JP2009158535A - Organic light-emitting device, method of manufacturing the same, and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic light-emitting device having high efficiency and long service life. <P>SOLUTION: The organic light-emitting device 10 includes: an anode 2; a cathode 6; and a laminate sandwiched between the anode 2 and the cathode 6 and including at least a first organic compound layer (hole injection layer 3), a second organic compound layer (hole transport layer 4) and a third organic compound layer (light-emitting layer 5) in this order, wherein the first organic compound layer (hole injection layer 3) contains aryl amine polymer and the second organic compound layer (hole transport layer 4) contains (meth) acrylic acid ester polymer having aryl amine skeleton. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic light emitting device, a method for manufacturing the same, and a display device.

  When manufacturing an organic light emitting element, the manufacturing process is classified into a dry method and a wet method. The dry method is a method in which a thin film is formed mainly using a low molecular weight material and using a vapor phase process such as a vacuum evaporation method. On the other hand, the wet method mainly uses a polymer material in a 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.

  Here, in the dry method such as the vacuum evaporation method, the production apparatus is a batch type, and a thin film made of the constituent material of the element is also formed in a part that is not necessary for light emission of the element in the element production. For this reason, much more material than necessary is consumed unnecessarily, so it can be said that this is a problematic method from the viewpoint of productivity.

  On the other hand, when an organic light emitting device is manufactured using a wet method, production by a continuous process is possible. For example, the type, position, and the like of the coating liquid to be applied by a droplet discharge method such as an inkjet coating method and a dispenser coating method can be selected. In these methods, so-called patterning can be performed in which materials are selected and applied only to the necessary portions of the element, and productivity can be greatly improved.

  For this reason, in recent years, there has been an increasing interest in forming organic compound layers such as a charge injection layer, a charge transport layer, and a light emitting layer constituting an organic light emitting element by using a coating method with high productivity.

  For example, when the hole injection layer is formed by a coating method, a mixture of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (hole injection material) is used as a constituent material (hole injection material) of the hole injection layer used ( PEDOT / PSS) is known (see Non-Patent Document 1). Since this PEDOT / PSS is water-soluble, when forming a thin film as an upper layer from the PEDOT / PSS film, a coating solution prepared by dissolving the constituent materials of the layer in an organic solvent is used. Can be used to form a thin film and stack the thin film. However, an organic light-emitting device using PEDOT / PSS has excellent initial characteristics, but has a problem in that luminance deterioration is significant when used for a long time. In order to improve this luminance deterioration, an organic light emitting device in which an intermediate layer which is an insoluble polymer is incorporated between a PEDOT / PSS film and a light emitting layer has been reported (see Patent Documents 1 and 2).

  On the other hand, in order to improve the efficiency and durability of the organic light emitting device, it is effective to have a device structure in which a plurality of organic compound layers are stacked. Here, in the case of laminating an organic compound layer by a coating method, when applying a solution containing the constituent material of the next layer on the organic compound layer serving as the base, there is a problem that the organic compound layer serving as the base dissolves. It is necessary to avoid it. Here, as a method for preventing dissolution of the organic compound layer serving as a base, a method using a difference in solubility in a solvent has been reported (see Patent Document 3). In addition, a method of insolubilizing the thin film itself by using a crosslinking agent to induce a crosslinking reaction of the thin film which is the underlying organic compound layer has been reported (see Patent Documents 4 and 5).

  However, in the method using the difference in solubility with respect to the solvent, there is a problem that the usable material is naturally restricted because the solvent that can be used for lamination is limited from the viewpoint of the solubility of the constituent material of each layer. In the method of insolubilization using a crosslinking agent, since the crosslinking agent adversely affects the charge transport properties of the material constituting the layer, sufficient initial characteristics such as luminous efficiency and durability characteristics such as luminance deterioration due to long-time emission are sufficient. There was a problem of not.

JP 2005-183404 A JP-A-2005-243300 JP-A-11-251065 Japanese Patent Laid-Open No. 11-87605 JP 2005-340042 A Appl. Phys. Lett. , 75, 1679 (1999)

  An object of the present invention is to provide an organic light-emitting device with high efficiency and long life. Another object of the present invention is to provide a method for manufacturing an organic light-emitting device that makes it possible to manufacture an organic light-emitting device with high efficiency and a long lifetime by a coating method.

  The organic light-emitting device of the present invention comprises an anode, a cathode, and at least a first organic compound layer, a second organic compound layer, and a third organic compound layer sandwiched between the anode and the cathode. A laminate that is included in order, the anode or the cathode, the first organic compound layer, the first organic compound layer, the second organic compound layer, and the second organic compound. A layer and the third organic compound layer are in contact with each other, the first organic compound layer contains an arylamine polymer, and the second organic compound layer has an arylamine skeleton (meth) acrylic acid An ester polymer is included.

  ADVANTAGE OF THE INVENTION According to this invention, a highly efficient and long-life organic light emitting element can be provided. In addition, according to the present invention, it is possible to provide a method for manufacturing an organic light-emitting element that makes it possible to manufacture an organic light-emitting element with high efficiency and a long lifetime by a coating method.

  First, the organic light emitting device of the present invention will be described. The organic light-emitting device of the present invention comprises an anode, a cathode, and at least a first organic compound layer, a second organic compound layer, and a third organic compound layer sandwiched between the anode and the cathode. It is comprised from the laminated body contained in order.

  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 hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 6 are sequentially provided on a substrate 1.

  FIG. 2 is a cross-sectional view showing a second embodiment of the organic light emitting device of the present invention. The organic light emitting device 20 in FIG. 2 is provided with an electron injection layer 7 between the light emitting layer 5 and the cathode 6 in the organic light emitting device 10 in FIG.

  FIG. 3 is a cross-sectional view showing a third embodiment of the organic light-emitting device of the present invention. The organic light emitting device 30 of FIG. 3 is provided with an electron transport layer 8 between the light emitting layer 5 and the electron injection layer 7 in the organic light emitting device 20 of FIG.

  However, FIG. 1 to FIG. 3 are just basic device configurations, and the configuration of the organic light-emitting device of the present invention is not limited to these. For example, various layer configurations such as providing an insulating layer, an adhesive layer or an interference layer at the interface between the electrode and the organic compound layer, or two different hole injection layers or hole transport layers are possible. . In the organic light emitting device of the present invention, the anode or cathode and the first organic compound layer are in contact with each other. Further, the first organic compound layer and the second organic compound layer are in contact with each other. Further, the second organic compound layer and the third organic compound layer are in contact with each other.

