 1.0 g (3.64 mmol)
2,2-bipyridyl: 0.57 g (3.64 mmol)
Cyclooctadiene: 0.39 g (3.64 mmol)
Toluene: 50ml

  Next, the reaction solution was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, the organic layer was extracted with toluene and dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: toluene), then reprecipitated with methanol, and the precipitate was collected by filtration. 0.54 g (yield 60%) of 1-7 was obtained as a yellow amorphous substance.

<Example 1>
The organic light emitting device shown in FIG. 7 was produced.

  First, indium tin oxide (ITO) was formed on a glass substrate (substrate 1) by a sputtering method to form an anode 2. At this time, the film thickness of the anode 2 was 120 nm. Next, the substrate with ITO thin film was ultrasonically washed successively with acetone and isopropyl alcohol (IPA), boiled and washed with IPA, and then dried. Further, UV / ozone cleaning was performed. The substrate treated as described above was used as a transparent conductive support substrate.

  Next, Exemplified Compound No. 1-2 was dissolved in chloroform, and Exemplified Compound No. A coating solution having a concentration of 1-2 of 0.5% by weight was prepared. This coating solution was dropped onto the transparent conductive support substrate and spin coated to form a hole injection layer 7 (buffer layer). At this time, the thickness of the hole injection layer 7 was set to 30 nm.

Next, the following reagent and solvent were mixed to prepare a coating solution.
Ir (ppy) ₃ (tris (2-phenylpyridine) iridium) which is a luminescent compound shown below, manufactured by Tosco Corporation: 0.01 part by mass PBD which is an electron transporting compound shown below (trade name: 2) -(4-tert-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole), manufactured by Aldrich: 0.3 parts by mass PVK (trade name: Poly (9) -Vinylcarbazole), Mn = 35000), manufactured by Aldrich: 0.7 parts by mass 1,2-dichlorobenzene, manufactured by Kishida Chemical Co .: 99 parts by mass

  Next, this coating solution was dropped on the hole injection layer 7, and spin coating was performed at 1000 rpm for 1 minute to form a thin film. Next, the light emitting layer 3 was formed by heating at 80 degreeC for 30 minutes, and evaporating the solvent in a thin film. At this time, the thickness of the light emitting layer 3 was 50 nm.

Next, the electron injection layer 8 was formed by depositing lithium fluoride on the light emitting layer 3 by a vacuum deposition method. At this time, the thickness of the electron injection layer 8 was 0.5 nm, the degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa, and the deposition rate was 0.05 nm / sec.

Next, the metal layer used as the cathode 4 was formed by vapor-depositing aluminum. At this time, the thickness of the cathode 4 was 100 nm, the degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa, and the film formation rate was 1.0 nm / sec to 1.2 nm / sec.

  Next, in a nitrogen atmosphere, a protective glass plate was placed and sealed with an acrylic resin adhesive. An organic light emitting device was obtained as described above.

When a 6V DC voltage was applied to the obtained device using an ITO electrode as an anode and an aluminum electrode as a cathode, a current flowed through the device. The current density at this time was 4.8 mA / cm ² . At this time, green light emission with a luminance of 870 cd / m ² was observed. Furthermore, when the element was continuously driven with the current density maintained at 10 mA / cm ² , the initial luminance was 1780 cd / m ² and the luminance after 50 hours was 1330 cd / m ² .

<Example 2>
In Example 1, the constituent material (hole injection material) of the hole injection layer 7 was changed to Example Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except for 1-4. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 1-8 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 4>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 1-10 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 5>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 1-17 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 6>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 1-18 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 7>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was produced in the same manner as in Example 1 except that the conditions were 2-1. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 8>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 2-6 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 9>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 2-10 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 10>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 2-12 was selected. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 11>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 2-13. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 12>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, Exemplified Compound No. A device was fabricated in the same manner as in Example 1 except that 2-19 was used. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
In Example 1, the hole injecting material was changed to Exemplified Compound No. Instead of 1-2, 4-polyethylenedioxythiophene / polystyrenesulfonic acid (PEDOT / PSS, trade name: Vitron P Al-4083, manufactured by Bayer) shown below was used. Moreover, PEDOT / PSS was formed into a film by the spin coat method, and it heated at 120 degreeC for 30 minutes, and the 35-nm-thick hole injection layer 7 was formed.

  Except for these, an element was fabricated in the same manner as in Example 1. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 13>
The organic light emitting device shown in FIG. 7 was produced.

  On the glass substrate (substrate 1), indium tin oxide (ITO) was formed by sputtering to form the anode 2. At this time, the film thickness of the anode 2 was 120 nm. The substrate with the ITO thin film was sequentially ultrasonically washed with acetone and isopropyl alcohol (IPA), boiled and washed with IPA, and then dried. Further, UV / ozone cleaning was performed. The substrate treated as described above was used as a transparent conductive support substrate.

