JP5307954B1 - Organic light emitting device, method for producing the same and use thereof - Google Patents

Abstract

  The present invention is an organic light emitting device having a plurality of adjacent organic compound layers, which is superior to the conventional organic light emitting device in the insolubilizing property of the underlayer, and the underlayer is excellent in the charge transportability, and has excellent light emission characteristics. It aims at providing an organic light emitting element shown. The organic light emitting device of the present invention comprises a first electrode, a first organic compound layer formed on the first electrode, and a second organic compound 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, wherein the first organic compound layer contains a non-crosslinked polymer and a crosslinked polymer. The non-crosslinked polymer and the cross-linked polymer both include a repeating unit including a structure having charge transportability, and the absolute value of the difference between the ionization potential of the non-cross-linked polymer and the ionization potential of the cross-linked polymer is 0 It is 0.2 eV.

Description

  The present invention relates to an organic light emitting device, a method of manufacturing the same, and uses thereof, and more particularly, to an organic light emitting device having an organic compound layer containing a noncrosslinked polymer having charge transportability and a crosslinked polymer, a method of manufacturing the same and a use thereof.

  In recent years, application studies of organic light emitting elements (hereinafter also referred to as “organic EL elements”) have been actively conducted. The organic EL element is composed of a pair of electrodes consisting of an anode and a cathode and one or more organic compound layers formed between them, and a voltage is applied between the anode and the cathode to make holes from the anode and the cathode respectively. And inject electrons, and the injected electrons and holes emit light using energy generated by recombination in the organic compound layer. That is, the organic EL element utilizes a phenomenon in which the light emitting material of the organic compound layer is excited by the energy due to the charge recombination, and light is generated when returning from the excited state to the ground state again.

  Although several methods, such as a vapor deposition method and a coating method, are known as a manufacturing method of an organic compound layer, the method using the coating method is actively examined from the simplicity of the process. In the case of forming an organic compound layer using a coating method, a coating film is formed by applying a coating solution in which an organic material is dissolved, and the organic compound layer is formed by further drying this film.

  However, in the case of forming the laminated structure of the organic compound layer by the coating method, particularly when the coating liquid is applied for the purpose of forming another organic compound layer, using the organic compound layer already formed as a base layer, The underlayer may be dissolved by the solvent in the coating solution. When the underlayer is dissolved, the thickness of the underlayer may change, or the material forming the underlayer may be mixed into the newly formed organic compound layer, and the intended organic light emitting device There was a case that could not be obtained.

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

  In Patent Document 1, after forming a film by applying a coating solution containing a polymer having a carrier transporting property or light emitting property and a low molecular weight crosslinking agent, an insolubilized film is formed by crosslinking the low molecular weight crosslinking agent in the organic compound layer. doing. However, since these crosslinkers have poor charge transportability, the charge transportability of the organic compound layer is lowered by the addition, and the crosslinkers themselves sometimes function as carrier traps. For this reason, there is a problem that the performance of the organic light emitting device is lowered when the additive is increased to enhance the curability. In addition, when the addition amount is reduced to suppress the adverse effect due to the addition of the crosslinking agent, there is a problem that the insolubilization of the organic compound layer becomes insufficient and it becomes difficult to manufacture the intended organic light emitting device.

In Patent Document 2, by using a crosslinking agent exhibiting charge transportability as a crosslinking agent added to an organic material forming an organic compound layer, it is possible to suppress the property deterioration of the organic compound layer and at the same time, to the solvent of the organic compound layer. It is disclosed that solubility 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 consisting only of this crosslinking agent is described It is done.

  However, depending on the combination of compounds, the charge mobility of the organic compound layer obtained by mixing a crosslinker exhibiting such charge transportability with a charge transportable organic material and crosslinking the crosslinker after coating film formation is dependent on the combination of compounds. In some cases, the charge mobility of the organic compound layer consisting of only the organic material and the crosslinking agent may be lower than that of the organic compound layer, and such property deterioration is remarkable when the mixing ratio of the crosslinking agent is increased. Was insolubilized enough.

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

  The present invention has been made in view of the problems of the above-described conventional techniques, and in an organic light emitting device having a plurality of adjacent organic compound layers, the base layer has 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 which is excellent in transportability and exhibits good light emission characteristics.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, when forming an organic compound layer containing a non-crosslinked polymer having charge transportability and a cross-linked polymer on an electrode, the non-crosslinking The organic compound layer is excellent in charge transportability 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, and the organic compound layer contains many crosslinked polymers. And capable of improving solvent resistance (herein, solvent resistance means poor solubility in organic solvents), and an organic light emitting device having the organic compound layer Found that they exhibit good light emission characteristics, and completed the present invention.

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

(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;
And 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 both include a repeating unit including a structure having charge transportability,
The organic light emitting element whose absolute value of the difference of the ionization potential of the said non-crosslinked polymer and the ionization potential of the said crosslinked polymer is 0-0.2 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 charge transportability.

(3)
The non-crosslinked polymer and the cross-linked polymer according to (1) or (2), wherein the two structures having charge transportability contained in adjacent repeating units are linked by a linking group including a non-conjugated structure. Organic light emitting devices.