  As described above, the organic light emitting device of the present invention includes at least three organic compound layers. Examples of the organic compound layer include a hole injection layer, a hole transport layer, a light emitting layer, a hole / exciton blocking layer, an electron transport layer, and an electron injection layer.

  In the organic light emitting device of the present invention, the first organic compound layer includes an arylamine polymer, and the second organic compound layer includes a (meth) acrylic acid ester polymer having an arylamine skeleton. .

  First, the arylamine polymer contained in the first organic compound layer will be described. The arylamine polymer here is preferably a polymer represented by the following general formula (1).

In the formula (1), R ₁₁ and R ₁₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, an alkoxy group, or a halogen atom.

Examples of the alkyl group represented by R ₁₁ and R ₁₂ include a methyl group, an ethyl group, a propyl group, and an n-butyl group.

Examples of the aralkyl group represented by R ₁₁ and R ₁₂ include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Examples of the aryl group represented by R ₁₁ and R ₁₂ include a phenyl group, a biphenylyl group, and a terphenylyl group.

Examples of the alkoxy group represented by R ₁₁ and R ₁₂ include a methoxy group, an ethoxy group, and a propoxy group.

Examples of the halogen atom represented by R ₁₁ and R ₁₂ include fluorine, chlorine, bromine and the like.

  The alkyl group, the aralkyl group, and the aryl group that the aryl group may further have include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, and a trifluoromethyl group, a benzyl group, Aromatic groups such as aralkyl groups such as phenethyl group and naphthylmethyl group, aromatic hydrocarbon ring groups such as phenyl group, naphthyl group, anthryl group, pyrenyl group and fluorenyl group, carbazolyl group, dibenzofuryl group, dibenzothienyl group and thienyl group Aromatic heterocyclic group, alkoxy group such as methoxy group, ethoxy group, propoxy group, aryloxy group such as phenoxy group, naphthoxy group, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group Etc.

In the formula (1), Ar ₁₁ and Ar ₁₂ each represent a substituted or unsubstituted aryl group or a condensed polycyclic aromatic group.

Examples of the aryl group represented by Ar ₁₁ and Ar ₁₂ include a phenyl group, a biphenylyl group, and a terphenylyl group.

As the condensed polycyclic aromatic group represented by Ar ₁₁ and Ar ₁₂ , fluorenyl group, fluoranthenyl group, naphthyl group, phenanthryl group, dihydrophenanthrenyl group, pyrenyl group, perylenyl group, carbazolyl group, dibenzofuryl group And a dibenzothienyl group.

  The aryl group and the polycyclic aromatic group that the condensed polycyclic aromatic group may further have are alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, and trifluoromethyl group. Group, benzyl group, phenethyl group, aralkyl group such as naphthylmethyl group, aromatic hydrocarbon ring group such as phenyl group, naphthyl group, anthryl group, pyrenyl group, fluorenyl group, carbazolyl group, dibenzofuryl group, dibenzothienyl group, Aromatic heterocyclic group such as thienyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, aryloxy group such as phenoxy group, naphthoxy group, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, A nitro group, a cyano group, etc. are mentioned.

In the formula (1), Ar ₁₃ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted condensed polycyclic aromatic group.

Examples of the divalent aryl group represented by Ar ₁₃ include a phenylene group, a biphenylene group, and a terphenylene group.

As the divalent condensed polycyclic aromatic group represented by Ar ₁₃ , a divalent substituent having a basic skeleton such as fluorene, fluoranthene, naphthalene, phenanthrene, dihydrophenanthrene, pyrene, perylene, carbazole, dibenzofuran, dibenzothiophene, etc. Can be mentioned.

  The aryl group and the polycyclic aromatic group that the condensed polycyclic aromatic group may further have are alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, and trifluoromethyl group. Group, benzyl group, phenethyl group, aralkyl group such as naphthylmethyl group, aromatic hydrocarbon ring group such as phenyl group, naphthyl group, anthryl group, pyrenyl group, fluorenyl group, carbazolyl group, dibenzofuryl group, dibenzothienyl group, Aromatic heterocyclic group such as thienyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, aryloxy group such as phenoxy group, naphthoxy group, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, A nitro group, a cyano group, etc. are mentioned.

In the formula (1), Ar ₁₄ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted divalent condensed polycyclic aromatic group.

Examples of the divalent aryl group represented by Ar ₁₄ include a phenylene group and a biphenylene group.

Divalent substituted polycyclic aromatic groups represented by Ar ₁₄ are divalent substitutions based on fluorene, fluoranthene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, pyrene, perylene, carbazole, dibenzofuran, dibenzothiophene, etc. Groups.

  The aryl group and the polycyclic aromatic group that the condensed polycyclic aromatic group may further have include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, a 3-methylbutyl group, 2- Aromatic hydrocarbon rings such as alkyl groups such as ethylhexyl group, octyl group and trifluoromethyl group, aralkyl groups such as benzyl group, phenethyl group and naphthylmethyl group, phenyl group, naphthyl group, anthryl group, pyrenyl group and fluorenyl group Group, carbazolyl group, dibenzofuryl group, dibenzothienyl group, aromatic heterocyclic group such as thienyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, aryloxy group such as phenoxy group, naphthoxy group, fluorine atom, Examples thereof include halogen atoms such as chlorine atom, bromine atom and iodine atom, nitro group, cyano group and the like.

  In Formula (1), m represents an integer of 10 or more and 300 or less.

  In the formula (1), n represents an integer of 0 or more and 300 or less.

  In the arylamine polymer of the formula (1), the solubility of the polymer itself in the solvent can be appropriately adjusted according to the numerical values of m and n. Although not particularly defined, m is preferably 10 or more and 100 or less in that sufficient solubility in a solvent can be increased. Similarly, n is preferably 0 or more and 100 or less. 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.

  Specific examples of the arylamine polymer of the formula (1) are shown below. However, the present invention is not limited to these specific examples.

  Next, the (meth) acrylic acid ester polymer contained in the second organic compound layer will be described.

  The (meth) acrylic acid ester polymer contained in the second organic compound layer is a (meth) acrylic acid ester polymer having an arylamine skeleton, and is preferably a polymer represented by the following general formula (2). .