  Next, Exemplified Compound No. 1-1 was dissolved in chloroform to prepare a coating solution having a concentration of 0.5% by weight. This coating solution was dropped on the transparent conductive support substrate and spin coated to form the hole injection layer 7. At this time, the thickness of the hole injection layer 7 was set to 30 nm.

  Next, poly (9,9-dioctyl) fluorene (trade name: ADS129BE, manufactured by American Dye Source, Inc., Mw = 80000) shown below is dissolved in toluene to prepare a light emitting layer coating solution having a concentration of 1% by weight. did. This coating solution was dropped on the hole injection layer 7 and spin coated. Next, the light emitting layer 3 was formed by heat-drying for 30 minutes at 80 degreeC. At this time, the thickness of the light emitting layer 3 was 50 nm.

Next, the electron injection layer 8 was formed by depositing lithium fluoride on the light emitting layer 3 by a vacuum deposition method. At this time, the thickness of the electron injection layer 8 was 0.5 nm, the degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa, and the film formation rate was 0.05 nm / sec.

Next, the metal layer used as the cathode 4 was formed by vapor-depositing aluminum. At this time, the thickness of the cathode 4 was 100 nm, the degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa, and the film formation rate was 1.0 nm / sec to 1.2 nm / sec.

  Next, a protective glass plate was placed in a nitrogen atmosphere and sealed with an acrylic resin adhesive. An organic light emitting device was produced as described above.

When a 6V DC voltage was applied to the obtained device using an ITO electrode as an anode and an aluminum electrode as a cathode, a current flowed through the device. The current density at this time was 15 mA / cm ² . At this time, blue light emission with a luminance of 820 cd / m ² was observed. Furthermore, when the element was continuously driven with the current density maintained at 30 mA / cm ² , the initial luminance was 1650 cd / m ² and the luminance after 50 hours was 1260 cd / m ² .

<Example 14>
In Example 13, the constituent material of the hole injection layer 7 (hole injection material) was changed to Example Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-3 was selected. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 15>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-5 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 16>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-9 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 17>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-13 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 18>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-15 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 19>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-19 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 20>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 1-20 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 21>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-2 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 22>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-8 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 23>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-9 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 24>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that the thickness was changed to 2-15. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 25>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-16 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 26>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-17. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 27>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-18 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Example 28>
In Example 13, the hole injecting material was changed to Exemplified Compound No. In place of 1-1, Exemplified Compound No. A device was fabricated in the same manner as in Example 13 except that 2-20 was used. The device was evaluated in the same manner as in Example 13. The results are shown in Table 2.

<Comparative example 2>
In Example 13, the hole injecting material was changed to Exemplified Compound No. Instead of 1-1, PEDOT / PSS (trade name: Vitron P Al-4083, manufactured by Bayer) shown below was used. Moreover, PEDOT / PSS was formed into a film by the spin coat method, and it heated at 120 degreeC for 30 minutes, and the 35-nm-thick hole injection layer 7 was formed.

  Except for these, an element was fabricated in the same manner as in Example 1. The device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 29>
The organic light emitting device shown in FIG. 7 was produced.

  On the glass substrate (substrate 1), indium tin oxide (ITO) was formed by sputtering to form the anode 2. At this time, the film thickness of the anode 2 was 120 nm. Next, this substrate with an ITO thin film was sequentially ultrasonically washed with acetone and isopropyl alcohol (IPA), boiled and washed with IPA, and then dried. Further, UV / ozone cleaning was performed. The substrate treated as described above was used as a transparent conductive support substrate.

  Next, PEDOT / PSS (trade name: Vitron PAl-4083, manufactured by Bayer) is formed on this transparent conductive support substrate by a spin coating method, and then heated at 120 ° C. for 30 minutes, A hole injection layer 7 was formed. At this time, the thickness of the hole injection layer 7 was set to 35 nm.

Next, a coating liquid composition was prepared by mixing the following reagents and solvent.
Exemplified Compound No. as a host 1-6: 1 part by mass The green phosphorescent material shown below as a guest (compound obtained in accordance with the synthesis method described in Dalton Transactions 2005, 1583-1590): 0.01 part by mass Chloroform: 99 parts by mass

  Next, this coating solution was dropped on the hole injection layer 7 and film formation was performed by spin coating at a rotation speed of 1000 rpm for 1 minute. next. The light emitting layer 3 was formed by heating at 80 ° C. for 30 minutes to evaporate the solvent in the film. At this time, the thickness of the light emitting layer 3 was 80 nm.

Next, lithium fluoride was deposited on the light emitting layer 3 by a vacuum deposition method to form the electron injection layer 8. At this time, the thickness of the electron injection layer 8 was 0.5 nm, the degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa, and the film formation rate was 0.05 nm / sec.

Next, the metal layer used as the cathode 4 was formed by vapor-depositing aluminum. At this time, the thickness of the cathode 4 was 100 nm, the degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa, and the film formation rate was 1.0 nm / sec to 1.2 nm / sec.

  Next, in a nitrogen atmosphere, a protective glass plate was placed and sealed with an acrylic resin adhesive. An organic light emitting device was obtained as described above.