(4)
Any one of (1) to (3), wherein the structure having charge transportability possessed by the repeating unit of the non-crosslinked polymer and the structure possessing charge transportability possessed by the repeating unit of the crosslinked polymer are the same structure The organic light emitting element as described in.

(5)
The organic light emitting device according to any one of (1) to (4), wherein the charge transportable structure 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).

（一般式（１）〜（３）において、各Ａはそれぞれ独立に、電荷輸送性を有する構造を表し、Ｘ¹およびＸ⁵はそれぞれ独立に、−Ｏ−、−Ｓ−、または置換基を有してもよい炭素数１〜２０のアルキレン基（但し、該アルキレン基における１つまたは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−に置換されてよく、Ａに結合していない１つまたは隣接しない２つ以上のメチレン基は−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−Ｎ（Ｒ^Y）−、−ＣＯ−Ｎ（Ｒ^Y）−、アリーレン基に置換されていてもよい）を表し、
Ｘ²〜Ｘ⁴はそれぞれ独立に、単結合、−Ｏ−、−Ｓ−、または置換基を有してもよい炭素数１〜２０のアルキレン基（但し、該アルキレン基における１つまたは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−に置換されてよく、Ａに結合していない１つまたは隣接しない２つ以上のメチレン基は−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−Ｎ（Ｒ^Y）−、−ＣＯ−Ｎ（Ｒ^Y）−、アリーレン基に置換されていてもよい）を表し、Ｒ^Yは、水素原子、炭素数１〜４のアルキル基、アリール基、またはアラルキル基を表わし、ａは０または１である。）
（７）
前記一般式（３）におけるａが０であり、
前記架橋ポリマーが、前記第１の重合性化合物１００質量％に対して、第２の重合性化合物が１０〜１００質量％となる範囲で前記第１の重合性化合物と、第２の重合性化合物とを共重合して得られたものである（６）に記載の有機発光素子。

(In the general formulas (1) to (3), each A independently represents a structure having charge transportability, and X ¹ and X ⁵ each independently represent -O-, -S-, or a substituent An alkylene group having 1 to 20 carbon atoms which may be substituted, provided that one or two or more non-adjacent methylene groups in the alkylene group may be substituted by -O- or -S- and be bonded to A not one or more methylene groups not adjacent to each _{-SO -, - SO 2 -,} - CO -, - COO -, - N (R Y) -, - CO-N (R Y) -, an arylene group And may be replaced by
Each of X ^{2 to} X ⁴ independently 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 two of the alkylene groups are not adjacent. Two or more methylene groups may be substituted by -O-, -S- and one or two non-adjacent methylene groups not bonded to A may be -SO-, -SO _2- , -CO- And -COO-, -N ( ^RY )-, -CO-N ( ^RY )-, which may be substituted with an arylene group; and R ^Y is a hydrogen atom, an alkyl having 1 to 4 carbon atoms Represents a group, an aryl group or an aralkyl group, a is 0 or 1; )
(7)
A in the general formula (3) is 0,
The first polymerizing compound and the second polymerizing compound in the range where the second polymerizing compound is 10 to 100 mass% with respect to 100 mass% of the first polymerizing compound as the crosslinked polymer The organic light-emitting device according to (6), which is obtained by copolymerizing

(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).

（一般式（４）において、Ｒ²およびＲ³のいずれか一方は下記一般式（５）で表される基であり、
前記一般式（４）におけるＲ¹〜Ｒ¹⁵および下記一般式（５）におけるＲ¹⁶〜Ｒ²⁹のいずれか二つは、前記一般式（１）〜（３）におけるＸ¹〜Ｘ⁵または水素原子への結合手であり、
前記一般式（５）で表される基および前記結合手ではないＲ¹〜Ｒ¹⁵は、それぞれ独立に水素原子、ハロゲン原子、シアノ基、アミノ基、炭素数１〜１０のアルキル基、または炭素数１〜１０のアルコキシ基である。）

(In the 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) Bond to an atom,
The group represented by the general formula (5) and R ^{1 to} R ¹⁵ which are not the bond each independently represent a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or carbon It is a number 1-10 alkoxy group. )

（一般式（５）において、前記結合手ではないＲ¹⁶〜Ｒ²⁹は、それぞれ独立に水素原子、ハロゲン原子、シアノ基、アミノ基、炭素数１〜１０のアルキル基、または炭素数１〜１０のアルコキシ基であり、ｂは０または１であり、ｂが1の場合において、連結した芳香環のＲ同士が互いに結合して縮合環を形成してもよい。）
（９）
前記第１の有機化合物層に含まれる前記架橋ポリマーと前記非架橋ポリマーとの質量比が５０：５０〜９５：５である（１）〜（８）のいずれか一項に記載の有機発光素子。

(In the general formula (5), each of R ^{16 to} R ²⁹ which is not the bond is independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms In the case where b is 0 or 1 and b is 1, Rs of linked aromatic rings may be bonded to each other to form a fused ring).
(9)
The organic light-emitting device according to any one of (1) to (8), wherein the mass ratio of the crosslinked polymer to 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 charge transportability represented by A is 240 to 1000.