In the formula (2), A ₂₁ and A ₂₂ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms.

Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms represented by A ₂₁ and A ₂₂ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and an octylene group. These divalent hydrocarbon groups may further have branches such as a methyl group, an ethyl group, a propyl group, and a butyl group. When the number of carbon atoms is 2 or more, one of the methylenes contained in these divalent hydrocarbon groups may be replaced with an ether bond.

In the formula (2), Ar ₂₁ and Ar ₂₂ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted condensed polycyclic aromatic group.

The aryl group represented by Ar ₂₁ and Ar ₂₂ refers to a monovalent aryl group containing two or more benzene rings. For example, a biphenylyl group etc. are mentioned.

The condensed polycyclic aromatic group represented by Ar ₂₁ and Ar ₂₂ refers to a condensed polycyclic aromatic group containing two or more benzene rings. Examples thereof include a fluorenyl group, a fluoranthenyl group, a naphthyl group, a phenanthryl group, a dihydrophenanthryl group, a pyrenyl group, a perylenyl group, a carbazolyl group, a dibenzofuryl group, and a dibenzothienyl group. Preferably, it is a fluorenyl group.

  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 butyl group, a tert-butyl group, or a trifluoromethyl group, a benzyl group , Aralkyl groups such as phenethyl group and naphthylmethyl group, aromatic hydrocarbon ring groups such as phenyl group, naphthyl group, anthryl group, pyrenyl group, fluorenyl group, carbazolyl group, dibenzofuryl group, dibenzothienyl group, thienyl group, etc. Aromatic heterocyclic group, alkoxy group such as methoxy group, ethoxy group, propoxy group, aryloxy group such as phenoxy group, naphthoxy group, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group Groups and the like.

In the formula (2), Ar ₂₃ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted divalent condensed polycyclic aromatic group.

The divalent aryl group represented by Ar ₂₃ refers to a divalent aryl group containing two or more benzene rings. For example, a biphenylene group etc. are mentioned.

The divalent condensed polycyclic aromatic group represented by Ar ₂₃ refers to a divalent condensed polycyclic aromatic group containing two or more benzene rings. Examples thereof include divalent substituents having a basic skeleton of fluorene, fluoranthene, phenylnaphthalene, phenanthrene, dihydrophenanthrene, pyrene, perylene, benzoanthracene, carbazole, dibenzofuran, dibenzothiophene, and the like.

  Examples of the substituent that the divalent aryl group and the divalent condensed polycyclic aromatic group may further have include a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, and a trifluoromethyl group. Alkyl groups, benzyl groups, phenethyl groups, naphthylmethyl groups and other aralkyl groups, phenyl groups, naphthyl groups, anthryl groups, pyrenyl groups, fluorenyl groups and other aromatic hydrocarbon ring groups, carbazolyl groups, dibenzofuryl groups, dibenzothienyl groups Group, aromatic heterocyclic group such as thienyl group, alkoxy group such as methoxy group, ethoxy group and propoxy group, aryloxy group such as phenoxy group and naphthoxy group, halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom An atom, a nitro group, a cyano group, etc. are mentioned.

In the formula (2), R ₂₁ and R ₂₂ each represent a hydrogen atom or a methyl group.

  The (meth) acrylic polymer of the formula (2) is obtained by heating and polymerizing a specific (meth) acrylic ester compound. The specific structure of the (meth) acrylic acid ester compound will be described later.

  In the organic light-emitting device of the present invention, the arylamine polymer contained in the first organic compound layer and the (meth) acrylate compound contained in the second organic compound layer are both specific arylamines excellent in charge transport function A compound containing a structure. By including organic compounds having a common partial structure in layers adjacent to each other, charge injection from the electrode and charge transport in the layer are improved.

  Further, a compound having an arylamine skeleton has been known as a hole transporting material for a long time, and is a substance capable of adjusting HOMO energy to a high level due to an electron donating amine. In organic light-emitting devices, it is generally known that HOMO energy is a parameter that strongly affects the light-emitting efficiency and durability of the device. Therefore, the HOMO energy of each of the first organic compound layer containing the arylamine polymer of formula (1) and the second organic compound layer containing the (meth) acrylic acid ester polymer of formula (2) is specified. It becomes possible to finely adjust the value within the range. As described above, the organic light-emitting device of the present invention is laminated so that the first organic compound layer and the second organic compound layer are adjacent to each other. Therefore, the organic compound layers having the same HOMO energy are stacked adjacent to each other, and the charge injection property between the layers is improved.

  Next, other constituent members constituting the organic light emitting device of the present invention will be described.

  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 zinc indium 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 constituent material of the cathode should have a work function as small as possible. For example, it is possible to use a simple 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 of these metals. it can. Further, a metal oxide such as indium tin oxide (ITO) can be used. Here, 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.

  In addition, a protective layer or a sealing layer can be provided for the purpose of preventing contact with oxygen, moisture, or the like on the produced organic light emitting device. 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.

The manufacturing method of the organic light emitting element of this invention is characterized by including the process shown below.
(I) A step of forming a first organic compound layer made of an arylamine polymer on the lower electrode by a coating method (hereinafter referred to as a first step).
(Ii) A step of forming a thin film made of a (meth) acrylic acid ester compound having an arylamine skeleton on the first organic compound layer by a coating method (hereinafter referred to as a second step).
(Iii) A step of heating and curing the thin film formed in the second step to form a second organic compound layer (hereinafter referred to as a third step).
(Iv) A step of forming a third organic compound layer on the second organic compound layer by a coating method (hereinafter referred to as a fourth step).

  First, the first step will be described. The arylamine polymer constituting the first organic compound layer formed by the first step is an arylamine polymer represented by the formula (1).

  When forming the first organic compound layer comprising the arylamine polymer of the formula (1) by the coating method, a first coating composition described below is prepared, and this first coating composition is prepared. It is better to apply and form a thin film. If this first coating composition is used, it becomes possible to produce an organic compound layer constituting an organic light-emitting device, in particular, a charge injection layer or a charge transport layer by a coating method, which is relatively inexpensive and has a large area of organic material. A light-emitting element can be easily manufactured.

  Here, the first coating composition contains at least one arylamine polymer of the formula (1). One kind of the arylamine polymer of the formula (1) may be used alone, or two or more kinds may be mixed and used.

