WO2013069432A1

WO2013069432A1 - Organic light emitting element, method for manufacturing same, and use of same

Info

Publication number: WO2013069432A1
Application number: PCT/JP2012/077044
Authority: WO
Inventors: 正彦鳥羽; 崇寺島
Original assignee: 昭和電工株式会社
Priority date: 2011-11-07
Filing date: 2012-10-19
Publication date: 2013-05-16
Also published as: JP2013229627A; JP5307954B1; JPWO2013069432A1

Abstract

The purpose of the present invention is to provide an organic light emitting element which has a plurality of adjacent organic compound layers and which exhibits excellent insolubilization properties and charge transport properties of the base layer and good emission characteristics in comparison to conventional organic light emitting elements. An organic light emitting element of the present invention comprises: a first electrode; a first organic compound layer that is formed on the first electrode; a second organic compound layer that is formed adjacent to the first organic compound layer; and a second electrode that is formed on the second organic compound layer. The first organic compound layer contains a non-crosslinked polymer and a crosslinked polymer, and both of the non-crosslinked polymer and the crosslinked polymer have a repeating unit that contains a charge-transporting structure. The absolute value of the difference between the ionization potential of the non-crosslinked polymer and the ionization potential of the crosslinked polymer is 0-0.2 eV.

Description

ORGANIC LIGHT EMITTING DEVICE, ITS MANUFACTURING METHOD, AND ITS APPLICATION

The present invention relates to an organic light-emitting device, a method for producing the same, and an application thereof, and more particularly to an organic light-emitting device having an organic compound layer containing a non-crosslinked polymer and a crosslinked polymer having charge transport properties, a method for producing the organic light-emitting device.

In recent years, application research on organic light-emitting elements (hereinafter also referred to as “organic EL elements”) has been actively conducted. An organic EL element is composed of a pair of electrodes composed of an anode and a cathode and one or a plurality of organic compound layers formed between the electrodes. By applying a voltage between the anode and the cathode, holes are respectively formed from the anode and the cathode. And electrons are injected, and light is emitted using energy generated by recombination of the injected electrons and holes in the organic compound layer. That is, the organic EL element utilizes a phenomenon in which light is generated when the light emitting material of the organic compound layer is excited by the energy due to this charge recombination and returns from the excited state to the ground state again.

A plurality of methods such as a vapor deposition method and a coating method are known as a method for producing an organic compound layer, and a method using a coating method has been actively studied because of the simplicity of the process. When an organic compound layer is formed using a coating method, a coating film is formed by coating a coating solution in which an organic material is dissolved, and this film is dried to form an organic compound layer.

However, when a laminated structure of an organic compound layer is formed by a coating method, particularly when an already formed organic compound layer is used as a base layer and a coating solution is applied for the purpose of forming another organic compound layer, The underlayer was sometimes dissolved by the solvent in the coating solution. When the underlying layer is dissolved, the thickness of the underlying layer may change, or the material constituting the underlying layer may be mixed into the newly formed organic compound layer. In some cases, it could not be obtained.

In order to solve the above problems, a method of using a compound having a crosslinking group such as an epoxy group as a material for forming an underlayer and crosslinking and insolubilizing this compound by applying external energy after coating film formation has already been studied. ing.

In Patent Document 1, an insolubilized film is formed by coating a coating solution containing a carrier transporting or light-emitting polymer and a low molecular crosslinking agent and then crosslinking the low molecular crosslinking agent in the organic compound layer. is doing. However, since these cross-linking agents are poor in charge transport properties, the charge transport properties of the organic compound layer are lowered by addition, and the cross-linking agents themselves sometimes function as carrier traps. For this reason, there is a problem in that the performance of the organic light emitting device is lowered when the additive is increased in order to improve curability. In addition, if the amount added is reduced in order to suppress the adverse effects due to the addition of the cross-linking agent, insolubilization of the organic compound layer becomes insufficient, which makes it difficult to produce the intended organic light-emitting device.

In Patent Document 2, by using a cross-linking agent exhibiting charge transportability as a cross-linking agent added to the organic material forming the organic compound layer, it is possible to suppress deterioration in characteristics of the organic compound layer and It is disclosed that dissolution resistance can also be imparted, and as a crosslinking agent exhibiting charge transportability, a compound exhibiting a high charge mobility of 10 ⁻⁹ cm ² / V · s or more in a thin film composed only of this crosslinking agent is described. Has been.

However, the charge mobility of the organic compound layer obtained by mixing such a charge transporting organic material with a crosslinking agent exhibiting such charge transporting property and crosslinking the crosslinking agent after coating film formation depends on the combination of the compounds. In some cases, the charge mobility of the organic compound layer consisting only of the organic material or the cross-linking agent may be lower than that of the organic compound layer. There is a problem that cannot be sufficiently insolubilized.

JP-A-2005-243300 JP 2010-129825 A

The present invention has been made in view of the above-described problems of the prior art, and in an organic light emitting device having a plurality of adjacent organic compound layers, the underlayer has a solvent resistance and charge compared to the conventional organic light emitting device. An object of the present invention is to provide an organic light-emitting device that is excellent in transportability and exhibits good light-emitting properties.

As a result of intensive studies to solve the above problems, the present inventors have found that when the organic compound layer containing a non-crosslinked polymer having a charge transport property and a crosslinked polymer is formed on the electrode, the non-crosslinked By setting the absolute value of the difference between the ionization potential of the polymer and the ionization potential of the crosslinked polymer to 0.2 eV or less, the organic compound layer has excellent charge transport properties, and the organic compound layer has a large amount of crosslinked polymer. Organic light-emitting device that can be contained, can improve solvent resistance (herein, solvent resistance means poor solubility in organic solvents), and has an organic compound layer Was found to exhibit good luminescent properties, and the present invention was completed.

That is, the present invention relates to the following (1) to (16), for example.

(1)
A first electrode;
A first organic compound layer formed on the first electrode;
A second organic compound layer formed adjacent to the first organic compound layer;
An organic light emitting device having a second electrode formed on the second organic compound layer,
The first organic compound layer contains a non-crosslinked polymer and a crosslinked polymer;
The non-crosslinked polymer and the crosslinked polymer each include a repeating unit including a structure having charge transportability,
An organic light emitting device in which an absolute value of a difference between an ionization potential of the non-crosslinked polymer and an ionization potential of the crosslinked polymer is 0 to 0.2 eV.

(2)
The crosslinked polymer is a polymer formed by polymerizing at least a first polymerizable compound;
The organic light-emitting device according to (1), wherein the first polymerizable compound is a compound including a structure having a charge transporting property.

(3)
In the non-crosslinked polymer and the crosslinked polymer, the two structures having charge transporting properties included in adjacent repeating units are linked by a linking group containing a nonconjugated structure. Organic light emitting device.

(4)
(1) to (3) any one of (1) to (3), wherein the structure having the charge transport property of the repeating unit of the non-crosslinked polymer and the structure having the charge transporting property of the repeating unit of the crosslinked polymer are the same structure. The organic light-emitting device described in 1.

(5)
The organic light-emitting device according to any one of (1) to (4), wherein the structure having a charge transporting property is a triphenylamine derivative.

(6)
The non-crosslinked polymer is a polymer comprising at least one repeating unit selected from the following general formula (1) and the following general formula (2):
The organic light-emitting device according to any one of (2) to (5), wherein the first polymerizable compound is a compound represented by the following general formula (3).

In (formula (1) to (3), respectively each A independently represents a structure having a charge transport, respectively X ¹ and X ⁵ are independently, -O -, - S-, or a substituent An alkylene group having 1 to 20 carbon atoms that may have (provided that one or two or more non-adjacent methylene groups in the alkylene group may be substituted with —O— or —S— and bonded to A; One non-adjacent or two or more non-adjacent methylene groups are —SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, an arylene group Which may be substituted with
X ² to X ⁴ are each independently a single bond, —O—, —S—, or an optionally substituted alkylene group having 1 to 20 carbon atoms (provided that one or not in the alkylene group is not adjacent) Two or more methylene groups may be substituted with —O— or —S—, and one or more methylene groups not bonded to A may be —SO—, —SO ₂ —, —CO—. , —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, which may be substituted with an arylene group), and R ^Y represents a hydrogen atom, an alkyl having 1 to 4 carbon atoms. Represents a group, an aryl group, or an aralkyl group, and a is 0 or 1; )
(7)
A in the general formula (3) is 0;
The first polymerizable compound and the second polymerizable compound in a range in which the crosslinked polymer is 10 to 100% by mass of the second polymerizable compound with respect to 100% by mass of the first polymerizable compound. The organic light-emitting device according to (6), which is obtained by copolymerization of

(8)
The organic light-emitting device according to (6), wherein A in the general formulas (1) to (3) is represented by the following general formula (4).

(In General Formula (4), one of R ² and R ³ is a group represented by the following General Formula (5),
Any two of R ¹ to R ¹⁵ in the general formula (4) and R ¹⁶ to R ²⁹ in the following general formula (5) are X ¹ to X ⁵ or hydrogen in the general formulas (1) to (3). A bond to an atom,
The group represented by the general formula (5) and R ¹ to R ¹⁵ that are not a bond are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or carbon. An alkoxy group of 1 to 10; )

(In the general formula (5), R ¹⁶ to R ²⁹ which are not a bond are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. In the case where b is 0 or 1 and b is 1, the linked aromatic rings R may be bonded to each other to form a condensed ring.
(9)
The organic light-emitting device according to any one of (1) to (8), wherein a mass ratio of the crosslinked polymer and the non-crosslinked polymer contained in the first organic compound layer is 50:50 to 95: 5. .

(10)
The organic light-emitting device according to any one of (6) to (8), wherein the formula weight of the structure having a charge transport property represented by A is 240 to 1000.

(11)
X ³ and X ⁴ in the general formula (3) may have a substituent having 10 or more atoms constituting the shortest chain connecting A and the vinyl group in the general formula (3) A group (provided that one or two or more methylene groups in the alkylene group may be substituted with —O— or —S—, and one or two or more methylene groups not bonded to A) May be substituted with —SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, an arylene group, and R ^Y is (A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group.) The organic light-emitting device according to any one of (6) to (8) and (10).

(12)
The first organic compound layer includes an electron acceptor in an amount of 0.1 to 10% by mass with respect to a total of 100% by mass of the non-crosslinked polymer and the crosslinked polymer (1) to (11). Organic light emitting device.