(11)
Alkylene which X ³ and X ⁴ in the above-mentioned general formula (3) may have a substituent whose atom which constitutes the shortest chain which connects A and a vinyl group in general formula (3) is 10 or more Group, provided that one or more non-adjacent methylene groups in the alkylene group may be substituted by -O- or -S- and one or more non-adjacent methylene groups not bound to A Is optionally substituted by -SO-, -SO _2- , -CO-, -COO-, -N (R ^Y )-, -CO-N (R ^Y )-or an arylene group, and R ^Y is The organic light-emitting device according to any one of (6) to (8) and (10), which is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group.

(12)
The first organic compound layer according to any one of (1) to (11), wherein the electron acceptor comprises 0.1 to 10% by mass with respect to a total of 100% by mass of the non-crosslinked polymer and the crosslinked polymer Organic light emitting devices.

(13)
A coating solution used for producing an organic light emitting device, comprising:
A non-crosslinked polymer, a first polymerizable compound capable of forming a crosslinked polymer, and a solvent,
The non-crosslinked polymer is a compound containing a repeating unit containing a structure having charge transportability, and the first polymerizable compound containing a structure having charge transportability,
The coating solution whose absolute value of the difference of the ionization potential of the said non-crosslinked polymer and the ionization potential of the crosslinked polymer formed by superposing | polymerizing a said 1st polymeric compound is 0.2 eV or less.

(14)
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 film;
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, and a second step adjacent to the first organic compound layer Forming a second electrode on the second organic compound layer, and forming the second organic compound layer on the second organic compound layer,
The first polymerizable compound is a compound including a structure having charge transportability, and the non-crosslinked polymer and the crosslinked polymer both include a repeating unit including a structure having charge transportability,
The manufacturing method of the organic light emitting element whose absolute value of the difference of the ionization potential of the said non-crosslinked polymer and the ionization potential of the said crosslinked polymer is 0.2 eV or less.

(15)
The illuminating device provided with the organic light emitting element as described in any one of (1)-(12).

(16)
The display apparatus provided with the organic light emitting element as described in any one of (1)-(12).

  The organic light emitting device of the present invention comprises 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. In the present invention, for the purpose of forming a second organic compound layer, dissolution is suppressed even when a coating solution is applied, and the first organic compound layer is excellent in charge transportability, so the present invention The organic light emitting device of the present invention exhibits good light emission characteristics.

FIG. 1 is a cross-sectional view for explaining an example of the structure of the organic light emitting device of the present invention. FIG. 2 is a conceptual view showing the path of a probe (probe) when measuring the thickness of the 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 comprises a first electrode, a first organic compound layer formed on the first electrode, and a second organic compound formed adjacent to the first organic compound layer. It is an organic light emitting element which has a compound layer and the 2nd electrode formed on the said 2nd organic compound layer. In the organic light emitting device of the present invention, the first organic compound layer contains a non-crosslinked polymer and a crosslinked polymer, and the non-crosslinked polymer and the crosslinked polymer both have a structure having charge transportability. It contains a repeating unit, and 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 comprises at least one light emitting layer. The second organic compound layer may be a light emitting layer, or the 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).

  An embodiment for carrying out 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 according to the present invention, and is provided on the anode 12 provided on the substrate 11, the first organic compound layer 13 and the first organic compound layer 13. The second organic compound layer 14 and the cathode 15 which are stacked adjacent to each other are sequentially provided.

  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, and the second organic compound layer (light emitting layer) Recombine) and emit light.

[substrate]
As a material of the substrate 11, when it is desired to extract light from the substrate 11 side of the organic light emitting element 10 (when the surface on the substrate 11 side is the light extraction surface, ie, the light emitting surface), the wavelength of the light to be emitted is Is preferably transparent. Specifically, when the light to be emitted is visible light, glass such as soda glass or non-alkali glass; transparent plastic such as acrylic resin, methacrylic resin, polycarbonate resin, polyester resin, nylon resin; silicon etc. may be mentioned.

  If it is not necessary to extract light from the surface of the organic light emitting element 10 on the side of the substrate 11, the material of the substrate 11 is not limited to transparent one, and opaque one may 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) Materials made of a single material of the above, or alloys of these, or 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, depending on the required mechanical strength.

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

  As a material satisfying such conditions, conductive metal oxides, metals, and alloys can be used. Here, examples of the conductive metal oxide include ITO (indium tin oxide) and IZO (indium zinc oxide). Further, as the metal, copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta), niobium (Nb) and the like can be mentioned. And alloys and stainless steels containing these metals can also be used. As a transparent material used to form a transparent anode, for example, conductive glass composed of indium oxide, zinc oxide, tin oxide, ITO (indium tin oxide) which is a complex thereof, IZO (indium zinc oxide), etc. And gold, platinum, silver and copper. Among these, ITO, IZO and tin oxide are preferable. Alternatively, a transparent conductive film made of an organic substance such as polyaniline or a derivative thereof or 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 it is desired to extract light from the substrate 11 side of the organic light emitting element 10. Moreover, when it is not necessary to take out light from the board | substrate 11 side of the organic light emitting element 10, it is 2 nm-2 mm, for example.

  The material of the substrate 11 may be the same as that of the anode 12. In this case, the substrate 11 may double 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 a first polymerizable compound capable of forming the crosslinked polymer on a first electrode, and then applying the solution to the first electrode. It is formed by polymerizing a polymerizable compound.