  Moreover, you may form a film | membrane combining the arylamine polymer of Formula (1), and another organic compound. Examples of organic compounds that can be used in combination with the arylamine polymer of the formula (1) include, for example, triarylamine derivatives, phenylenediamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, oxazole derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, poly (vinylcarbazole), poly (silylene), poly (thiophene), and the like, but are not limited thereto.

  Examples of the solvent used for preparing the first coating composition include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, n-dodecylbenzene, and methylnaphthalene, and ethers such as tetrahydrofuran, dioxane, and diglyme. Solvent, halogen solvents such as chloroform, monochlorobenzene, 1,2-dichlorobenzene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, methanol, Examples thereof include alcohol solvents such as ethanol and n-propanol. These solvents may be used alone or in combination of two or more. Moreover, the film thickness of the arylamine polymer thin film can be adjusted by adjusting the viscosity of these solvents and the concentration of the arylamine polymer in the solution.

  The content of the arylamine polymer of the formula (1) contained in the first coating composition is preferably 0.05% by weight or more and 20% by weight or less, more preferably 0%, based on the whole composition. .1% by weight or more and 5% by weight or less.

  As a method for applying the first coating composition on the electrode, specifically, a cast method, a spin coat method, a slit coater method, a printing method, an ink jet method, a dispense method, a spray method, a dip method, an LB film method, etc. Is mentioned.

  The film thickness of the first organic compound layer formed by the first step is less than 5 μm, preferably 500 nm or less, and more preferably 5 nm to 500 nm.

  Next, the second step will be described. The (meth) acrylic acid ester compound having an arylamine skeleton constituting the thin film formed by the second step is preferably a (meth) acrylic acid ester compound represented by the following general formula (3).

In Formula (3), A ₂₁ and A ₂₂ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms. Ar ₂₁ and Ar ₂₂ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted monovalent condensed polycyclic aromatic group. Ar ₂₃ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted divalent condensed polycyclic aromatic group. R ₂₁ and R ₂₂ each represent a hydrogen atom or a methyl group.

Specific examples of A ₂₁ , A ₂₂ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃ are the same as the specific examples of the (meth) acrylate polymer of the formula (2). Specific examples of the substituent that the aryl group represented by Ar ₂₁ and Ar ₂₂ and the condensed polycyclic aromatic group may further have are the same as the specific example of the (meth) acrylic acid ester polymer of the formula (2). It is. Furthermore, specific examples of the substituent that the divalent aryl group represented by Ar ₂₃ and the divalent condensed polycyclic aromatic group may further include a specific example of the (meth) acrylate polymer of the formula (2). Similar to the example.

  Next, specific examples of the arylamine compound having a polymerizable functional group of the present invention are shown below as exemplary compounds. However, the present invention is not limited to these specific examples.

  In performing the second step, when forming a thin film by a wet method such as a coating method, a second coating composition containing a (meth) acrylic acid ester compound of formula (3) is prepared, and this second step is performed. A method of forming a film by applying the coating composition is preferred.

  Here, the second coating composition contains at least one (meth) acrylic acid ester compound of the formula (3). One (meth) acrylic acid ester compound of the formula (3) may be used alone, or two or more types may be mixed and used.

  Furthermore, a thin film can also be formed by combining the (meth) acrylic acid ester compound of formula (3) with another organic compound. Examples of organic compounds that can be used in combination with the (meth) acrylic acid ester compound of formula (3) include triarylamine derivatives, phenylenediamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, and pyrazolones. Derivatives, oxazole derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, phthalocyanine derivatives, porphyrin derivatives, and poly (vinyl carbazole), poly (silylene), poly (thiophene), and the like, but are not limited thereto. .

  Examples of the solvent used in the second coating composition include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, n-dodecylbenzene, and methylnaphthalene, ether solvents such as tetrahydrofuran, dioxane, and diglyme, chloroform, Halogen solvents such as monochlorobenzene and 1,2-dichlorobenzene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate and n-butyl acetate, methanol, ethanol, n- Examples thereof include alcohol solvents such as propanol. These solvents may be used alone or in combination of two or more. Moreover, the film thickness of the thin film which consists of a (meth) acrylic acid ester compound can be adjusted by adjusting the viscosity of these solvents and the density | concentration of the (meth) acrylic acid ester compound in a solution.

  The content of the (meth) acrylic acid ester compound of the formula (3) contained in the second coating composition is preferably 0.05% by weight or more and 20% by weight or less based on the whole composition, and more Preferably, they are 0.1 weight% or more and 5 weight% or less.

  Specific examples of the coating method include a cast method, a spin coat 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.

  By the way, when forming the thin film which consists of a (meth) acrylic acid ester compound by the apply | coating method, a film | membrane can also be formed combining with a suitable binder resin.

  The binder resin can be selected from various binder resins. For example, polyvinyl carbazole resin, polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, polyacrylic resin, polymethacrylic resin, polyvinyl butyral resin, polyvinyl acetal resin, diallyl phthalate resin, phenol resin, epoxy resin, silicone resin, polysulfone Examples thereof include, but are not limited to, resins and urea resins. The form of the binder resin may be a homopolymer or a copolymer polymer. In addition, one type of binder resin may be used alone, or two or more types may be mixed and used.

  Moreover, when forming the thin film which consists of a (meth) acrylic ester compound by the apply | coating method, a thin film can also be formed, after adding a polymerization initiator to a 2nd coating composition. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, photopolymerization initiators, and the like.

  The second coating composition is preferably prepared using a solvent that does not dissolve the arylamine polymer of formula (1). By doing so, a thin film to be the second organic compound layer can be formed and laminated on the upper portion of the first organic compound layer.

  Next, the third step will be described. When the thin film made of the (meth) acrylic acid ester compound formed in the second step is heat-cured, the heating temperature is not particularly limited, but is generally in the range of 130 ° C to 200 ° C.

  The film thickness of the second organic compound layer formed by performing the third step is less than 5 μm, preferably 500 nm or less, more preferably 5 nm to 500 nm.

  In the organic light-emitting device of the present invention, when another organic compound layer is formed on the first organic compound layer containing the arylamine polymer of the formula (1) by a coating method, a layer is formed from the first organic compound layer. It is required that the constituent substances do not dissolve.