(13)
A coating solution used for manufacturing an organic light emitting device,
A non-crosslinked polymer, a first polymerizable compound capable of forming a crosslinked polymer, and a solvent,
The non-crosslinked polymer includes a repeating unit including a structure having a charge transporting property, and the first polymerizable compound is a compound including a structure having a charge transporting property;
A coating solution in which an absolute value of a difference between an ionization potential of the non-crosslinked polymer and an ionization potential of a crosslinked polymer formed by polymerizing the first polymerizable compound is 0.2 eV or less.

(14)
On the first electrode, a step of applying a solution containing a non-crosslinked polymer, a first polymerizable compound capable of forming a crosslinked polymer, and a solvent to form a coating film;
Polymerizing the first polymerizable compound in the coating film to form a first organic compound layer containing a non-crosslinked polymer and a crosslinked polymer; and a second adjacent to the first organic compound layer. A step of forming the organic compound layer by coating, and a step of forming a second electrode on the second organic compound layer,
The first polymerizable compound is a compound including a structure having charge transporting properties, and the non-crosslinked polymer and the crosslinked polymer each include a repeating unit including a structure having charge transporting properties;
A method for manufacturing an organic light emitting device, wherein an absolute value of a difference between an ionization potential of the non-crosslinked polymer and an ionization potential of the crosslinked polymer is 0.2 eV or less.

(15)
(1) An illuminating device comprising the organic light-emitting element according to any one of (12).

(16)
(1) A display device comprising the organic light-emitting device according to any one of (12).

The organic light-emitting device of the present invention contains a non-crosslinked polymer and a crosslinked polymer, and has a first organic compound layer having a small absolute value of the difference in ionization potential between the two. For the purpose of forming the second organic compound layer, the layer is suppressed in dissolution even when a coating solution is applied, and the first organic compound layer is excellent in charge transporting property. This organic light emitting device exhibits good light emitting characteristics.

FIG. 1 is a cross-sectional view illustrating an example of the structure of the organic light emitting device of the present invention. FIG. 2 is a conceptual diagram showing a course of a probe (probe) when measuring the thickness of an organic compound layer using a stylus type surface shape measuring apparatus.

Next, the present invention will be specifically described.

The organic light emitting device of the present invention includes a first electrode, a first organic compound layer formed on the first electrode, and a second organic layer formed adjacent to the first organic compound layer. An organic light-emitting device having a compound layer and a second electrode formed on the second organic compound layer. In the organic light-emitting device of the present invention, the first organic compound layer includes a non-crosslinked polymer and a crosslinked polymer, and the non-crosslinked polymer and the crosslinked polymer both have a structure having a charge transporting property. Including a repeating unit, the absolute value of the difference between the ionization potential of the non-crosslinked polymer and the ionization potential of the crosslinked polymer is 0 to 0.2 eV.

The organic light emitting device of the present invention includes at least one light emitting layer. The second organic compound layer may be a light emitting layer, or a light emitting layer may be formed between the second organic compound layer and the second electrode. The organic light emitting device may include a plurality of light emitting layers, and may further include an organic compound layer different from the light emitting layer. For example, an electron injection layer, an electron transport layer, a hole blocking layer, or the like may be provided between the second organic compound layer and the cathode (second electrode).

DETAILED DESCRIPTION Embodiments for implementing the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing an example of the configuration of the organic light emitting device 10 of the present invention. On the anode 12, the first organic compound layer 13, and the first organic compound layer 13 provided on the substrate 11. A second organic compound layer 14 and a cathode 15 which are laminated adjacently are provided in this order.

The anode 12 and the cathode 15 in FIG. 1 correspond to the first electrode and the second electrode in the present invention, respectively. In the organic light emitting device shown in FIG. 1, by applying a voltage between the anode 12 and the cathode 15, holes are injected from the anode 12 and electrons are injected from the cathode 15, so that the second organic compound layer (light emitting layer) ) To recombine and emit light.

[substrate]
As a material of the substrate 11, when light is to be extracted from the substrate 11 side of the organic light emitting element 10 (when the surface on the substrate 11 side is a surface from which light is extracted, that is, a light emitting surface), the wavelength of the emitted light is And transparent. Specifically, when the emitted light is visible light, glass such as soda glass and non-alkali glass; transparent plastic such as acrylic resin, methacrylic resin, polycarbonate resin, polyester resin, and nylon resin;

When it is not necessary to extract light from the surface of the organic light emitting element 10 on the substrate 11 side, the material of the substrate 11 is not limited to a transparent material, and an opaque material can be used. Specifically, in addition to the above materials, copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta), or niobium (Nb) ), Alloys thereof, or materials made of stainless steel can also be used.

The thickness of the substrate 11 is preferably 0.1 to 10 mm, more preferably 0.25 to 2 mm, although it depends on the required mechanical strength.

[anode]
When a voltage is applied between the anode 12 and the cathode 15, holes are injected into the first organic compound layer 13. The material used for the anode 12 is not particularly limited as long as it has electrical conductivity, but preferably has a sheet resistance of 1000Ω / □ or less in a temperature range of −5 to 80 ° C. More preferably, it is 100Ω / □ or less.

¡Conductive metal oxides, metals, and alloys can be used as materials that satisfy these conditions. Here, examples of the conductive metal oxide include ITO (indium tin oxide) and IZO (indium zinc oxide). Examples of the metal include copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta), niobium (Nb), and the like. An alloy containing these metals and stainless steel can also be used. Examples of the transparent material used for forming the transparent anode include conductive glass made of indium oxide, zinc oxide, tin oxide, ITO (indium tin oxide) which is a composite thereof, IZO (indium zinc oxide), or the like. , Gold, platinum, silver and copper. Among these, ITO, IZO, and tin oxide are preferable. Further, a transparent conductive film made of an organic material such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.

The thickness of the anode 12 is preferably 2 nm to 1 μm, and more preferably 20 to 500 nm in order to obtain high light transmittance when light is to be extracted from the substrate 11 side of the organic light emitting device 10. Further, when it is not necessary to extract light from the substrate 11 side of the organic light emitting element 10, the thickness is, for example, 2 nm to 2 mm.

The material of the substrate 11 may be the same material as the anode 12. In this case, the substrate 11 may also serve as the anode 12.

[First organic compound layer]
The first organic compound layer 13 in the organic light emitting device of the present invention contains a non-crosslinked polymer and a crosslinked polymer. In addition, the first organic compound layer 13 is usually formed by applying a solution containing the non-crosslinked polymer and the first polymerizable compound capable of forming the crosslinked polymer on the first electrode, and then It is formed by polymerizing a polymerizable compound.

Both the non-crosslinked polymer and the crosslinked polymer according to the present invention include a repeating unit including a structure having a charge transporting property.

In addition, since the absolute value of the ionization potential difference between the non-crosslinked polymer and the crosslinked polymer is 0 to 0.2 eV, more preferably 0 to 0.1 eV, and still more preferably 0.01 to 0.05 eV, It is possible to prevent a decrease in performance.

The absolute value of the difference in ionization potential is obtained from the ionization potential measured as follows. A first polymerizable compound described later and a second polymerizable compound described later if necessary are dissolved in a solvent, and a coating solution of 1 to 3% by mass is prepared in total of both polymerizable compounds. Using this coating solution, a film is formed on a transparent support substrate by spin coating (1000 to 5000 rpm). The coating film is dried to polymerize the polymerizable compound. The value obtained by measuring the ionization potential of the obtained film by atmospheric photoelectron spectroscopy is defined as the ionization potential of the crosslinked polymer. Similarly, instead of the first polymerizable compound and the second polymerizable compound, a coating solution in which the non-crosslinked polymer is dissolved is used and the ionization potential of the obtained film is set as the ionization potential of the non-crosslinked polymer. The absolute value of the difference between the ionization potentials can be calculated from the ionization potential of the crosslinked polymer and the ionization potential of the non-crosslinked polymer. Here, as the solvent, the same solvents that can be used for forming the first organic compound layer described later can be used, and the same solvents are used for the measurement of the non-crosslinked polymer and the measurement of the crosslinked polymer. Moreover, the method and conditions of drying and polymerization can employ | adopt the method which can be used for manufacture of the below-mentioned organic light emitting element, and the measurement of a non-crosslinked polymer and the measurement of a crosslinked polymer are performed on the same conditions. In addition, although the process of superposing | polymerizing is originally unnecessary for preparation of the film | membrane which consists of a non-crosslinked polymer, in order to align the ionization potential and measurement conditions of the film | membrane which consists of a crosslinked polymer, it heat-processes on the same conditions.

The non-crosslinked polymer is not particularly limited, but it is preferable to use a polymer composed of at least one repeating unit selected from the following general formula (1) and general formula (2).

The crosslinked polymer is usually a polymer obtained by polymerizing the first polymerizable compound. Even if the crosslinked polymer is a polymer obtained only from the first polymerizable compound as a monomer, The copolymer obtained by superposing | polymerizing 1 polymeric compound and 2nd polymeric compound may be sufficient.

The first polymerizable compound is not particularly limited, but a compound containing a structure having a charge transporting property is usually used, and a compound represented by the general formula (3) described later is preferably used.

As the second polymerizable compound, for example, a polymerizable compound having only one vinyl group in the molecule is used, and a compound having no charge transporting property or a compound having charge transporting property may be used. Good. As the second polymerizable compound, usually a vinyl compound having no charge transporting property is used. For example, a substituted or unsubstituted linear terminal alkene, a substituted or unsubstituted styrene, an acrylate ester, a methacrylate ester. And vinyl acetate. The number of carbons contained in these compounds is preferably in the range of 4 to 20, more specifically 1-octene, 4-phenyl-1-butene, styrene, α-methylstyrene, ethyl methacrylate, etc. A compound can be illustrated.

(Structure with charge transport properties)
Each of the non-crosslinked polymer and the crosslinked polymer contained in the first organic compound layer has a repeating unit including a structure having a charge transporting property.

A known material can be used for the structure having a charge transporting property, and examples thereof include compounds described in Chemical Reviews, Vol. 107, pp. 953-1010, 2007. In the organic light-emitting device of the present invention, In order not to reduce the charge transport property of the first organic compound layer, the absolute value of the difference between the ionization potential of the crosslinked polymer and the ionization potential of the non-crosslinked polymer is 0 to 0.2 eV, preferably 0 to 0.1 eV, Preferably, a voltage of 0.01 to 0.05 eV is used. By satisfying such a condition, a decrease in charge mobility of the first organic compound layer is suppressed, and a decrease in light emission efficiency of the organic light emitting device of the present invention is suppressed. In addition, since such a crosslinked polymer does not adversely affect the charge mobility of the first organic compound layer, it can be present at a higher ratio than conventional and the solvent resistance is also improved.