  The non-crosslinked polymer according to the present invention and the cross-linked polymer both include a repeating unit including a structure having charge transportability.

  In addition, since the absolute value of the difference in ionization potential 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 the decline of performance.

  The absolute value of the difference in ionization potential is determined from the ionization potential measured as follows. The 1st polymeric compound mentioned later and the 2nd polymeric compound mentioned later as needed are dissolved in a solvent, and a 1-3 mass% coating liquid is adjusted with a sum total of both polymeric compounds. Using this coating solution, a film is formed on a transparent support substrate by spin coating (1000 to 5000 rpm). The coating is dried and the polymerizable compound is polymerized. The ionization potential of the obtained film is measured by photoelectron spectroscopy in the atmosphere to obtain the ionization potential of the crosslinked polymer. Similarly, using the coating solution in which the non-crosslinked polymer is dissolved instead of the first polymerizable compound and the second polymerizable compound, the ionization potential of the obtained film is made the ionization potential of the non-crosslinked polymer. The absolute value of the difference of the ionization potential can be calculated from the ionization potential of the crosslinked polymer and the ionization potential of the non-crosslinked polymer. Here, as the solvent, those similar to those which can be used for the formation of the first organic compound layer described later can be used, and the same ones 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 superposition | polymerization can employ | adopt the method which can be used for manufacture of the below-mentioned organic light emitting element, and measurement of non-crosslinked polymer and measurement of crosslinked polymer are performed on the same conditions. In addition, although the process to polymerize is unnecessary originally for preparation of the film | membrane which consists of non-crosslinked polymers, in order to make the ionization potential and measurement conditions of the film | membrane which consists of crosslinked polymers equal, heat processing is performed 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 general formula (1) and the general formula (2) described later.

  The cross-linked polymer is usually a polymer obtained by polymerizing the first polymerizable compound, but the cross-linked polymer may be a polymer obtained only from the first polymerizable compound as a monomer, It may be a copolymer obtained by polymerizing the first polymerizable compound and the second polymerizable compound.

  The first polymerizable compound is not particularly limited, but normally, a compound containing a structure having charge transportability is used, and it is preferable to use a compound represented by the following general formula (3).

  As the second polymerizable compound, for example, a polymerizable compound having only one vinyl group in the molecule is used, and even if it is a compound having no charge transporting property, it is a compound having a charge transporting property. Good. As the second polymerizable compound, a vinyl compound not having charge transportability is usually used. For example, substituted or unsubstituted linear terminal alkene, substituted or unsubstituted styrene, acrylic acid ester, methacrylic acid ester And vinyl acetate. The number of carbons contained in these compounds is preferably in the range of 4 to 20, and more specifically, 1-octene, 4-phenyl-1-butene, styrene, α-methylstyrene, ethyl methacrylate and the like The compounds can be exemplified.

(Structure with charge transportability)
The non-crosslinked polymer and the crosslinked polymer contained in the first organic compound layer each have a repeating unit containing a structure having charge transportability.

  As the structure having charge transportability, known materials can be used, 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 transportability 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, one having a concentration of 0.01 to 0.05 eV is used. By satisfying such conditions, the decrease in charge mobility of the first organic compound layer can be suppressed, and the decrease in light emission efficiency of the organic light emitting device of the present invention can be 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 rate than in the prior art, and the solvent resistance is also improved.

  In addition, as a structure having charge transportability, a triphenylamine derivative is preferable in that an organic light emitting device having high hole injection ability and hole transport ability and high light emission efficiency can be obtained, and is represented by the following general formula (4) Is more preferred. That is, it is more preferable that A in general formula (1)-(3) mentioned later is represented by following General formula (4).

  In addition, when 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 the ionization potential becomes small and the charge transportability is lowered. It is preferable because the first organic compound layer can be obtained as a solvent resistant film without causing the reaction.

  Moreover, as a structure having charge transportability represented by A in the general formulas (1) to (3) described later, the formula weight of the structure is preferably 240 to 1000, and more preferably 400 to 1000. preferable. Within this range, it is preferable because the solvent resistance of the first organic compound layer is excellent and the heat resistance is also excellent.

（一般式（４）において、Ｒ²およびＲ³のいずれか一方は下記一般式（５）で表される基であり、好ましくはＲ³が下記一般式（５）で表される基である。前記一般式（４）におけるＲ¹〜Ｒ¹⁵および下記一般式（５）におけるＲ¹⁶〜Ｒ²⁹のいずれか二つは、一般式（１）〜（３）におけるＸ¹〜Ｘ⁵または水素原子への結合手であり、前記一般式（５）で表される基および前記結合手ではないＲ¹〜Ｒ¹⁵は、それぞれ独立に水素原子、ハロゲン原子、シアノ基、アミノ基、炭素数１〜１０のアルキル基、または炭素数１〜１０のアルコキシ基であり、好ましくは水素原子、炭素数１〜１０のアルキル基である。）

(In the general formula (4), one of R ² and R ³ is a group represented by the following general formula (5), 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) which is a bond to an atom and R ^{1 to} R ¹⁵ which is not the bond are each independently a hydrogen atom, a halogen atom, a cyano group, an amino group, 1 carbon atom -10 alkyl group or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