  On the other hand, the arylamine polymer of the formula (1) constituting the first organic compound layer is a polymer having a structure in which monomer units are linked in a straight chain. Here, the linear arylamine polymer generally has high solubility in an organic solvent. For this reason, in order to prevent the arylamine polymer from dissolving when another organic layer is laminated by a coating method, the types of solvents that can be coated on the first organic compound layer are limited. If the kind of solvent which can be apply | coated is limited, the kind of organic material which can be formed into a film by application | coating will also be limited. Therefore, in order to increase the types of usable organic materials, the first organic compound layer is preferably insolubilized.

  In the method for producing an organic light-emitting device of the present invention, a thin film containing a (meth) acrylic acid ester compound having an arylamine skeleton is applied on the first organic compound in order to insolubilize the first organic compound layer. A method of forming a film and performing heat treatment is employed. When the second organic compound layer formed by this method is subjected to heat treatment, the (meth) acrylic acid ester compound constituting the thin film causes a polymerization reaction, so that the layer itself is insolubilized.

  By the way, the (meth) acrylic acid ester compound of the formula (3) undergoes an intermolecular crosslinking reaction by a radical polymerization reaction by heating, a polymerization initiator or the like. By this intermolecular crosslinking reaction, a (meth) acrylic acid ester polymer thin film having an arylamine skeleton is formed. Since this thin film is a polymer thin film composed of a compound having a crosslinked structure, the thin film is insoluble in the solvent. For this reason, even if another organic compound layer is laminated on the thin film by a coating method as the next fourth step, the already formed polymer thin film is not dissolved by the solvent. Further, by forming this polymer thin film, it is possible to prevent not only the polymer thin film itself but also the material constituting the layer below the polymer thin film from being dissolved by the solvent contained in the paint. Therefore, in the method for manufacturing an organic light-emitting element of the present invention, an element having a stable laminated body in which the materials constituting the layers are not mixed can be manufactured.

  As described above, after forming a thin film to be the second organic compound layer in the second step, (meth) acrylic acid ester which is a constituent material of the thin film is subjected to heat treatment in the third step. The compound undergoes a polymerization reaction, and the thin film becomes a thin film insoluble in the solvent. By forming such a thin film, the first organic compound layer becomes insoluble in the organic solvent in the same manner as the second organic compound layer. Therefore, in the fourth step, the thin film that is the second organic compound layer is formed. A thin film that becomes the third organic compound layer can be formed and laminated on the upper portion by a coating method.

  Three layers (first organic compound layer, second organic compound layer, third organic compound) which are the main components of the organic light-emitting device of the present invention by the four steps shown in (i) to (iv) above. Layer) can be formed by a coating method. On the other hand, the arylamine polymer represented by formula (1) and the (meth) acrylic acid ester compound represented by formula (3) are not suitable for film formation by vapor deposition. For this reason, when forming three layers used as the main structure of the organic light emitting element of this invention, a vapor deposition method cannot be employ | adopted.

  The organic light emitting device manufactured by the manufacturing method of the present invention described above has a laminated structure composed of at least three organic compound layers. Specific examples of the organic compound layer include a hole injection layer, a hole transport layer, a light emitting layer, a hole / exciton blocking layer, an electron transport layer, and an electron injection layer. Among these layers, the layers corresponding to the first organic compound layer, the second organic compound layer, and the third organic compound layer described above are formed by a coating method. On the other hand, organic compound layers other than these three layers can be formed by any method such as vacuum deposition or solution coating. The film thickness of the organic light emitting device produced here is less than 5 μm, preferably 1 μm or less, and more preferably 5 nm or more and 500 nm or less.

  A display device such as a display can be configured by appropriately combining the organic light-emitting elements of the present invention. That is, the display device 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 device 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. 4 is a schematic cross-sectional view showing a part of the display device of the present invention. The display device 40 shown in FIG. 4 is provided adjacent to the organic light emitting element portion 42 provided on the substrate 41, the circuit portion 43 disposed outside the organic light emitting element portion 42, and the circuit portion 43. Data wiring 44. Here, the circuit unit 43 is provided with a drive transistor (TFT1) 451, a switching transistor (TFT2) 452, and a storage capacitor (Ch) 46.

  In FIG. 4, only one organic light emitting element is shown, but when actually constructing a display device, a plurality of organic light emitting elements are arranged two-dimensionally. A specific example of a display device in which organic light emitting elements are two-dimensionally arranged will be described later. In the present embodiment, the organic light emitting element section 42 is formed by laminating a lower electrode 47, an organic compound layer 48, and an upper electrode 49 in this order. In the organic light emitting element section 42, the organic compound layer 48 includes at least the first organic compound layer, the second organic compound layer, and the third organic compound layer.

  FIG. 5 is a diagram showing details of the circuit configuration in the circuit section of the display device of FIG. The circuit shown in FIG. 5 is 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 50 shown in FIG. 5 includes a drive transistor (TFT 1) 451, a switching transistor (TFT 2) 452, a storage capacitor (Ch) 46, and an organic light emitting element 51. Since the circuit configuration is well known, detailed description of the operation is omitted.

  By the way, the organic light emitting device of the present invention can be used as a single light emitting point and used as an exposure light source for a display device such as a display, an illumination device, or an electrophotographic image forming apparatus.

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

  FIG. 6 is a schematic view showing a display device in which the organic light emitting element portion and the circuit portion shown in FIGS. 4 and 5 are arranged in a matrix with one pixel.

  In the display device 60 of FIG. 6, the pixel 61 is connected to the gate driver 62 and the source driver 63 via a wiring, and enters a light emitting state or a non-light emitting state by a driving pulse supplied from each driver.

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

  The display device of the present invention may be in 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 device of the present invention is mounted may be used. Alternatively, the display device of the present invention can be used for an electronic imaging device such as a digital camera or a display unit of a mobile phone.

  FIG. 7 is a schematic diagram showing a configuration example in which the display device of FIG. 6 is made into a panel module. The panel module 70 of FIG. 7 is obtained by integrating an interface driver 71, a gate driver 62, and a source driver 63 with a housing 72 in addition to the display device 60 shown in FIG. 6. In the panel module 70 of FIG. 7, although not shown, a component (interface) necessary for connection to an external device such as a connection terminal is built in the housing 72.