Moreover, as a structure having charge transportability, a triphenylamine derivative is preferable in that an organic light-emitting device having excellent hole injection ability and hole transport ability and high luminous efficiency can be obtained, and is represented by the following general formula (4). The structure is more preferred. That is, it is more preferable that A in the general formulas (1) to (3) described later is represented by the following general formula (4).

In addition, if the structure having charge transportability contained in the non-crosslinked polymer and the structure having charge transportability contained in the polymerizable compound are the same, the absolute value of the difference in ionization potential is reduced and the charge transportability is lowered. This is preferable because the first organic compound layer can be obtained as a solvent-resistant film without the above.

In the general formulas (1) to (3) to be described later, the structure having a charge transporting property represented by A is preferably 240 to 1000, more preferably 400 to 1000. preferable. Within this range, the first organic compound layer is preferred because it is excellent in solvent resistance and heat resistance.

(In General Formula (4), one of R ² and R ³ is a group represented by the following General Formula (5), and preferably R ³ is a group represented by the following General Formula (5). Any two of R ¹ to R ¹⁵ in the general formula (4) and R ¹⁶ to R ²⁹ in the following general formula (5) are X ¹ to X ⁵ or hydrogen in the general formulas (1) to (3). The group represented by the general formula (5) and R ¹ to R ¹⁵ which are bonds to the atom and are not bonds are independently a hydrogen atom, a halogen atom, a cyano group, an amino group, or a carbon number of 1 An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

(In the general formula (5), R ¹⁶ to R ²⁹ which are not a bond are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkoxy group, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, b is 0 or 1, and when b is 1, Rs of the linked aromatic rings are bonded to each other to be condensed. A ring may be formed.)
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, tert-butyl group, 1-pentyl group and 2-pentyl group. Group, 3-pentyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 4-methylpentyl group, 2-ethylbutyl group, n-heptyl group 2-heptyl group, 3-heptyl group, 4-heptyl group, n-octyl group, 2-octyl group, 3-octyl group, 4-octyl group, n-ethylhexyl group, n-nonyl group, 2-nonyl group , 3-nonyl group, 4-nonyl group, 5-nonyl group, n-decyl group and the like, preferably methyl group or ethyl group.

Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tertiary butoxy group, pentyloxy group, hexyloxy group, 2 -An ethylhexyloxy group, an octyloxy group, etc. are mentioned, Preferably they are a methoxy group or an ethoxy group.

In the case where b is 1, in the case where Rs of linked aromatic rings are bonded to each other to form a condensed ring, at least one R of R ¹ to R ⁵ and R ²⁶ to R ²⁹ are combined. And at least one R in combination forms a condensed ring. In this case, the group forming the condensed ring is usually an alkylene group having 1 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms.

Specific examples of the structure represented by the general formula (4) are shown below. In the following specific examples, the description of the bond to X ¹ to X ⁵ or a hydrogen atom in the general formulas (1) to (3) described later is omitted.

(Non-crosslinked polymer)
The non-crosslinked polymer contained in the first organic compound layer of the organic light-emitting device of the present invention includes a repeating unit having charge transporting properties. The non-crosslinked polymer is not particularly limited, but it is preferable that the two structures having charge transporting properties included in adjacent repeating units are linked by a linking group containing a nonconjugated structure. In other words, the non-crosslinked polymer is preferably linked without conjugating two structures having charge transporting properties contained in adjacent repeating units via a linking group. That is, when the non-crosslinked polymer is a polymer containing the charge transporting structure in the main chain, the non-crosslinked polymer has a non-crosslinked portion between two adjacent structures having the charge transporting property in the main chain. It preferably contains a conjugated structure. In the case where the non-crosslinked polymer is a polymer containing the charge transporting structure in the side chain, the main chain of the non-crosslinked polymer is a non-conjugated structure, or the structure having the charge transporting property and the main chain are It is preferable that they are connected via a non-conjugated structure. Examples of the linking group containing a non-conjugated structure include a C 1-20 alkylene group and a group containing an aliphatic ether bond.

The non-crosslinked polymer is preferably a polymer composed of at least one repeating unit selected from the following general formula (1) and the following general formula (2), and the repeating unit represented by the following general formula (2) More preferably, the polymer consists of

(In the general formulas (1) and (2), each A independently represents a structure having a charge transporting property, and X ¹ represents —O—, —S—, or a carbon which may have a substituent. An alkylene group of 1 to 20 (provided that one or two or more methylene groups not adjacent to each other in the alkylene group may be substituted with —O— or —S—, and one or adjacent not bonded to A) Two or more methylene groups are not substituted with —SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, or an arylene group. X ² represents a single bond, —O—, —S—, or an alkylene group having 1 to 20 carbon atoms which may have a substituent (provided that one or not in the alkylene group) Two or more methylene groups may be substituted with —O— or —S—, and are not bonded to A. One or two or more methylene groups not adjacent to each other are replaced by —SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, an arylene group Preferably represents a single bond, and R ^Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group.)
In addition, as a preferable aspect of the structure which has the charge transport property represented by said A, it is as having demonstrated in the above-mentioned (structure which has charge transport property).

In the alkylene group having 1 to 20 carbon atoms which may have a substituent, when there is no substituent, that is, as the alkylene group having 1 to 20 carbon atoms, for example, ethylene group, propylene group, butylene group, pentamethylene Group, hexamethylene group, heptamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tetradecamethylene group and the like.

Further, in the alkylene group having 1 to 20 carbon atoms which may have a substituent, when it has a substituent, that is, as the alkylene group having 1 to 20 carbon atoms having a substituent, for example, 1-ethoxy-2, Examples include 5-hexylene group, 1,5-dimethoxy-2,3-pentylene group, 1-ethoxy-2- (2-ethoxyethoxy) ethylene group, 1-butylsulfonyl-1,4-butylene group.

In the alkylene group having 1 to 20 carbon atoms which may have a substituent, when an methylene group is substituted with an arylene group, an arylene group having 6 to 21 carbon atoms is preferable. Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group.

When R ^Y is an alkyl group having 1 to 4 carbon atoms, examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, tert group -A butyl group is mentioned.

When R ^Y is an aryl group, it is preferably an aryl group having 6 to 21 carbon atoms. Examples of the aryl group include phenyl group, tolyl group, xylyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group and the like.

When R ^Y is an aralkyl group, it is preferably an aralkyl group having 7 to 21 carbon atoms. Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group and the like.

Specific examples of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are shown below.

(First polymerizable compound)
The crosslinked polymer contained in the first organic compound layer of the organic light-emitting device of the present invention includes a repeating unit including a structure having a charge transporting property. The crosslinked polymer is usually a polymer formed by polymerizing at least a first polymerizable compound, and the first polymerizable compound is usually a compound having a structure having a charge transporting property.

The first polymerizable compound is a compound including a structure having a charge transporting property and is a polymerizable compound capable of forming a crosslinked polymer. As the first polymerizable compound, a compound containing a polymerizable group and a structure having charge transportability is used. The first polymerizable compound usually contains two or more polymerizable groups in the compound.

Examples of the polymerizable group of the first polymerizable compound include a vinyl group, an ethynyl group, a butenyl group, an acryloyl group, an acryloylamino group, a methacryloyl group, a methacryloylamino group, a vinyloxy group, a vinylamino group, a silanol group, and a cyclopropyl group. , A cyclobutyl group, an epoxy group, an oxetanyl group, a diketenyl group, an epithio group, a lactone group, and a lactam group, preferably a vinyl group or an acryloyl group among these polymerizable groups A methacryloyl group is preferred, and a vinyl group is most preferred. As the cross-linked polymer, it is preferable that two structures having charge transporting properties contained in adjacent repeating units are connected by a linking group containing a non-conjugated structure, More preferably, the structure having a charge transporting property is linked to the linking main chain by a linking group containing a non-conjugated structure. That is, it is preferable that the crosslinked polymer is connected without conjugating two structures having charge transporting properties contained in adjacent repeating units via a linking group. For example, when the polymerizable group is a vinyl group, it is preferable because the linking group has a methylene group having a non-conjugated structure.

The first polymerizable compound is preferably a compound represented by the following general formula (3).

(In General Formula (3), A represents a structure having a charge transporting property, and X ⁵ represents —O—, —S—, or an alkylene group having 1 to 20 carbon atoms which may have a substituent (provided that In the alkylene group, one or two or more methylene groups that are not adjacent to each other may be substituted with —O— or —S—, and one or two or more methylene groups that are not bonded to A are —SO 2 -, -SO _2- , -CO-, -COO-, -N (R ^Y )-, -CO-N (R ^Y )-, which may be substituted with an arylene group), X ³ , X ⁴ is independently a single bond, -O -, - S-, or an optionally substituted alkylene group having 1 to 20 carbon atoms (provided that one of the alkylene group or not adjacent two or more The methylene group may be substituted by -O-, -S-, one or adjacent not bound to A Two or more methylene groups are not substituted with —SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, or an arylene group. R ^Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and a is 0 or 1.

In addition, as a preferable aspect of the structure having the charge transporting property represented by A, it is as described in the above section (Structure having charge transporting property).

X ⁵ is preferably an alkylene group having 1 to 20 carbon atoms which may have a substituent (provided that one or two or more methylene groups not adjacent to the alkylene group are substituted with —O— or —S—). And one or more methylene groups not bonded to A may be —SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—. N (R ^Y ) —, which may be substituted with an arylene group). The alkylene group having 1 to 20 carbon atoms which may have a substituent in X ⁵ is preferably an alkylene group having 6 to 14 carbon atoms which may have a substituent.

As examples and preferred embodiments of the alkylene group having 1 to 20 carbon atoms which may have a substituent used herein and R ^Y , the substituent in the general formula (1) and the general formula (2) may be used. Examples thereof may include an alkylene group having 1 to 20 carbon atoms and the same examples and preferred embodiments of R ^Y.

The first polymerizable compound preferably has a structure having a long chain length as a spacer between a structure having charge transporting properties and a polymerizable group such as a vinyl group. A long chain length is preferable because crosslinking is easily developed and the solvent resistance of the first organic compound layer is increased.