（一般式（５）において、前記結合手ではないＲ¹⁶〜Ｒ²⁹は、それぞれ独立に水素原子、ハロゲン原子、シアノ基、アミノ基、炭素数１〜１０のアルキル基、または炭素数１〜１０のアルコキシ基であり、好ましくは水素原子、炭素数１〜１０のアルキル基であり、ｂは０または１であり、ｂが1の場合において、連結した芳香環のＲ同士が互いに結合して縮合環を形成してもよい。）
前記炭素数１〜１０のアルキル基としては例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、２−ブチル基、ｔｅｒｔ−ブチル基、１−ペンチル基、２−ペンチル基、３−ペンチル基、３−メチルブチル基、１，１−ジメチルプロピル基、ｎ−ヘキシル基、２−ヘキシル基、３−ヘキシル基、４−メチルペンチル基、２−エチルブチル基、ｎ−ヘプチル基、２−ヘプチル基、３−ヘプチル基、４−ヘプチル基、ｎ−オクチル基、２−オクチル基、３−オクチル基、４−オクチル基、ｎ−エチルヘキシル基、ｎ−ノニル基、２−ノニル基、３−ノニル基、４−ノニル基、５−ノニル基またはｎ−デシル基等が挙げられ、好ましくはメチル基またはエチル基である。

(In the general formula (5), each of R ^{16 to} R ²⁹ which is not the bond is independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms In the case of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, b is 0 or 1, and b is 1 and Rs of linked aromatic rings are bonded to each other to form a condensation. It may form a ring.)
As said C1-C10 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, tert- butyl group, 1-pentyl group, 2-pentyl group is mentioned, for example 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 And 3-nonyl group, 4-nonyl group, 5-nonyl group, n-decyl group and the like, with preference given to methyl group or ethyl group.

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

In the case where b is 1, when Rs of linked aromatic rings are bonded to each other to form a fused ring, at least one R of the R ^{1 to} R ⁵ and the R ^{26 to} R ²⁹ And at least one R bond together to form a fused ring. In this case, the group forming the fused ring is usually an alkylene group having 1 to 10 carbon atoms or an alkenylene group having 2 to 10 carbon atoms.

The specific example of the structure represented by General formula (4) is shown below. In the following embodiment, thus omitting some bond to X ¹ to X ^5, or a hydrogen atom in the general formula below (1) to (3).

（非架橋ポリマー）
本発明の有機発光素子の第１の有機化合物層に含有される、非架橋ポリマーは電荷輸送性を有する繰り返し単位を含む。前記非架橋ポリマーとしては、特に限定はないが、隣接する繰り返し単位に含まれる２つの前記電荷輸送性を有する構造が、非共役構造を含む連結基によって、連結されていることが好ましい。すなわち、非架橋ポリマーは隣接する繰り返し単位に含まれる２つの前記電荷輸送性を有する構造が、連結基を介して共役することなく連結することが好ましい。つまり、非架橋ポリマーが、前記電荷輸送性を有する構造を主鎖に含むポリマーである場合、非架橋ポリマーの主鎖のうち、隣り合う２つの電荷輸送性を有する構造の間の部分に、非共役構造を含むことが好ましい。また非架橋ポリマーが、前記電荷輸送性を有する構造を側鎖に含むポリマーである場合、非架橋ポリマーの主鎖が非共役構造であるか、前記電荷輸送性を有する構造と、主鎖とが非共役構造を介して連結されていることが好ましい。非共役構造を含む連結基の例としては、炭素数１〜２０のアルキレン基、脂肪族エーテル結合を含む基が挙げられる。

(Non-crosslinked polymer)
The non-crosslinked polymer contained in the first organic compound layer of the organic light emitting device of the present invention contains a repeating unit having charge transportability. The non-crosslinked polymer is not particularly limited, but it is preferable that two structures having charge transportability contained in adjacent repeating units are linked by a linking group including a non-conjugated structure. That is, in the non-crosslinked polymer, it is preferable that the two structures having charge transportability contained in adjacent repeating units be linked via a linking group without being conjugated. That is, in the case where the non-crosslinked polymer is a polymer containing in the main chain the structure having charge transportability, in the main chain of the non-crosslinkable polymer, a portion between two adjacent structures having charge transportability It is preferred to include a conjugated structure. When the non-crosslinked polymer is a polymer containing a structure having the charge transporting property 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 Preferably, they are linked via a non-conjugated structure. Examples of the linking group containing a non-conjugated structure include an alkylene group having 1 to 20 carbon atoms and a group containing an aliphatic ether bond.

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

（一般式（１）、（２）において、各Ａはそれぞれ独立に、電荷輸送性を有する構造を表し、Ｘ¹は、−Ｏ−、−Ｓ−、または置換基を有してもよい炭素数１〜２０のアルキレン基（但し、該アルキレン基における１つまたは互いに隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−に置換されてよく、Ａに結合していない１つまたは隣接しない２つ以上のメチレン基は−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−Ｎ（Ｒ^Y）−、−ＣＯ−Ｎ（Ｒ^Y）−、アリーレン基に置換されていてもよい）を表し、Ｘ²は、単結合、−Ｏ−、−Ｓ−、または置換基を有してもよい炭素数１〜２０のアルキレン基（但し、該アルキレン基における１つまたは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−に置換されてよく、Ａに結合していない１つまたは隣接しない２つ以上のメチレン基は−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−Ｎ（Ｒ^Y）−、−ＣＯ−Ｎ（Ｒ^Y）−、アリーレン基に置換されていてもよい）、好ましくは単結合を表し、Ｒ^Yは、水素原子、炭素数１〜４のアルキル基、アリール基、またはアラルキル基を表す。）
なお、前記Ａで表わされる電荷輸送性を有する構造の好ましい態様としては、前記（電荷輸送性を有する構造）の項で説明したとおりである。