[Evaluation of HOMO level]
Of the materials used in each Example and each Comparative Example, the HOMO energy of the material itself was evaluated. Here, the HOMO energy corresponds to an energy difference between the highest occupied molecular orbital (HOMO) of the material itself and the vacuum level, and is synonymous with the ionization potential. As a method for evaluating HOMO energy, a method of evaluating from a value measured by photoelectron spectroscopy was adopted. A photoelectron spectrometer AC-2 (manufactured by Riken Kikai Co., Ltd.) was used as a measuring apparatus for photoelectron spectroscopy.

  <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, after drying the organic layer with anhydrous sodium sulfate, 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 1-2]

(I) The following reagents and solvent were charged into a 200 ml three-necked flask.
Intermediate compound [6]: 3.0 g (5.27 mmol)
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. Obtained 0.90 g (yield 58%) of 1-2 as yellow amorphous.

  <Synthesis Example 3> [Exemplary Compound No. Synthesis of 1-4]

(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. 1-4 was obtained as white amorphous in 0.65 g (yield 42%).

<Synthesis Example 4> [Exemplary Compound No. Synthesis of 2-1]
In the flask, the following reagents and solvent were charged, and the flask was cooled in an ice water bath.
Dihydroxy compound represented by the following formula: 1.0 g (1.37 mmol)

トリエチルアミン：０．４９ｇ（４．８０ｍｍｏｌ）
テトラヒドロフラン：１０ｍｌ

Triethylamine: 0.49 g (4.80 mmol)
Tetrahydrofuran: 10ml

  Next, 0.37 g (4.11 mmol) of acrylic acid chloride was dropped into the reaction solution while keeping the temperature of the reaction solution at 10 ° C. or lower. After completion of the dropwise addition, the temperature of the reaction solution was gradually raised, and the reaction was continued for another 30 minutes while maintaining the temperature of the reaction solution at 50 ° C.

  After completion of the reaction, the reaction solution was cooled. Next, 100 ml of ethyl acetate and 50 ml of 10% aqueous sodium hydroxide solution were added to the reaction solution and stirred, and then a liquid separation operation was performed to recover the organic layer. The collected organic layer was further washed twice with 30 ml of ion exchange water and dried over magnesium sulfate.

  Next, the solvent in the organic layer was removed using a rotary evaporator to obtain a crude product. This crude product was purified using silica gel column chromatography. Specifically, about 10 g of silica gel was used, and toluene was initially used as a developing solvent, and a toluene / tetrahydrofuran mixed solvent (mixing ratio: 10/1) was used from the middle.

  Finally, the fraction corresponding to the target compound is recovered, and the solvent is removed under reduced pressure. As a result, 0.77 g of 2-1 was obtained.

<Synthesis Example 5> [Exemplary Compound No. Synthesis of 2-8]
Synthesis was carried out in the same manner as in Synthesis Example 4 using the following amounts of each synthesis reagent.
Dihydroxy compound represented by the following structural formula: 1.0 g (1.12 mmol)

トリエチルアミン：０．４２ｇ（３．９２ｍｍｏｌ）
テトラヒドロフラン：１０ｍｌ
アクリル酸クロライド：０．３０ｇ（３．３６ｍｍｏｌ）

Triethylamine: 0.42 g (3.92 mmol)
Tetrahydrofuran: 10ml
Acrylic acid chloride: 0.30 g (3.36 mmol)

  After completion of the reaction, purification is carried out in the same manner as in Synthesis Example 4 to obtain the target exemplified compound No. 0.75g of 2-8 was obtained.

<Synthesis Example 6> [Exemplary Compound No. Synthesis of 2-9]
Synthesis was carried out in the same manner as in Synthesis Example 4 using the following amounts of each synthesis reagent.
Dihydroxy compound represented by the following structural formula: 1.0 g (1.24 mmol)

トリエチルアミン：０．４４ｇ（４．３４ｍｍｏｌ）
テトラヒドロフラン：１０ｍｌ
アクリル酸クロライド：０．３３ｇ（３．７２ｍｍｏｌ）

Triethylamine: 0.44 g (4.34 mmol)
Tetrahydrofuran: 10ml
Acrylic acid chloride: 0.33 g (3.72 mmol)

  After completion of the reaction, purification is carried out in the same manner as in Synthesis Example 4 to obtain the target exemplified compound No. 0.72 g of 2-9 was obtained.

<Synthesis Example 7> [Exemplary Compound No. Synthesis of 2-10]
Synthesis was carried out in the same manner as in Synthesis Example 4 using the following amounts of each synthesis reagent.
Dihydroxy compound represented by the following structural formula: 1.0 g (1.19 mmol)

トリエチルアミン：０．４３ｇ（４．１８ｍｍｏｌ）
テトラヒドロフラン：１０ｍｌ
アクリル酸クロライド：０．３２ｇ（３．５７ｍｍｏｌ）

Triethylamine: 0.43 g (4.18 mmol)
Tetrahydrofuran: 10ml
Acrylic acid chloride: 0.32 g (3.57 mmol)

  After completion of the reaction, purification is carried out in the same manner as in Synthesis Example 4 to obtain the target exemplified compound No. 0.77g of 2-10 was obtained.

<Synthesis Example 8> [Exemplary Compound No. Synthesis of 2-15]
Synthesis was carried out in the same manner as in Synthesis Example 4 using the following amounts of each synthesis reagent.
Dihydroxy compound represented by the following structural formula: 1.0 g (1.19 mmol)

トリエチルアミン：０．４３ｇ（４．１８ｍｍｏｌ）
テトラヒドロフラン：１０ｍｌ
メタクリル酸クロライド：０．３７ｇ（３．５７ｍｍｏｌ）

Triethylamine: 0.43 g (4.18 mmol)
Tetrahydrofuran: 10ml
Methacrylic acid chloride: 0.37 g (3.57 mmol)

  After completion of the reaction, purification is carried out in the same manner as in Synthesis Example 4 to obtain the target exemplified compound No. 0.78 g of 2-15 was obtained.

[Example 1]
The organic light emitting device shown in FIG. 2 was produced.