From this viewpoint, X ³ and X ⁴ are each an alkylene group (provided that the atom constituting the shortest chain connecting A and the vinyl group in Formula (3) is 10 or more, which may have a substituent (provided that In the alkylene group, one or two or more methylene groups that are not adjacent to each other may be substituted with —O— or —S—, and one or two or more methylene groups that are not bonded to A are — SO—, —SO ₂ —, —CO—, —COO—, —N (R ^Y ) —, —CO—N (R ^Y ) —, an arylene group may be substituted, and R ^Y represents a hydrogen atom Represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group thereof.) The alkylene group preferably has 10 to 14 atoms constituting the shortest chain, The number of atoms constituting the chain is 12-14 Preferred in La.

Specific examples of the compound represented by the general formula (3) are shown below.

If the structure of the first polymerizable compound having a charge transporting property is high and the molecular weight of the first polymerizable compound is small, phase separation is likely to occur in the coating film forming stage, and the resistance of the non-crosslinked polymer portion after the crosslinking is increased. Solvent property may be lowered. Therefore, it is preferable that a is 1 in the first polymerizable compound represented by the general formula (3).

In the prior art, if the ratio of the polymerizable compound to the non-crosslinked polymer used when forming the organic compound layer is too high, the effect of adding the polymerizable compound becomes apparent in the characteristics of the organic compound layer, and the non-crosslinked polymer It has been preferred not to add too much polymerizable compound since the inherent properties will be reduced. On the other hand, in the present invention, when the amount of the first polymerizable compound used when forming the first organic compound layer is increased, that is, when the proportion of the crosslinked polymer existing in the first organic compound layer is increased. Even so, it is preferable to use the first organic compound layer in order to improve the solvent resistance without deteriorating the characteristics of the first organic compound layer.

In the organic light-emitting device of the present invention, the mass ratio of the crosslinked polymer and the non-crosslinked polymer (crosslinked polymer: non-crosslinked polymer) contained in the first organic compound layer is preferably 50:50 to 95: 5 . In the present invention, the amount of the crosslinked polymer in the mass ratio is calculated from the amount of the polymerizable compound used when forming the first organic compound layer, and the amount of the non-crosslinked polymer forms the first organic compound layer. This is the amount of non-crosslinked polymer used in the process. If the ratio of the non-crosslinked polymer exceeds the above range, crystallization of the polymerizable compound tends to occur when the first organic compound layer is formed, and smooth film formation may be difficult.

From the viewpoint of power efficiency of the organic light emitting device, the mass ratio of the crosslinked polymer to the non-crosslinked polymer is more preferably 50:50 to 75:25, and further preferably 60:40 to 75:25. preferable.

From the viewpoint of the luminous efficiency of the organic light emitting device, the mass ratio of the crosslinked polymer to the non-crosslinked polymer is more preferably 80:20 to 95: 5, and further preferably 90:10 to 95: 5. preferable.

If the molecular weight of the first polymerizable compound is too small, it tends to be difficult to form a flat and uniform film when a solution containing the non-crosslinked polymer and the first polymerizable compound is applied. If the molecular weight is too large, the ratio of the cross-linking group occupying the first polymerizable compound is relatively lowered, the reactivity when obtaining the cross-linked polymer from the first polymerizable compound is lowered, and the first organic compound layer Since insolubilization may be difficult and heat resistance may be lowered, the molecular weight of the first polymerizable compound is preferably 300 to 2000, and more preferably 500 to 1800.

(Second polymerizable compound)
As described above, the crosslinked polymer included in the first organic compound layer may be a polymer formed only from the first polymerizable compound or a polymer formed from the first polymerizable compound and the second polymerizable compound. There may be.

The second polymerizable compound may be a compound having no charge transporting property or a compound having charge transporting property. Further, the second polymerizable compound usually contains one polymerizable group in the compound. As the second polymerizable compound, usually a vinyl compound having no charge transporting property is used. For example, a substituted or unsubstituted linear terminal alkene, a substituted or unsubstituted styrene, an acrylate ester, a methacrylate ester. And vinyl acetate.

The crosslinked polymer according to the present invention may be a polymer formed only from the first polymerizable compound, but the first polymerizable compound is a compound represented by the general formula (3), and the general formula (3 When a in 0) is 0, the crosslinked polymer is preferably a polymer formed from the first polymerizable compound and the second polymerizable compound.

When a in the general formula (3) is 0, the cross-linked polymer is in a range where the second polymerizable compound is 10 to 100% by mass with respect to 100% by mass of the first polymerizable compound. It is preferable to be obtained by copolymerizing the first polymerizable compound and the second polymerizable compound.

This is because in order for the first organic compound layer to be excellent in solvent resistance, it is desired that the non-crosslinked polymer is incorporated in the crosslinked polymer. For this purpose, the non-crosslinked polymer has sufficient cavities. This is because it is preferable. In the general formula (3), when a is 1, a crosslinked polymer having sufficient cavities can be obtained even without the second polymerizable compound, but when a is 0, the first ratio is as described above. This is because, in the crosslinked polymer obtained by copolymerizing the polymerizable compound and the second polymerizable compound, sufficient cavities are easily formed.

(Electron acceptor)
The structure having the charge transport property of the non-crosslinked polymer and the crosslinked polymer improves the charge mobility by forming a charge transfer complex with the electron acceptor. Therefore, the organic light emitting device of the present invention includes the first organic light emitting element. The compound layer preferably contains an electron acceptor.

When the first organic compound layer contains an electron acceptor, the electron acceptor is preferably contained in an amount of 0.1 to 10% by mass with respect to 100% by mass in total of the non-crosslinked polymer and the crosslinked polymer.

The electron acceptor is not particularly limited, and a known compound can be used. Examples of the electron acceptor include N, N′-dicyano-2,3,5,6-tetrafluoro-1,4-quinonediimine (F4DCNQI), 7,7,8,8-tetracyanoquinodimethane (TCNQ). 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ), 11,11,12,12-tetracyanonaphth-2,6-quinodimethane, and the like.

When the material is selected without controlling the absolute value of the difference between the ionization potential of the non-crosslinked polymer and the ionization potential of the crosslinked polymer to 0.2 eV or less as in the prior art, the electron affinity of the electron acceptor and the non-crosslinked polymer The electron acceptor forms a charge transfer complex with one of the cross-linked polymer and the non-cross-linked polymer because there is a difference between the gap between the ionization potential of the polymer and the gap between the electron affinity of the electron acceptor and the ionization potential of the cross-linked polymer. Although easy, it was difficult to form a charge transfer complex with the other. As a result, the charge mobility was not improved so much. In the present invention, since the absolute value of the difference between the ionization potential of the non-crosslinked polymer and the ionization potential of the cross-linked polymer is controlled to 0.2 eV or less, the electron acceptor can be a non-crosslinked polymer, a cross-linked polymer, or a charge transfer complex. Therefore, the first organic compound layer exhibits good charge transfer characteristics. In general, since the ionization potential of the electron acceptor is larger than the ionization potential of the non-crosslinked polymer and the crosslinked polymer, even if the electron acceptor is contained in the first organic compound layer, the charge transfer property is hardly affected.

In the present invention, the absolute value of the difference between the ionization potential of the non-crosslinked polymer and the ionization potential of the cross-linked polymer is obtained by the methods described in the examples, respectively. The absolute value of the difference can be calculated.

(solvent)
The first organic compound layer is usually formed by coating, and a solution containing the first polymerizable compound capable of forming the non-crosslinked polymer and the crosslinked polymer is used for the coating. As the solvent of the solution, a solvent capable of dissolving the non-crosslinked polymer and the first polymerizable compound, the second polymerizable compound which may be contained, an electron acceptor, and the like is desired. Specific examples of the solvent include aromatic solvents such as toluene, xylene, and anisole, alkyl halide solvents such as chloroform and dichloroethane, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, dimethoxy Examples thereof include ether solvents such as ethane and THF, and these solvents can be used in combination. Of these, toluene, xylene, anisole and mixed solvents thereof are preferred. The above solution preferably contains a total of 0.1 to 5% by mass of solutes such as the non-crosslinked polymer and the first polymerizable compound, the second polymerizable compound, and the electron acceptor in these solvents. More preferably, it is contained in an amount of 1 to 3% by mass.

(Polymerization initiator)
When forming the first organic compound layer, the coating solution may contain a polymerization initiator. The polymerization initiator can be properly used for thermal polymerization and photopolymerization. When the above-mentioned polymerizable compound has a polymerizable double bond such as vinyl group, butenyl group, acryloyl group, acryloylamino group, methacryloyl group, methacryloylamino group, vinyloxy group, vinylamino group as a polymerizable group, radical polymerization starts. An agent can be used. Moreover, when it has an epoxy group, a cationic polymerization initiator and an anionic polymerization initiator can be used. When it has a group that undergoes cationic polymerization such as an oxetanyl group, a cationic polymerization initiator can be used.

Thermal radical polymerization initiators include azo compounds such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobisisovaleronitrile, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone Ketone peroxides such as peroxides, diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, dialkyls such as dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide Peroxides, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) Peroxyketals such as butane, t-butyl pero Cipivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy -3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, t-butylperoxy 2-ethylhexanoate, t- Examples thereof include alkyl peroxy esters such as hexyl peroxy 2-ethylhexanoate, and percarbonates such as diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate, and t-butyl peroxy isopropyl carbonate.

Examples of the photo radical polymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]. -2-Monfolinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1- Acetophenone derivatives such as ON, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-trimethylsilylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide and other benzophenone derivatives, benzoin, benzoin ethyl ether, benzoin propyl ether , Be Zone in isobutyl ether, benzoin derivatives such as benzoin isopropyl ether, methylphenyl glyoxylate, benzoin dimethyl ketal, etc. 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

Examples of the thermal cationic polymerization initiator include cationic or protonic acid catalysts such as triflic acid salts, boron trifluoride ether complex compounds, boron trifluoride, ammonium salts, phosphonium salts, sulfonium salts, and the like. Onium salts can be used.

As the photocationic polymerization initiator, the cation moiety is sulfonium, iodonium, diazonium, ammonium, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe cation, and the anion moiety is Onium salts composed of BF4-, PF6-, SbF6-, [BX4]-(wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups).