(In the general formulas (1) and (2), each A independently represents a structure having charge transportability, and X ¹ represents -O-, -S-, or carbon optionally having 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 by -O- or -S-, and one or adjacent to A which is not bonded Two or more methylene groups not substituted are substituted by -SO-, -SO _2- , -CO-, -COO-, -N ( ^RY )-, -CO-N ( ^RY )-, and an arylene group And X ² is a single bond, -O-, -S-, or an alkylene group having 1 to 20 carbon atoms which may have a substituent, provided that one or two of the alkylene groups are not adjacent. Two or more methylene groups may be substituted by -O-, -S- and 1 not bound to A. Or two or more adjacent methylene groups are substituted to -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 a structure which has a charge transportability represented by said A, it is as having demonstrated by the term of the above-mentioned (structure which has charge transportability).

  In the above-mentioned alkylene group having 1 to 20 carbon atoms which may have a substituent, when it does not have a substituent, that is, as the alkylene group having 1 to 20 carbon atoms, for example, ethylene group, propylene group, butylene group, pentamethylene group Groups, hexamethylene groups, heptamethylene groups, decamethylene groups, undecamethylene groups, dodecamethylene groups, tetradecamethylene groups and the like.

  Moreover, when it has a substituent in the said C1-C20 alkylene group which may have a substituent, ie, as a C1-C20 alkylene group which has a substituent, 1-ethoxy-2, 5-hexylene group, 1,5-dimethoxy-2,3-pentylene group, 1-ethoxy-2- (2-ethoxyethoxy) ethylene group, 1-butylsulfonyl-1,4-butylene group and the like can be mentioned.

  Moreover, when the methylene group is substituted by the arylene group in the C1-C20 alkylene group which may have a substituent, a C6-C21 arylene group is preferable. Examples of the arylene group include phenylene group, tolylene group, xylylene group, biphenylene group, naphthylene group, anthrylene group, phenanthrylene group and the like.

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

When said 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 and naphthylethyl group.

  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.

（第１の重合性化合物）
本発明の有機発光素子の第１の有機化合物層に含有される、架橋ポリマーとしては、電荷輸送性を有する構造を含む繰り返し単位を含んでいる。前記架橋ポリマーは通常は、少なくとも第１の重合性化合物を重合することにより形成されるポリマーであり、該第１の重合性化合物は通常、電荷輸送性を有する構造を含む化合物である。

(First polymerizable compound)
The crosslinked polymer contained in the first organic compound layer of the organic light emitting device of the present invention contains a repeating unit containing a structure having charge transportability. 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 containing a structure having charge transportability.

  The first polymerizable compound is a compound containing a structure having charge transportability, and is a polymerizable compound capable of forming a crosslinked polymer. As the first polymerizable compound, a compound including 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.

  As a polymerizable group which the first polymerizable compound has, 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, a cyclopropyl group It is preferable to have at least one member selected from the group consisting of cyclobutyl group, epoxy group, oxetanyl group, diketenyl group, epithio group, lactone group, and lactam group, and among these polymerizable groups, vinyl group and acryloyl group And methacryloyl groups are preferred, and vinyl groups are most preferred. As the crosslinked polymer, it is preferable that two structures having charge transportability contained in adjacent repeating units are linked by a linking group containing a non-conjugated structure, and two of the above contained in adjacent repeating units More preferably, the structure having charge transportability is linked to the linking main chain by a linking group containing a non-conjugated structure. That is, in the crosslinked polymer, it is preferable that the two structures having charge transportability contained in adjacent repeating units are linked via a linking group without being conjugated. For example, when the said polymeric group is a vinyl group, since a coupling group has the methylene group which is a nonconjugated structure, it is preferable.

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

（一般式（３）において、Ａは電荷輸送性を有する構造を表し、Ｘ⁵は、−Ｏ−、−Ｓ−、または置換基を有してもよい炭素数１〜２０のアルキレン基（但し、該アルキレン基における１つまたは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−に置換されてよく、Ａに結合していない１つまたは隣接しない２つ以上のメチレン基は−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−Ｎ（Ｒ^Y）−、−ＣＯ−Ｎ（Ｒ^Y）−、アリーレン基に置換されていてもよい）を表し、Ｘ³、Ｘ⁴はそれぞれ独立に、単結合、−Ｏ−、−Ｓ−、または置換基を有してもよい炭素数１〜２０のアルキレン基（但し、該アルキレン基における１つまたは隣接しない２つ以上のメチレン基は−Ｏ−、−Ｓ−に置換されてよく、Ａに結合していない１つまたは隣接しない２つ以上のメチレン基は−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−Ｎ（Ｒ^Y）−、−ＣＯ−Ｎ（Ｒ^Y）−、アリーレン基に置換されていてもよい）を表し、Ｒ^Yは、水素原子、炭素数１〜４のアルキル基、アリール基、またはアラルキル基を表わし、ａは０または１である）。