When a 7V DC voltage was applied to the obtained organic light-emitting device using an ITO electrode as an anode and an aluminum electrode as a cathode, a current flowed through the device. The current density at this time was 20 mA / cm ^2. At this time, light emission with a luminance of 1070 cd / m ² was observed. Further, while maintaining the current density 30 mA / cm ^2, was continuously driven element, the initial luminance was 1610cd / m ^2, the luminance after 50 hours was 900 cd / m ^2.

<Example 30>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 1-7 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 31>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 1-11 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 32>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 1-12 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 33>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 1-14 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 34>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 1-16 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 35>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 2-3 was selected. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 36>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 2-4 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 37>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 2-5 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 38>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 2-7 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 39>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 2-11 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Example 40>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. In place of 1-6, Exemplified Compound No. 1 A device was fabricated in the same manner as in Example 29 except that 2-14 was used. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

<Comparative Example 3>
In Example 29, the host of the light-emitting layer 3 was used as an example compound No. A device was produced in the same manner as in Example 29 except that poly (9,9-dioctyl) fluorene shown below was used instead of 1-6. In addition, the device was evaluated in the same manner as in Example 29. The results are shown in Table 3.

It is sectional drawing which shows 1st embodiment in the organic light emitting element of this invention. It is sectional drawing which shows 2nd embodiment in the organic light emitting element of this invention. It is sectional drawing which shows 3rd embodiment in the organic light emitting element of this invention. It is sectional drawing which shows 4th embodiment in the organic light emitting element of this invention. It is sectional drawing which shows 5th embodiment in the organic light emitting element of this invention. It is sectional drawing which shows 6th embodiment in the organic light emitting element of this invention. It is sectional drawing which shows 7th embodiment in the organic light emitting element of this invention. It is a cross-sectional schematic diagram which shows arrangement | positioning of the organic light emitting element on a board | substrate, the circuit arrange | positioned on the exterior, and a data line. It is a figure which shows the detail of a structure of the circuit of FIG. FIG. 10 is a schematic diagram illustrating a state in which a display is configured by arranging the organic light-emitting elements and circuits illustrated in FIGS. 8 and 9 in a matrix as one pixel. It is a schematic diagram which shows the structure which made the display shown in FIG. 10 into the panel module.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Light emitting layer 4 Cathode 5 Hole transport layer 6 Electron transport layer 7 Hole injection layer or buffer layer 8 Electron injection layer 9 Hole / exciton blocking layer 10, 20, 30, 40, 50, 60, 70 Organic light emitting device

Claims (8)

An anode and a cathode;
A layer made of an organic compound sandwiched between the anode and the cathode,
An organic light-emitting device, wherein the layer made of the organic compound contains at least one arylamine polymer represented by the following general formula (1).

(In the formula (1), R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a halogen atom or an alkoxy group. Ar ₁ and Ar ₂ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted condensed polycyclic aromatic group, provided that either Ar ₁ or Ar ₂ is a substituted or unsubstituted fluorenyl group. Ar ₃ represents an arylene group composed of two or more substituted or unsubstituted benzene rings or a substituted or unsubstituted divalent condensed polycyclic aromatic group, and Ar ₄ represents a substituted or unsubstituted arylene. Represents a group or a substituted or unsubstituted divalent condensed polycyclic aromatic group, m represents an integer of 10 or more and 200 or less, and n represents an integer of 0 or more and 200 or less.) An anode and a cathode;
A layer made of an organic compound sandwiched between the anode and the cathode,
An organic light-emitting device, wherein the layer made of the organic compound contains at least one arylamine polymer represented by the following general formula (2).

(In the formula (2), R ₃ and R ₄ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a halogen atom or an alkoxy group. Ar ₅ and Ar ₆ each represents a substituted or unsubstituted aryl group or a substituted or unsubstituted condensed polycyclic aromatic group, provided that either Ar ₅ or Ar ₆ is a substituted or unsubstituted fluorenyl group. Ar ₇ represents an arylene group consisting of two or more substituted or unsubstituted benzene rings or a substituted or unsubstituted divalent condensed polycyclic aromatic group, and Ar ₈ represents a substituted or unsubstituted arylene. Represents a group or a substituted or unsubstituted divalent condensed polycyclic aromatic group, and o represents an integer of 10 to 200.)   The organic light-emitting element according to claim 1, wherein the layer made of the organic compound includes a hole injection layer and a light-emitting layer, and the hole injection layer is in contact with the light-emitting layer.   The organic light emitting device according to claim 3, wherein the arylamine polymer is contained in the hole injection layer or the light emitting layer.   The organic light emitting device according to claim 3, wherein the light emitting layer is formed by a coating method.   6. A display comprising a plurality of the organic light-emitting elements according to claim 1 and a drive circuit for the organic light-emitting elements.   A panel module comprising the display according to claim 6 and an interface with an external device.   A portable display device on which the display according to claim 6 is mounted.

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