Anionic polymerization initiator, melamine, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptacilimidazole, 2-ethyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [ '-Methylimidazolyl- (1')]-ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino- 6- [2′-Ethyl-4′-imidazolyl- (1 ′)]-ethyl-S-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-S— Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 4,4′-methylenebis (2-ethyl-5-methylimidazole) ), Such as 1-dodecyl-2-methyl-3-benzyl-imidazolium chloride, imidazoles and the like.

Polymerization initiator may or may not be used. When a polymerization initiator is used, the amount used is not particularly limited, but is usually 0 mass with respect to a total of 100 parts by mass of the first polymerizable compound and the second polymerizable compound. More than 10 parts by mass, preferably 1 to 10 parts by mass.

[Second organic compound layer]
The second organic compound layer is formed adjacent to the first organic compound layer. The second organic compound layer is usually formed by coating on the first organic compound layer.

The first organic compound layer is excellent in solvent resistance because it contains a crosslinked polymer. For this reason, the second organic compound layer is formed by coating, for example, when the second organic compound layer is formed by coating using a solution containing a solvent capable of dissolving the non-crosslinked polymer and the first polymerizable compound. Even if it exists, a 1st organic compound layer does not melt | dissolve. For this reason, even when the second organic compound layer is formed by coating, the film thickness of the first organic compound layer is changed, or the material constituting the first organic compound layer is the second organic compound layer. The performance of the organic light emitting device is not deteriorated due to mixing in the compound layer. Therefore, as a solvent used for forming the second organic compound layer, any solvent that dissolves the material of the second organic compound layer well and has excellent coating properties without considering the dissolution of the first organic compound layer is arbitrary. You can choose to use. Specific examples of the solvent include those exemplified as those used for forming the first organic compound layer.

The second organic compound layer varies depending on the structure of the organic light emitting device of the present invention, and examples thereof include a hole transport layer and a light emitting layer. In addition, when the 2nd organic compound layer is not a light emitting layer, the organic light emitting element of this invention has a light emitting layer as another layer.

[Hole transport layer]
When the second organic compound layer is used as the hole transport layer, a known material can be used as the hole transport material. For example, TPD (N, N′-diphenyl-N, N′-di (3-methylphenyl) -1,1′-biphenyl-4,4′diamine), α-NPD (4,4′-bis [N Low molecular triphenylamine derivatives such as-(1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine); Polyvinyl carbazole; polymer compounds obtained by polymerizing a triphenylamine derivative by introducing a polymerizable substituent, and the like. In particular, since an organic compound layer is formed by coating film formation, it is desirable to include a polymer compound. The hole transport material may be used alone or in combination of two or more. Moreover, you may laminate | stack the positive hole transport layers formed from different hole transport materials. The thickness of the hole transport layer depends on the conductivity of the hole transport layer and cannot be generally limited, but is preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.

[Light emitting layer]
When the second organic compound layer is used as the light emitting layer, a known material can be used as a material for forming the light emitting layer.

As the organic compound for forming the light emitting layer of the organic light emitting device of the present invention, the light emitting small molecule described in Hiroshi Omori: Applied Physics, Vol. 70, No. 12, pp. 1419-1425 (2001) Examples thereof include compounds and luminescent polymer compounds. In terms of high luminous efficiency, the phosphorescent compound is preferably a phosphorescent compound. Examples of the phosphorescent compound include known transition metal complexes including ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, platinum, and gold. Among these, iridium complexes and platinum complexes are preferable.

The phosphorescent compound is preferably a metal complex represented by the following general formula (11).

(In the general formula (11), M represents iridium or platinum, the ring represented by A represents a nitrogen-containing heteroaromatic ring containing a nitrogen atom bonded to M, and the ring represented by B bonded to M. Represents an aromatic ring or a heteroaromatic ring containing a carbon atom, wherein ring A and ring B are bonded to each other, L represents a bidentate ligand, s represents an integer of 1 to 3, and t represents 0 to 2 And s + t is 2 or 3.)
The light emitting layer in the organic EL device produced by the method of the present invention is preferably a layer containing the phosphorescent compound. However, it is possible to suppress crystallization of the light emitting compound at the time of coating and forming the light emitting layer. For the purpose of supplementing the charge transporting property, a hole transporting compound, an electron transporting compound, or a polymer compound obtained by polymerizing these may be contained. Examples of the hole transporting compound used for these purposes include TPD (N, N′-diphenyl-N, N′-di (3-methylphenyl) -1,1′-biphenyl-4,4′diamine. ), Α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) ) Triphenylamine derivatives such as triphenylamine), polyvinyl carbazole, and polymers obtained by introducing a polymerizable functional group into the triphenylamine derivative, such as disclosed in JP-A-8-157575. And triphenylamine skeleton polymer compounds, polyparaphenylene vinylene, polydialkylfluorene, etc., and examples of the electron transporting compound include: Low molecular weight materials such as quinolinol derivative metal complexes such as Alq3 (tris (8-hydroxyquinolinate) aluminum (III)), oxadiazole derivatives, triazole derivatives, imidazole derivatives, triazine derivatives, triarylborane derivatives, Known electron transporting compounds such as those obtained by introducing a polymerizable functional group into a low molecular electron transporting compound to form a polymer, for example, poly PBD disclosed in JP-A-10-1665 can be used.

[cathode]
The material used for the cathode 15 is not particularly limited as long as it has electrical conductivity like the anode 12. However, a material having a low work function and being chemically stable is preferable. Specific examples include materials such as Al, MgAg alloy, Al and alkali metal alloys such as AlLi, and Al and alkaline earth metal alloys such as AlCa. However, the material of the cathode 15 is, for example, the anode 12 when it is desired to extract light from the cathode 15 side of the organic light emitting element 10 (when the surface on the cathode 15 side is a surface from which light is extracted, that is, a light emitting surface). In addition, it is preferable to use a material that is transparent to the emitted light.

The thickness of the cathode 15 is preferably 0.01 μm to 1 μm, more preferably 0.05 μm to 0.5 μm.

[Other layers and members]
The organic light emitting device of the present invention may have, for example, an electron transport layer, a hole blocking layer, an electron injection layer, etc. as other layers. The organic light emitting device of the present invention may have a protective cover or the like as another member.

(Electron transport layer)
An electron transport layer may be provided between the second organic compound layer 14 and the cathode 15. Examples of materials that can be used for the electron transport layer include quinoline derivatives, oxadiazole derivatives, perylene derivatives, pyridine derivatives, pyrimidine derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorene derivatives, and the like. More specifically, tris (8-quinolinolato) aluminum (abbreviation: Alq), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum, bis [2- (2-hydroxyphenyl) benzothiazolate] Examples thereof include zinc and 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole.

(Hole blocking layer)
In addition, in order to prevent holes from passing through the light emitting layer between the second organic compound layer 14 and the electron transport layer and to efficiently recombine holes and electrons in the light emitting layer, A block layer may be provided. In order to form the hole blocking layer, a known material such as a triazole derivative, an oxadiazole derivative, or a phenanthroline derivative is used.

(Electron injection layer)
An electron injection layer may be provided adjacent to the cathode 15 for the purpose of increasing the efficiency of electron injection from the cathode 15. For the electron injection layer, a metal material having a work function lower than that of the cathode 15 is preferably used. For example, alkali metals (Na, K, Rb, Cs), alkaline earth metals (Sr, Ba, Ca, Mg), rare earths Metals (Pr, Sm, Eu, Yb) can be used, but fluorides, chlorides and oxides of these metals are also preferably used. The thickness of the electron injection layer is preferably 0.05 to 50 nm, more preferably 0.1 to 20 nm, and still more preferably 0.5 to 10 nm.

(Protective cover)
It is preferable to use the organic light emitting element 10 for the organic light emitting element 10 stably for a long period of time and to attach a protective layer and a protective cover (not shown) for protecting the organic light emitting element 10 from the outside. As a material for the protective layer, a high molecular compound, a metal oxide, a metal fluoride, a metal boride, a silicon compound such as silicon nitride, silicon oxide, or the like can be used. Moreover, these laminated bodies can also be used.

As the protective cover, a glass plate, a plastic plate with a surface subjected to low water permeability treatment, a metal, or the like can be used. It is preferable that the protective cover is sealed with a thermosetting resin or a photo-curing resin and bonded to the element substrate. In this case, it is preferable to use a spacer because a predetermined space can be maintained and the organic light emitting element 10 can be prevented from being damaged. If an inert gas such as nitrogen, argon, or helium is sealed in this space, it becomes easy to prevent the upper cathode 16 from being oxidized.

Particularly, it is preferable to use helium because heat conductivity is high, and thus heat generated from the organic light emitting device 10 can be effectively transmitted to the protective cover when a voltage is applied. Further, by installing a desiccant such as barium oxide in this space, it becomes easy to suppress the moisture adsorbed in the manufacturing process of the organic light emitting element from damaging the organic light emitting element 10.

[Method for Manufacturing Organic Light-Emitting Element]
In the method for producing an organic light emitting device of the present invention, the organic light emitting device is usually produced using the coating solution of the present invention.

The coating solution of the present invention is a coating solution used for manufacturing an organic light emitting device, and includes the non-crosslinked polymer, the first polymerizable compound capable of forming a crosslinked polymer, and the solvent.

In the method for producing an organic light-emitting device of the present invention, a coating film is formed by applying a solution containing the first polymerizable compound capable of forming the non-crosslinked polymer and the crosslinked polymer and a solvent on the first electrode. Adjoining the first organic compound layer, a step of polymerizing the first polymerizable compound in the coating film to form a first organic compound layer containing a non-crosslinked polymer and a crosslinked polymer; A step of forming a second organic compound layer by coating, and a step of forming a second electrode on the second organic compound layer. As the non-crosslinked polymer, the first polymerizable compound, the solvent and the like used in the method for producing an organic light emitting device of the present invention, those described above can be used. That is, the first polymerizable compound is a compound including a structure having a charge transporting property, and the non-crosslinked polymer and the crosslinked polymer both include a repeating unit including a structure having a charge transporting property. In the method for producing an organic light emitting device of the present invention, the absolute value of the difference between the ionization potential of the non-crosslinked polymer and the ionization potential of the crosslinked polymer is 0.2 eV or less. In another method for manufacturing an organic light emitting device, at least one of the first organic compound layer and the second organic compound layer may be formed by a method other than coating.