(In General Formula (3), A represents a structure having charge transportability, and X ⁵ is —O—, —S—, or an alkylene group having 1 to 20 carbon atoms which may have a substituent (wherein One or two or more non-adjacent methylene groups in the alkylene group may be substituted with -O- or -S-, and one or two non-adjacent methylene groups not bound to A are -SO _{-, - SO 2 -, -} CO -, - COO -, - N (R Y) -, - CO-N (R Y) -, represents also may) be substituted in the arylene group, X ^3, X ⁴ each independently 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 two or more non-adjacent groups in the alkylene group A methylene group may be substituted by -O-, -S-, and one or adjacent not bound to A. Two or more methylene groups not substituted are substituted by -SO-, -SO _2- , -CO-, -COO-, -N ( ^RY )-, -CO-N ( ^RY )-, and 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, and a is 0 or 1).

  In addition, as a preferable aspect of a structure which has a charge transportability represented by said A, it is as having demonstrated by the term of the above-mentioned (structure which has charge transportability).

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 non-adjacent methylene groups in the alkylene group are substituted by -O- or -S- And one or two or more non-adjacent methylene groups which are not bound to A are -SO-, -SO _2- , -CO-, -COO-, -N (R ^Y )-, -CO- N (R ^Y )-, which may be substituted with an arylene group). Further, in the X ^5, alkylene group having 1 to 20 carbon atoms which may have a substituent is preferably an alkylene group having carbon atoms of 6 to 14 which may have a substituent.

Examples of the alkylene group having 1 to 20 carbon atoms which may have a substituent, and the ^RY described above and preferred embodiments used herein include the substituent in the general formula (1) and the general formula (2). The same thing as the illustration and the suitable aspect of a C1-C20 alkylene group which may be and the said R ^Y is mentioned.

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

From this point of view, X ³ and X ⁴ may be substituted alkylene groups in which the number of atoms constituting the shortest chain connecting A and the vinyl group in General Formula (3) is 10 or more (however, And 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 two non-adjacent methylene groups not bonded to A may be- _{SO -, - SO 2 -,} - CO -, - COO -, - N (R Y) -, - CO-N (R Y) -, may be substituted in the arylene radical, R ^Y is a hydrogen atom Preferably represents an alkyl group having 1 to 4 carbon atoms, an aryl group or an aralkyl group thereof, and the alkylene group preferably has 10 to 14 atoms constituting the shortest chain, and the shortest 12 to 14 atoms constituting the chain Preferred in La.

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

第１の重合性化合物における電荷輸送性を有する構造の結晶性が高く第１の重合性化合物の分子量が小さいと、塗布成膜段階で相分離が起こりやすく、架橋後も非架橋ポリマー部分の耐溶剤性が低くなる場合がある。そのため、前記一般式（３）で表される第１の重合性化合物においてａが１であることが好ましい。

When the crystallinity of the structure having charge transportability in the first polymerizable compound is high and the molecular weight of the first polymerizable compound is small, phase separation easily occurs in the coating film formation step, and the resistance of the non-crosslinked polymer portion is also after crosslinking. Solvent resistance may be reduced. Therefore, in the first polymerizable compound represented by the general formula (3), a is preferably 1.

  In the prior art, when the ratio of the polymerizable compound to the non-crosslinked polymer used to form the organic compound layer is too high, the effect of the addition of the polymerizable compound becomes apparent in the characteristics of the organic compound layer and the non-crosslinked polymer is It has been preferred not to add too many polymerisable compounds as this would reduce the intrinsic properties. On the other hand, in the present invention, the amount of the first polymerizable compound used when forming the first organic compound layer is increased, that is, the ratio of the crosslinked polymer present in the first organic compound layer is increased. Even if it does, it does not reduce the characteristic of the 1st organic compound layer, but in order to improve solvent resistance rather, it is preferred to use many.

  In the organic light emitting device of the present invention, the mass ratio of the crosslinked polymer to the noncrosslinked polymer contained in the first organic compound layer (crosslinked polymer: noncrosslinked polymer) 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. Amount of non-crosslinked polymer used in the When the ratio of the non-crosslinked polymer exceeds the above range, crystallization of the polymerizable compound is likely to occur when forming the first organic compound layer, 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 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.

  When 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. When the molecular weight is too large, the proportion of the crosslinking group occupying the first polymerizable compound relatively decreases, and the reactivity in obtaining the crosslinked polymer from the first polymerizable compound decreases, and the first organic compound layer The molecular weight of the first polymerizable compound is preferably 300 to 2,000, and more preferably 500 to 1, because the insolubilization may be difficult or the heat resistance may decrease.

(Second polymerizable compound)
As described above, the crosslinked polymer of the first organic compound layer is a polymer formed of only the first polymerizable compound and a polymer formed of the first polymerizable compound and the second polymerizable compound. It may be.