  An anode 2 was formed by forming a film of indium tin oxide (ITO) on a glass substrate (substrate 1) by sputtering. At this time, the film thickness of the anode 2 was 120 nm. Next, the substrate on which this ITO was formed was ultrasonically washed successively with acetone and isopropyl alcohol (IPA), then boiled and washed with IPA, and then dried. Next, the substrate on which the ITO film was formed was UV / ozone cleaned. 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 chloroform solution having a concentration of 0.5% by weight (hereinafter referred to as a coating material for forming a hole injection layer in this example). Next, the hole injection layer 3 was formed by dropping the coating material for forming the hole injection layer on the anode 2 and spin-coating it. At this time, the thickness of the hole injection layer 3 was 15 nm.

  Next, Exemplified Compound No. 2-10 was dissolved in methyl isobutyl ketone to prepare a methyl isobutyl ketone solution having a concentration of 0.5% by weight (hereinafter referred to as a coating material for forming a hole transport layer in this example). Next, this hole transport layer forming coating was dropped onto the hole injection layer 3 and spin coated to form a thin film. Next, the hole transport layer 4 was formed by heating the thin film at 200 ° C. for 30 minutes and curing. At this time, the film thickness of the hole transport layer 4 was 15 nm. In addition, exemplary compound No. which comprises the said thin film by performing heat processing. 2-10 caused a crosslinking reaction, and the thin film was cured. For this reason, the hole transport layer 4 became a film insoluble in the solvent.

  Next, the following reagents and solvents were mixed to prepare a light emitting layer forming coating.

Ir (ppy) ₃ (tris (2-phenylpyridine) iridium): 0.01 part by mass PBD (2- (4-biphenyl) -5- (4-butylphenyl) -1,3,4-oxadiazole) : 0.3 parts by mass PVK (polyvinylcarbazole, Mn = 35000): 0.7 parts by mass

クロロベンゼン：９９質量部

Chlorobenzene: 99 parts by mass

  Next, this coating material for light emitting layer formation was dripped on the positive hole transport layer 4, and the thin film was formed by spin-coating for 1 minute at 1000 rpm. Next, the light emitting layer 5 was formed by heating at 120 degreeC for 30 minutes, and evaporating the solvent in the said thin film. At this time, the thickness of the light emitting layer 5 was 100 nm.

Next, the electron injection layer 7 was formed by vapor-depositing lithium fluoride on the light emitting layer 5 by a vacuum evaporation method. At this time, the film thickness of the electron injection layer 7 was set to 0.5 nm, the degree of vacuum during vapor deposition was set to 1.0 × 10 ⁻⁴ Pa, and the film formation rate was set to 0.01 nm / sec.

Next, the cathode 6 was formed by vapor-depositing aluminum on the electron injection layer 7 by a vacuum evaporation method. At this time, the film thickness of the cathode 6 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 DC voltage of 7 V 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 29 mA / cm ² , and green light emission with a luminance of 3010 cd / m ² was observed. Further, when the current density was maintained at 10 mA / cm ² and continuous driving was performed for 50 hours, the current density was changed from 960 cd / m ² (initial luminance) to 700 cd / m ² (luminance after 50 hours).

[Example 2]
In Example 1, Exemplified Compound No. In place of 1-1, Exemplified Compound No. The hole injection layer 3 was formed using 1-2. Except for this, an organic light emitting device was produced in the same manner as in Example 1. The obtained device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
In Example 1, Exemplified Compound No. In place of 1-1, Exemplified Compound No. The hole injection layer 3 was formed using 1-4. Except for this, an organic light emitting device was produced in the same manner as in Example 1. The obtained device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
In Example 1, Exemplified Compound No. In place of 2-10, Exemplified Compound No. The hole transport layer 4 was formed using 2-15. Except for this, an organic light emitting device was produced in the same manner as in Example 1. The obtained device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
In Example 1, Exemplified Compound No. In place of 2-10, Exemplified Compound No. The hole transport layer 4 was formed using 2-12. Except for this, an organic light emitting device was produced in the same manner as in Example 1. The obtained device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]
In Example 1, Exemplified Compound No. In place of 2-10, Exemplified Compound No. The hole transport layer 4 was formed using 2-1. Except for this, an organic light emitting device was produced in the same manner as in Example 1. The obtained device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, Exemplified Compound No. Comparative compound No. 1 shown in the following formula instead of 1-1 1 (4-polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), trade name: Vitron P Al-4083, manufactured by Bayer) was used. In addition, comparative compound No. 1 was dropped and spin coated, followed by heating at 120 ° C. for 30 minutes to form a hole injection layer 3 having a thickness of 30 nm. Except for these, an organic light emitting device was produced in the same manner as in Example 1. The obtained device was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 7]
The organic light emitting device shown in FIG. 2 was produced.

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

  Next, Exemplified Compound No. 1-1 was dissolved in p-xylene to prepare a p-xylene solution having a concentration of 0.5% by weight (hereinafter referred to as a hole injection layer forming coating material in this example). The hole injection layer 3 was formed by dropping this hole injection layer-forming coating material on the anode 2 and spin-coating it. At this time, the thickness of the hole injection layer 3 was 15 nm.

  Next, Exemplified Compound No. 2-10 was dissolved in methyl isobutyl ketone to prepare a methyl isobutyl ketone solution having a concentration of 0.5% by weight (hereinafter referred to as a coating material for forming a hole transport layer in this example). Next, this hole transport layer forming coating material was dropped on the hole injection layer 3 and spin coated to form a thin film. Next, the hole transport layer 4 was formed by heating the thin film at 200 ° C. for 30 minutes and curing. At this time, the film thickness of the hole transport layer 4 was 15 nm. In addition, exemplary compound No. which comprises the said thin film by performing heat processing. 2-10 caused a crosslinking reaction, and the thin film was cured. For this reason, the hole transport layer 4 became a film insoluble in the solvent.

Next, the following reagent and solvent were mixed to prepare a light emitting layer forming coating.
Exemplified Compound No. 2-10: 1 part by mass Green phosphorescent material represented by the following formula: 0.01 part by mass

クロロホルム：９９質量部

Chloroform: 99 parts by mass

  Next, this coating material for light emitting layer formation was dripped on the positive hole transport layer 4, and the thin film was formed by spin-coating for 1 minute at 1000 rpm. Next, the light emitting layer 5 was formed by heating at 80 degreeC for 30 minutes, and evaporating the solvent contained in the said thin film. At this time, the thickness of the light emitting layer 3 was 80 nm.