In the method for producing an organic light-emitting device of the present invention, a first non-crosslinked polymer composed of a repeating unit including a charge transporting structure and a crosslinked polymer including a charge transporting structure can be formed on the first electrode. A solution containing the polymerizable compound is applied to form a coating film, and the type and amount of each component contained in the solution are as described above. The method for applying the solution on the first electrode is not particularly limited, but usually a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar. Film formation can be performed using a coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, or the like.

When the first organic compound layer is formed by coating, it usually includes a step of drying the coating film after coating the solution and before polymerizing the polymerizable compound. The temperature at which the coating film is dried can be appropriately determined within a range in which the components in the coating film are not easily deteriorated by heat, depending on the type of solvent used in the solution, and is usually 50 to 300 ° C.

Further, the method for polymerizing the first polymerizable compound in the coating film is not particularly limited, and examples thereof include an ultraviolet irradiation method and a heating method. The conditions for the polymerization can be appropriately determined within a range in which the components in the coating film hardly deteriorate depending on the type of the polymerizable group of the first polymerizable compound. For example, when a radically polymerizable group such as a vinyl group, an ethynyl group, a butenyl group, an acryloyl group, an acryloylamino group, a methacryloyl group, a methacryloylamino group, a vinyloxy group, or a vinylamino group is polymerized by heating, a nitrogen or the like is usually used. 5 minutes to 5 hours at 80 to 300 ° C. in an active atmosphere. When the polymerization of the first polymerizable compound is performed by heating, it can be performed simultaneously with the drying step.

In addition, there is no particular limitation on a coating method when forming the second organic compound layer on the first organic compound layer, and the film is formed by using the same method as that for forming the first organic compound layer. It can be performed.

Further, when the organic light emitting device of the present invention has other layers, members, etc., they can be laminated and arranged by a known method.

[Usage]
The organic light-emitting device of the present invention is suitably used in an image display device as a matrix-type or segment-type pixel. In addition, the organic light emitting element is also suitably used as an illumination device such as a surface light source without forming pixels.

Specifically, the organic light-emitting device of the present invention includes a display device in a computer, a television, a mobile terminal, a mobile phone, a car navigation system, a sign, a signboard, a video camera viewfinder, a backlight, an electrophotography, illumination, and resist exposure. It is preferably used for a light irradiation device in a reading device, interior lighting, an optical communication system or the like.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Evaluation methods]
(1) <Ionization potential>
A non-crosslinked polymer or a polymerizable compound was dissolved in toluene to prepare a 2.0 mass% coating solution. Using this coating solution, a film was formed on a transparent support substrate by a spin coating method (2000 rpm, 30 seconds), and heat-treated at 140 ° C. for 2 hours in a nitrogen atmosphere to produce a film having a thickness of 50 nm. The ionization potential was measured by atmospheric photoelectron spectroscopy using AC-2 manufactured by Riken Keiki Co., Ltd.

(2) <Film thickness maintenance ratio>
(Preparation of laminates A and B)
In addition to the organic EL elements produced in the following examples and comparative examples, for the purpose of solvent resistance evaluation (calculation of maintenance rate), examples described later on blue glass (25 mm square, plate thickness 1.1 mm) Two laminates having only the first organic compound layer (thickness 50 nm) containing the crosslinked polymer and the non-crosslinked polymer were prepared by the procedure described in the comparative example, and the laminate A and the laminate B were obtained. .

(Thickness of organic compound layer)
A part of the organic compound layer of the laminate A is cut with a needle to expose the substrate (hereinafter, the exposed substrate surface is also referred to as “substrate exposed portion”), and a stylus type surface shape measuring device (ULVAC Dektak) is used. 6) is used to observe the surface of the laminate A on the organic compound layer side so as to cross the exposed portion of the substrate as shown in FIG. ")") Was measured.

(Solvent resistance)
The organic compound layer of the laminate B was subjected to the following dissolution test treatment.

After 0.10 ml of toluene was dropped on the organic compound layer of the laminate B, it was rotated at 3000 rpm for 30 seconds. This rotation started within 5 seconds after the dropwise addition of toluene. The sample was then left for 1 hour at 140 ° C. under a nitrogen atmosphere.

Thereafter, the thickness of the organic compound layer of the laminate B (hereinafter also referred to as “organic compound layer after the dissolution test treatment”) is measured by the same method as that of the laminate A, and is defined by the following formula: The “retention rate (%)” of the thickness of the organic compound layer was calculated.

Maintenance rate = Thickness of organic compound layer after dissolution test treatment / Thickness of organic compound layer before dissolution test treatment × 100
(3) <Measurement method of driving voltage, luminous efficiency, and power efficiency>
A voltage was applied stepwise to the organic light emitting device using a constant voltage power source (Keithley, SM2400), and the light emission starting voltage and the luminance of the organic light emitting device were quantified with a luminance meter (Topcon, BM-9). As a result, the luminous efficiency (ratio of the number of photons to the amount of current (number of electrons) at the time of lighting of 100 cd / m ² ) and power efficiency (ratio of luminous flux to input power) are calculated from the ratio of luminance to current density and driving voltage. Were determined.

[Synthesis Example 1]

Under a nitrogen atmosphere, 2,5-dimethyl-1,4-phenylenediamine (5.0 g, 37 mmol), 3-iodotoluene (33.0 g, 150 mmol) and dehydrated xylene (200 ml) were added to a 500 ml three-necked flask. And stirred at 50 ° C. To this, potassium tert-butoxide (17 g, 150 mmol), palladium acetate (0.50 g, 2.2 mmol) and tri-tert-butylphosphine (1.4 g, 6.9 mmol) were added in this order, and the mixture was stirred at 120 ° C. for 4 hours. Stir. The obtained reaction mixture was cooled to room temperature, water (100 ml) was added, and then the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane). The obtained crude product was recrystallized from methanol to obtain compound (a) (12.2 g, 25 mmol).

Next, in a nitrogen atmosphere, compound (a) (12.2 g, 25 mmol) and dehydrated N, N-dimethylformamide (DMF) (100 ml) were placed in a 300 ml three-necked flask and stirred at 80 ° C. A mixed solution of phosphorus oxychloride (4.0 g, 26 mmol) and DMF (20 ml) was added dropwise to this solution, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained reaction solution was put into a 500 ml beaker containing sodium hydrogen carbonate (20 g) and water (200 ml), and extracted with ethyl acetate. The extract was washed successively with water and saturated brine, dried over anhydrous sodium sulfate. After the solid was filtered off, the solvent was distilled off and the resulting residue was purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (b) (6.5 g, 12 mmol).

Next, in a nitrogen atmosphere, methyltriphenylphosphonium bromide (5.0 g, 14 mmol) and dehydrated tetrahydrofuran (THF) (100 ml) were placed in a 200 ml three-necked flask, and potassium tert-butoxide (1 0.7 g, 15 mmol) was added slowly. After stirring for 30 minutes under ice-cooling, a solution of compound (b) (6.5 g, 12 mmol) in THF (30 ml) was added dropwise and stirred at room temperature for 3 hours. Water (200 ml) was added to the obtained reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated brine, dried over anhydrous sodium sulfate. After filtering off the solid, the residue obtained by distilling off the solvent was purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (c) (5.1 g, 9.8 mmol).

The identification data of compound (c) is as follows.

Calcd _{_{_{(C 38 H 38 N 2)}}} C, 87.31; H, 7.33; N, 5.36. : Measured value C, 87.59; H, 7.24; N, 5.19.
Mass spectrum (FAB +): 522 (M +).
Next, the compound (c) (500 mg) was put into a sealed container, dehydrated toluene (9.9 mL) was added, and then a dehydrated toluene solution of azobisisobutyronitrile (AIBN) (0.1 M, 198 μL) was added. It was. This solution was subjected to freeze degassing operation 5 times, then sealed in a vacuum, and stirred at 60 ° C. for 60 hours to be reacted. The reaction solution was dropped into 500 mL of acetone to obtain a precipitate. Further, reprecipitation purification with toluene-acetone was repeated twice, and then the precipitate was vacuum dried at 50 ° C. overnight to obtain a non-crosslinked polymer (A). The obtained non-crosslinked polymer (A) had a weight average molecular weight of 34,000 and a molecular weight distribution index (Mw / Mn) of 2.31.

[Synthesis Example 2]

Under a nitrogen atmosphere, 2,5-dimethyl-1,4-phenylenediamine (5.0 g, 37 mmol), 3-iodotoluene (17.0 g, 78 mmol) and dehydrated xylene (200 ml) were added to a 500 ml three-necked flask. And stirred at 50 ° C. To this, potassium tert-butoxide (8.7 g, 78 mmol), palladium acetate (0.30 g, 1.3 mmol), tri-tert-butylphosphine (1.0 g, 4.9 mmol) were added in this order, and the mixture was heated at 120 ° C. Stir for 4 hours. The obtained reaction mixture was cooled to room temperature, water (100 ml) was added, and then the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (d) (9.5 g, 30 mmol). .

Next, under a nitrogen atmosphere, compound (d) (9.5 g, 30 mmol), 4-bromo-2-methylphenol (12.0 g, 64 mmol) and dehydrated xylene (200 ml) were placed in a 500 ml three-necked flask. Stir at 50 ° C. To this, potassium tert-butoxide (16 g, 140 mmol), palladium acetate (0.50 g, 2.2 mmol) and tri-tert-butylphosphine (1.4 g, 6.9 mmol) were added in this order, and the mixture was stirred at 120 ° C. for 4 hours. Stir. The resulting reaction mixture was cooled to room temperature, 1M aqueous hydrochloric acid (200 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: ethyl acetate) to obtain compound (e) (10 g, 19 mmol).

Next, under a nitrogen atmosphere, compound (e) (10 g, 19 mmol), potassium tert-butoxide (4.7 g, 42 mmol) and dehydrated DMF (100 ml) were placed in a 300 ml three-necked flask and stirred at room temperature for 1 hour. did. To the resulting reaction mixture was added dropwise a solution of 11-bromo-1-undecene (4.4 g, 19 mmol) and 1,8-dibromooctane (2.6 g, 9.5 mmol) in DMF (20 ml) at room temperature for 5 hours. Stir. Next, 500 ml of water was added to the reaction solution, followed by extraction with ethyl acetate, followed by purification by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain polymerizable compound B (1.5 g). 1.0 mmol).

The identification data of the polymerizable compound B is as follows.

Calcd _{_{_{(C 102 H 126 N 4 O}}} 4) C, 83.22; H, 8.63; N, 3.81. : Measured value C, 82.96; H, 8.77; N, 4.04.
Mass spectrum (FAB +): 1472 (M +).
[Example 1]
What formed indium tin oxide (ITO) into a film thickness of 120 nm on the glass substrate by the sputtering method was used as a transparent conductive support substrate. This was ultrasonically washed successively with acetone and isopropyl alcohol (IPA), then boiled and washed with IPA, and then dried. Furthermore, what was UV / ozone cleaned was used as a transparent conductive support substrate.

A mixture of the non-crosslinked polymer A obtained in Synthesis Example 1 and the polymerizable compound B obtained in Synthesis Example 2 in a mass ratio of 50:50 was dissolved in toluene to prepare a 2.0 mass% coating solution. . Using this coating solution, a film was formed on the surface of the transparent support substrate on which ITO was formed by spin coating (2000 rpm, 30 seconds), and heat-treated at 140 ° C. for 2 hours in a nitrogen atmosphere to give a film thickness of 50 nm. A cured film was prepared, and a hole injection layer (first organic compound layer) was formed.

Next, a mixture of the compound X represented by the following formula and the compound P represented by the following formula in a mass ratio of 10:90 was dissolved in toluene, and the total amount of the compound X and the compound P was 2.0% by mass. The coating solution was adjusted. Compound X was synthesized by the method described in JP-A-2005-200368, and compound P was synthesized by the method described in JP-A-2007-081392. Using this coating solution, a film was formed on the previously prepared film by spin coating (2000 rpm, 30 seconds), and heat-treated at 140 ° C. for 1 hour in a nitrogen atmosphere to form a 50 nm film, and the light emitting layer (Second organic compound layer) was formed.

Further, using a vapor deposition material composed of aluminum and lithium (lithium concentration 1 atom%), a metal layer film having a thickness of 150 nm is formed on the organic compound layer by a vacuum vapor deposition method, and the structure shown in FIG. An element was produced. The degree of vacuum during vapor deposition was 1.0 × 10 ⁻⁴ Pa and the film formation rate was 1.0 to 1.2 nm / sec. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Synthesis Example 3]
A polymerizable compound C represented by the following formula was synthesized in the same manner as in Synthesis Example 2 except that 5-bromo-1-pentene was used instead of 11-bromo-1-undecene.

The identification data of the polymerizable compound C is as follows.

Calcd _{_{_{(C 90 H 102 N 4 O}}} 4) C, 82.91; H, 7.89; N, 4.30. : Measured value C, 82.60; H, 7.98; N, 4.51.
Mass spectrometry (FAB +): 1303 (M +).

[Example 2]
A device of Example 2 was produced in the same manner as the device of Example 1 except that the polymerizable compound B of Example 1 was changed to the polymerizable compound C synthesized in Synthesis Example 3. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Synthesis Example 4]
The same procedure as in Synthesis Example 2 was performed, except that compound (g) was used instead of compound (e) and 15-bromo-1-pentadecene was used instead of 11-bromo-1-undecene. The represented polymerizable compound D was synthesized.

The identification data of the polymerizable compound D is as follows.

Calcd _{_{_{(C 106 H 134 N 4 O}}} 4) C, 83.31; H, 8.84; N, 3.67. : Measured value C, 82.97; H, 9.19; N, 3.66.
Mass spectrum (FAB +): 1528 (M +).

Compound (g) was synthesized by the following method.

Under a nitrogen atmosphere, 1,4-phenylenediamine (4.0 g, 37 mmol), 3-iodotoluene (17.0 g, 78 mmol) and dehydrated xylene (200 ml) were placed in a 500 ml three-necked flask and stirred at 50 ° C. did. To this, potassium tert-butoxide (8.7 g, 78 mmol), palladium acetate (0.30 g, 1.3 mmol), tri-tert-butylphosphine (1.0 g, 4.9 mmol) were added in this order, and the mixture was heated at 120 ° C. Stir for 4 hours. The obtained reaction mixture was cooled to room temperature, water (100 ml) was added, and then the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (f) (8.7 g, 30 mmol). .

Next, under a nitrogen atmosphere, a compound (f) (8.7 g, 30 mmol), 4-bromo-2-methylphenol (12.0 g, 64 mmol) and dehydrated xylene (200 ml) were placed in a 500 ml three-necked flask. Stir at 50 ° C. To this, potassium tert-butoxide (16 g, 140 mmol), palladium acetate (0.50 g, 2.2 mmol) and tri-tert-butylphosphine (1.4 g, 6.9 mmol) were added in this order, and the mixture was stirred at 120 ° C. for 4 hours. Stir. The resulting reaction mixture was cooled to room temperature, 1M aqueous hydrochloric acid (200 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: ethyl acetate) to obtain compound (g) (9.5 g, 19 mmol).

[Example 3]
A device of Example 3 was fabricated in exactly the same manner as the device of Example 1, except that the first polymerizable compound B of Example 1 was changed to the polymerizable compound D synthesized in Synthesis Example 4. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Synthesis Example 5]
A non-crosslinked polymer E represented by the following formula was synthesized in the same manner as in Synthesis Example 1 except that 25 mmol of the compound (h) represented by the following formula was used instead of the compound (c). The obtained non-crosslinked polymer had a weight average molecular weight of 24,800 and a molecular weight distribution index (Mw / Mn) of 2.13. Compound (h) was synthesized by the method described in Japanese Patent Application Laid-Open No. 2005-200638.

[Synthesis Example 6]

Under a nitrogen atmosphere, compound (i) (synthesized according to the method described in JP-A-2005-97589) (1.5 g, 3.8 mmol), compound (j) (1.3 g, 3.9 mmol) and dehydrated xylene (50 ml) were added and stirred at 50 ° C. To this, potassium tert-butoxide (0.45 g, 4.0 mmol), palladium acetate (0.10 g, 0.45 mmol), tri-tert-butylphosphine (0.25 g, 1.2 mmol) were added in order. Stir at 4 ° C. for 4 hours. The obtained reaction mixture was cooled to room temperature, water (50 ml) was added, and then the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (k) (2.0 g, 3. 1 mmol).

Next, under a nitrogen atmosphere, compound (k) (2.0 g, 3.1 mmol), compound (l) (0.87 g, 1.5 mmol) and dehydrated xylene (50 ml) were placed in a 200 ml three-necked flask. Stir at 50 ° C. To this, potassium tert-butoxide (0.45 g, 4.0 mmol), palladium acetate (0.10 g, 0.45 mmol), tri-tert-butylphosphine (0.25 g, 1.2 mmol) were added in order. Stir at 4 ° C. for 4 hours. The obtained reaction mixture was cooled to room temperature, water (50 ml) was added, and then the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain polymerizable compound F (2.2 g, 1. 3 mmol).

The identification data of the polymerizable compound F is as follows.

Calcd _{_{_{(C 125 H 140 N 4)}}} C, 88.39; H, 8.31; N, 3.30. : Measured value C, 88.65; H, 8.22; N, 3.04.
Mass spectrum (FAB +): 1698 (M +).
[Example 4]
The non-crosslinked polymer A of Example 1 was changed to the non-crosslinked polymer E synthesized in Synthesis Example 5, and the first polymerizable compound B was changed to the polymerizable compound F synthesized in Synthetic Example 6 to obtain the device of Example 1. The device of Example 4 was fabricated in exactly the same manner. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Example 5]
A device of Example 5 was produced in the same manner as the device of Example 4 except that the first polymerizable compound F of Example 4 was changed to the polymerizable compound D. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Example 6]
A device of Example 6 was produced in the same manner as the device of Example 1 except that the ratio of the non-crosslinked polymer A and the polymerizable compound B of Example 1 was changed to 5:95. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Example 7]
A device of Example 7 was produced in the same manner as the device of Example 1, except that F4TCNQ was added so that non-crosslinked polymer A, polymerizable compound B, and F4TCNQ were 50: 50: 1. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Synthesis Example 7]

Under a nitrogen atmosphere, a compound (e) (5.0 g, 9.5 mmol), potassium tert-butoxide (2.2 g, 20 mmol), and dehydrated DMF (50 ml) were placed in a 200 ml three-necked flask at room temperature. Stir for hours. To the resulting reaction mixture, a solution of 11-bromo-1-undecene (4.7 g, 20 mmol) in DMF (15 ml) was added dropwise and stirred at room temperature for 5 hours. Next, 200 ml of water was added to the reaction solution, followed by extraction with ethyl acetate, followed by purification by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain polymerizable compound I (6.6 g). 7.9 mmol).

The identification data of the polymerizable compound I are as follows.

Calcd _{_{_{(C 58 H 76 N 2 O}}} 2) C, 83.60; H, 9.19; N, 3.36. : Measured value C, 83.23; H, 9.30; N, 3.55.
Mass spectrum (FAB +): 833 (M +).
[Example 8]
The coating liquid for forming the hole injection layer used in Example 1 was prepared by adding 50 parts of the non-crosslinked polymer A synthesized in Synthesis Example 1, the polymerizable compound I synthesized in Synthesis Example 7, and styrene as the second polymerizable compound. A device of Example 8 was produced in the same manner as the device of Example 1 except that the toluene solution was contained in a mass ratio of 50:20 and containing 2.0% by mass of solid. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Synthesis Example 8]

Under a nitrogen atmosphere, a 500 ml three-necked flask was charged with tri (4-bromophenyl) amine (6.0 g, 12 mmol), N- (3-methylphenyl) aniline (2.2 g, 12 mmol), N- (3- Hydroxyphenyl) -m-toluidine (2.4 g, 12 mmol), N- (4-benzyloxyphenyl) -m-toluidine (3.5 g, 12 mmol) and dehydrated xylene (200 ml) were added and stirred at 50 ° C. To this, potassium tert-butoxide (5.6 g, 50 mmol), palladium acetate (0.50 g, 2.2 mmol), tri-tert-butylphosphine (1.4 g, 6.9 mmol) were added in order, and the mixture was heated at 120 ° C. Stir for 4 hours. The obtained reaction mixture was cooled to room temperature, water (200 ml) was added, and then the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (m) (1.3 g, 1. 4 mmol).

Next, under a nitrogen atmosphere, a compound (m) (1.3 g, 1.4 mmol), potassium tert-butoxide (0.20 g, 1.8 mmol) and dehydrated DMF (10 ml) were placed in a 200 ml three-necked flask. And stirred at room temperature for 1 hour. A solution of 1,8-dibromooctane (0.19 g, 0.70 mmol) in DMF (5 ml) was added dropwise to the resulting reaction mixture, and the mixture was stirred at room temperature for 5 hours. Next, 100 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (n) (1.4 g). 0.72 mmol).