Next, the electron injection layer 7 was formed by vapor-depositing lithium fluoride on the light emitting layer 5 by a vacuum evaporation method. At this time, the film thickness of the electron injection layer 7 was set to 0.5 nm, the degree of vacuum during vapor deposition was set to 1.0 × 10 ⁻⁴ Pa, and the film formation rate was set to 0.01 nm / sec.

Next, the cathode 6 was formed by vapor-depositing aluminum on the electron injection layer 7 by a vacuum evaporation method. At this time, the film thickness of the cathode 6 was set to 100 nm, the degree of vacuum during vapor deposition was set to 1.0 × 10 ⁻⁴ Pa, and the film formation rate was set to 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 DC voltage of 7 V 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 20 mA / cm ² , and red light emission with a luminance of 1200 cd / m ² was observed. Further, when the current density was maintained at 30 mA / cm ² and continuous driving was performed for 50 hours, the current density changed from 1800 cd / m ² (initial luminance) to 1100 cd / m ² (luminance after 50 hours).

[Example 8]
In Example 7, Exemplified Compound No. In place of 1-1, Exemplified Compound No. The hole injection layer 3 was formed using 1-2. Other than this, an organic light-emitting device was fabricated in the same manner as in Example 7. The obtained device was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Example 9]
In Example 7, Exemplified Compound No. In place of 1-1, Exemplified Compound No. The hole injection layer 3 was formed using 1-4. Other than this, an organic light-emitting device was fabricated in the same manner as in Example 7. The obtained device was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Example 10]
In Example 7, Exemplified Compound No. In place of 2-10, Exemplified Compound No. The hole transport layer 4 was formed using 2-8. Other than this, an organic light-emitting device was fabricated in the same manner as in Example 7. The obtained device was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Example 11]
In Example 7, Exemplified Compound No. In place of 2-10, Exemplified Compound No. The hole transport layer 4 was formed using 2-9. Other than this, an organic light-emitting device was fabricated in the same manner as in Example 7. The obtained device was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Example 12]
In Example 7, Exemplified Compound No. In place of 2-10, Exemplified Compound No. The hole transport layer 4 was formed using 2-1. Other than this, an organic light-emitting device was fabricated in the same manner as in Example 7. The obtained device was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Comparative Example 2]
In Example 7, Exemplified Compound No. Comparative compound No. 1 shown in the following formula instead of 1-1 2 (poly [(9,9-dihexylfluorene-2,7-diyl) -co- [pyridine-3,5-diyl)], manufactured by HW SANDS) was used. In addition, comparative compound No. A toluene solution having a concentration of 0.5% by weight in which 2 was dissolved was dropped and spin-coated, and then heated at 120 ° C. for 30 minutes to form a hole injection layer 3 having a thickness of 15 nm. Except for these, an organic light emitting device was produced in the same manner as in Example 7. The obtained device was evaluated in the same manner as in Example 7. The results are shown in Table 2.

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 a cross-sectional schematic diagram which shows a part of display apparatus of this invention. FIG. 5 is a diagram illustrating details of a circuit configuration in a circuit unit of the display device of FIG. 4. FIG. 6 is a schematic view showing a display device in which the organic light emitting element portion and the circuit portion shown in FIGS. 4 and 5 are arranged in a matrix form as one pixel. It is a schematic diagram which shows the structural example which made the display apparatus of FIG. 6 the panel module.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,41 Substrate 2 Anode 3 Light emitting layer 4 Cathode 5 Hole transport layer 6 Electron transport layer 7 Hole injection layer 8 Electron injection layer 10, 20, 30, 51 Organic light emitting device 40, 60 Display device 42 Organic light emitting device section 43 Circuit part 44 Data wiring 451 Drive transistor (TFT1)
452 Switching transistor (TFT2)
46 Holding capacity (Ch)
47 Lower electrode 48 Organic compound layer 49 Upper electrode 50 Circuit 61 Pixel 62 Case driver 63 Source driver 70 Panel module 71 Interface driver 72 Housing

Claims (8)

An anode and a cathode;
A laminate that is sandwiched between the anode and the cathode and includes at least a first organic compound layer, a second organic compound layer, and a third organic compound layer in this order,
The anode or the cathode, the first organic compound layer, the first organic compound layer and the second organic compound layer, and the second organic compound layer and the third organic compound layer; Are in contact with each other,
An organic light-emitting device, wherein the first organic compound layer includes an arylamine polymer, and the second organic compound layer includes a (meth) acrylic acid ester polymer having an arylamine skeleton. The organic light-emitting device according to claim 1, wherein the arylamine polymer is a compound represented by the following general formula (1).

(In Formula (1), R ₁₁ and R ₁₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, an alkoxy group, or a halogen atom. Ar ₁₁ and Ar ₁₂ each represent a substituted or unsubstituted aryl group or a condensed polycyclic aromatic group, and Ar ₁₃ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted condensed polycyclic aromatic group. Ar ₁₄ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted divalent condensed polycyclic aromatic group, m represents an integer of 10 to 300, and n represents Represents an integer of 0 or more and 300 or less.) The organic light-emitting device according to claim 1, wherein the (meth) acrylic acid ester polymer is a compound represented by the following general formula (2).

(In Formula (2), A ₂₁ and A ₂₂ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms. Ar ₂₁ and Ar ₂₂ are each a substituted or unsubstituted aryl group or a substituted or unsubstituted group. A substituted condensed polycyclic aromatic group, Ar ₂₃ represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted divalent condensed polycyclic aromatic group, R ₂₁ and R ₂₂ are Each represents a hydrogen atom or a methyl group.) The organic light-emitting device according to claim 3, wherein Ar ₂₁ and Ar ₂₂ are substituted or unsubstituted fluorenyl groups. Forming a first organic compound layer comprising an arylamine polymer on the lower electrode by a coating method;
Forming a thin film composed of a (meth) acrylic acid ester compound having an arylamine skeleton on the first organic compound layer by a coating method;
A step of heat-curing the thin film to form a second organic compound layer;
And a step of forming a third organic compound layer on the second organic compound layer by a coating method. The method for producing an organic light-emitting element according to claim 5, wherein the arylamine polymer is a compound represented by the following general formula (1).

The method for producing an organic light-emitting element according to claim 5, wherein the (meth) acrylic acid ester compound is a compound represented by the general formula (3).

  A display device comprising the organic light-emitting device according to claim 1.

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