Next, under a nitrogen atmosphere, compound (n) (1.4 g, 0.72 mmol) and tetrakis (triphenylphosphine) palladium (0.050 g, 0.043 mmol) were placed in a 100 ml three-necked flask, and 50 ml of THF was added. And dissolved. To this was added hydrazine monohydrate (3.0 g, 54 mmol) and heated to reflux for 12 hours. The obtained reaction mixture was put into 200 ml of water, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (o) (1. 2 g, 0.68 mmol).

Next, under a nitrogen atmosphere, a compound (o) (1.2 g, 0.68 mmol), potassium tert-butoxide (0.21 g, 1.9 mmol) and dehydrated DMF (25 ml) were placed in a 100 ml three-necked flask. And stirred at room temperature for 1 hour. A solution of 11-bromo-1-undecene (0.51 g, 2.2 mmol) in DMF (5 ml) was added dropwise to the resulting reaction mixture, and the mixture was stirred at room temperature for 5 hours. Next, 200 ml of water was added to the reaction solution, followed by extraction with ethyl acetate, followed by purification by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain polymerizable compound J (1.3 g). 0.63 mmol).

The identification data of the polymerizable compound J is as follows.

Elemental analysis: calculated value (C ₁₄₄ H ₁₅₀ N ₈ O ₄ ) C, 84.09; H, 7.35; N, 5.45. : Measured value C, 83.77; H, 7.58; N, 5.61.
Mass spectrum (FAB +): 2056 (M +).
[Comparative Example 1]
A device of Comparative Example 1 was produced in the same manner as the device of Example 1, except that the first polymerizable compound B of Example 1 was changed to the polymerizable compound J synthesized in Synthesis Example 7. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode in the device thus obtained.

[Synthesis Example 8]

In a nitrogen atmosphere, 2,4-diaminomesitylene (3.0 g, 20 mmol), 3-iodotoluene (8.7 g, 40 mmol) and dehydrated xylene (150 ml) were placed in a 300 ml three-necked flask and stirred at 50 ° C. did. To this, potassium-tert-butoxide (4.5 g, 40 mmol), palladium acetate (0.30 g, 1.3 mmol) and tri-tert-butylphosphine (1.0 g, 4.9 mmol) were added in this order, and the mixture was heated at 120 ° C. Stir for 4 hours. 4-Bromo-2-methylphenol (7.5 g, 40 mmol) and potassium-tert-butoxide (9.0 g, 80 mmol) were added to the obtained reaction mixture (p), and the mixture was further stirred at 120 ° C. for 4 hours. The reaction mixture was cooled to room temperature, water (150 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (q) (3.9 g, 7. 2 mmol).

Next, under a nitrogen atmosphere, compound (q) (3.9 g, 7.2 mmol), potassium tert-butoxide (1.7 g, 15 mmol) and dehydrated DMF (30 ml) were placed in a 200 ml three-necked flask at room temperature. For 1 hour. To the resulting reaction mixture was added dropwise a solution of 11-bromo-1-undecene (1.7 g, 7.3 mmol) and 1,8-dibromooctane (1.0 g, 3.7 mmol) in DMF (10 ml) at room temperature. Stir for 5 hours. Next, 200 ml of water was added to the reaction solution, followed by extraction with ethyl acetate, followed by purification by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain polymerizable compound K (0.50 g). 0.33 mmol).

The identification data of the polymerizable compound K is as follows.

Calcd _{_{_{(C 104 H 130 N 4 O}}} 4) C, 83.26; H, 8.73; N, 3.73. : Measured value C, 83.60; H, 8.68; N, 3.65.
Mass spectrometry (FAB +): 1500 (M +).
[Comparative Example 2]
A device of Comparative Example 2 was produced in the same manner as the device of Example 1 except that the polymerizable compound B of Example 1 was changed to the polymerizable compound K synthesized in Synthesis Example 8. Table 2 shows the results obtained by emitting light by applying a DC voltage in vacuum with the ITO electrode as the positive electrode and the aluminum-lithium electrode as the negative electrode.

Claims

A first electrode;
A first organic compound layer formed on the first electrode;
A second organic compound layer formed adjacent to the first organic compound layer;
An organic light emitting device having a second electrode formed on the second organic compound layer,
The first organic compound layer contains a non-crosslinked polymer and a crosslinked polymer;
The non-crosslinked polymer and the crosslinked polymer each include a repeating unit including a structure having charge transportability,
An organic light emitting device in which an absolute value of a difference between an ionization potential of the non-crosslinked polymer and an ionization potential of the crosslinked polymer is 0 to 0.2 eV.
The crosslinked polymer is a polymer formed by polymerizing at least a first polymerizable compound;
The organic light-emitting device according to claim 1, wherein the first polymerizable compound is a compound including a structure having a charge transporting property.
3. The organic according to claim 1, wherein in the non-crosslinked polymer and the crosslinked polymer, the two structures having charge transporting properties contained in adjacent repeating units are linked by a linking group containing a nonconjugated structure. Light emitting element.
The structure having the charge transport property possessed by the repeating unit of the non-crosslinked polymer and the structure having the charge transport property possessed by the repeating unit of the crosslinked polymer are the same structure. Organic light emitting device.
The organic light-emitting device according to any one of claims 1 to 4, wherein the structure having a charge transporting property is a triphenylamine derivative.
The non-crosslinked polymer is a polymer comprising at least one repeating unit selected from the following general formula (1) and the following general formula (2):
The organic light-emitting device according to any one of claims 2 to 5, wherein the first polymerizable compound is a compound represented by the following general formula (3).

(In the general formulas (1) to (3), each A independently represents a structure having charge transporting properties, and X 1 and X 5 each independently represents —O—, —S—, or a substituent. An alkylene group having 1 to 20 carbon atoms that may have (provided that one or two or more non-adjacent methylene groups in the alkylene group may be substituted with —O— or —S— and bonded to A; One non-adjacent or two or more non-adjacent methylene groups are —SO—, —SO 2 —, —CO—, —COO—, —N (R Y ) —, —CO—N (R Y ) —, an arylene group Which may be substituted with
X 2 to X 4 are each independently a single bond, —O—, —S—, or an optionally substituted alkylene group having 1 to 20 carbon atoms (provided that one or not in the alkylene group is not adjacent) Two or more methylene groups may be substituted with —O— or —S—, and one or more methylene groups not bonded to A may be —SO—, —SO 2 —, —CO—. , —COO—, —N (R Y ) —, —CO—N (R Y ) —, which may be substituted with an arylene group), and R Y represents a hydrogen atom, an alkyl having 1 to 4 carbon atoms. Represents a group, an aryl group, or an aralkyl group, and a is 0 or 1; )
A in the general formula (3) is 0;
The first polymerizable compound and the second polymerizable compound in a range in which the crosslinked polymer is 10 to 100% by mass of the second polymerizable compound with respect to 100% by mass of the first polymerizable compound. The organic light-emitting device according to claim 6, which is obtained by copolymerization of
The organic light-emitting device according to claim 6, wherein A in the general formulas (1) to (3) is represented by the following general formula (4).

(In General Formula (4), one of R 2 and R 3 is a group represented by the following General Formula (5),
Any two of R 1 to R 15 in the general formula (4) and R 16 to R 29 in the following general formula (5) are X 1 to X 5 or hydrogen in the general formulas (1) to (3). A bond to an atom,
The group represented by the general formula (5) and R 1 to R 15 that are not a bond are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or carbon. An alkoxy group of 1 to 10; )

(In the general formula (5), R 16 to R 29 which are not a bond are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. In the case where b is 0 or 1 and b is 1, the linked aromatic rings R may be bonded to each other to form a condensed ring.
The organic light emitting device according to any one of claims 1 to 8, wherein a mass ratio of the crosslinked polymer to the non-crosslinked polymer contained in the first organic compound layer is 50:50 to 95: 5.
The organic light emitting device according to any one of claims 6 to 8, wherein the formula weight of the structure having a charge transporting property represented by A is 240 to 1000.
X 3 and X 4 in the general formula (3) may have a substituent having 10 or more atoms constituting the shortest chain connecting A and the vinyl group in the general formula (3) A group (provided that one or two or more methylene groups in the alkylene group may be substituted with —O— or —S—, and one or two or more methylene groups not bonded to A) May be substituted with —SO—, —SO 2 —, —CO—, —COO—, —N (R Y ) —, —CO—N (R Y ) —, an arylene group, and R Y is The organic light-emitting device according to any one of claims 6 to 8, wherein the organic light-emitting device is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group.
The organic material according to any one of claims 1 to 11, wherein the first organic compound layer contains an electron acceptor in an amount of 0.1 to 10% by mass with respect to a total of 100% by mass of the non-crosslinked polymer and the crosslinked polymer. Light emitting element.
A coating solution used for manufacturing an organic light emitting device,
A non-crosslinked polymer, a first polymerizable compound capable of forming a crosslinked polymer, and a solvent,
The non-crosslinked polymer includes a repeating unit including a structure having a charge transporting property, and the first polymerizable compound is a compound including a structure having a charge transporting property;
A coating solution in which an absolute value of a difference between an ionization potential of the non-crosslinked polymer and an ionization potential of a crosslinked polymer formed by polymerizing the first polymerizable compound is 0.2 eV or less.
Applying a solution containing a non-crosslinked polymer, a first polymerizable compound capable of forming a crosslinked polymer, and a solvent on the first electrode to form a coating;
Polymerizing the first polymerizable compound in the coating film to form a first organic compound layer containing a non-crosslinked polymer and a crosslinked polymer; and a second adjacent to the first organic compound layer. A step of forming the organic compound layer by coating, and a step of forming a second electrode on the second organic compound layer,
The first polymerizable compound is a compound including a structure having charge transporting properties, and the non-crosslinked polymer and the crosslinked polymer each include a repeating unit including a structure having charge transporting properties;
A method for manufacturing an organic light emitting device, wherein an absolute value of a difference between an ionization potential of the non-crosslinked polymer and an ionization potential of the crosslinked polymer is 0.2 eV or less.
An illumination device comprising the organic light-emitting element according to any one of claims 1 to 12.
A display device comprising the organic light-emitting device according to any one of claims 1 to 12.