  The second polymerizable compound may be a compound not having charge transportability or a compound having charge transportability. The second polymerizable compound usually contains one polymerizable group in the compound. As the second polymerizable compound, a vinyl compound not having charge transportability is usually used. For example, substituted or unsubstituted linear terminal alkene, substituted or unsubstituted styrene, acrylic acid ester, methacrylic acid 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 above general formula (3), and the above 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 the range of 10 to 100% by mass of the second polymerizable compound with respect to 100% by mass of the first polymerizable compound. It is preferable that it is what was obtained by copolymerizing a 1st polymeric compound and a 2nd polymeric compound.

  The reason is that in order for the first organic compound layer to be excellent in solvent resistance, it is desirable that the non-crosslinked polymer be incorporated in the crosslinked polymer, and for this purpose, the non-crosslinked polymer has enough cavities. This is because it is preferable to In the general formula (3), when a is 1, a crosslinked polymer having a sufficient cavity can be obtained even without the second polymerizable compound, but when a is 0, the above-mentioned ratio is the first The crosslinkable polymer obtained by copolymerizing the polymerizable compound of the above and the second polymerizable compound is likely to form a sufficient cavity.

(Electron acceptor)
The structure having charge transportability possessed by the non-crosslinked polymer and the crosslinked polymer improves charge mobility by forming a charge transfer complex with an electron acceptor, and thus the organic light emitting device of the present invention comprises the first organic light emitting device. Preferably, the hydride layer 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.

  There is no limitation in particular as said electron acceptor, A well-known compound can be used. As the electron acceptor, for example, 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-benzoquinonedimethane (F4TCNQ), 11,11,12,12-tetracyanonaphtho-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 cross-linked 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 crosslinked polymer and the noncrosslinked polymer because there is a difference between the gap with the ionization potential of the electron acceptor and the gap between the electron affinity of the electron acceptor and the ionization potential of the crosslinked polymer. Even though it was easy, it was difficult to form a charge transfer complex with the other. As a result, the charge mobility did not improve 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 crosslinked polymer is controlled to 0.2 eV or less, both the electron acceptor and the non-crosslinked polymer and the crosslinked polymer have charge transfer complexes The first organic compound layer exhibits good charge transfer properties because it is possible to form In addition, since the ionization potential of the electron acceptor is generally 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, it hardly affects the charge transfer characteristics.

  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 crosslinked polymer is determined by the method described in each of the ionization potential of the non-crosslinked polymer and the ionization potential of the crosslinked polymer. , It can be determined by calculating the absolute value of the difference.

(solvent)
The first organic compound layer is usually formed by application, and the application uses a solution containing the first polymerizable compound capable of forming the non-crosslinked polymer and the crosslinked polymer. As a solvent of the solution, a solvent capable of dissolving the non-crosslinked polymer and the first polymerizable compound, and 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; halogenated alkyl solvents such as chloroform and dichloroethane; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; Ether solvents, such as ethane and THF, etc. are mentioned, These solvents can also be used in mixture. Among these, toluene, xylene, anisole and mixed solvents thereof are preferable. 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. And 1 to 3% by mass is more preferable.

(Polymerization initiator)
In forming the first organic compound layer, the coating solution may contain a polymerization initiator. The polymerization initiator can be used properly 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 and vinylamino group as a polymerizable group, radical polymerization initiation Agents 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 which carries out cationic polymerization, such as oxetanyl group, a cationic polymerization initiator can be used.

  As a thermal radical polymerization initiator, azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobisisovaleronitrile, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone Ketone peroxides such as peroxide, diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide etc., 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 peroxy Pivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy axelate -3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, t-butylperoxy 2-ethylhexanoate, t- Alkylperoxyesters such as hexylperoxy 2-ethylhexanoate; percarbonates such as diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyisopropylcarbonate and the like can be mentioned.

  As a radical photopolymerization initiator, for example, 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-one Acetophenone derivatives such as benzophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4-trimethylsilyl benzophenone, benzophenone derivatives such as 4-benzoyl-4'-methyl-diphenyl sulfide, benzoin, benzoin ethyl ether, benzoin propyl ether , Ben In isobutyl ether, benzoin derivatives such as benzoin isopropyl ether, methylphenyl glyoxylate, benzoin dimethyl ketal, etc. 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

  As a thermal cationic polymerization initiator, various cationic compounds such as triflic acid salts, boron trifluoride ether complex compounds, boron trifluoride and the like, or cationic acid or proton acid catalysts, ammonium salts, phosphonium salts and sulfonium salts 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 And BF4-, PF6-, SbF6-, [BX4]-(wherein X is a phenyl group substituted with at least two or more fluorine or trifluoromethyl groups).

  Anionic polymerization initiators, melamine, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptacylimidazole, 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- [2 ' -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.

  A polymerization initiator may or may not be used. When a polymerization initiator is used, the amount thereof used is not particularly limited, but is usually 0 parts by 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 weight, preferably 1 to 10 parts by weight.

[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 on the first organic compound layer by application.

  The first organic compound layer is excellent in solvent resistance because it contains a crosslinked polymer. Therefore, 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 the non-crosslinked polymer and the solvent capable of dissolving the first polymerizable compound. Even if the first organic compound layer does not dissolve. Therefore, even when the second organic compound layer is formed by coating, the film thickness of the first organic compound layer may change, or the material constituting the first organic compound layer may be the second organic compound layer. The performance degradation of the organic light emitting device due to mixing into the compound layer does not occur. Therefore, as the solvent used to form the second organic compound layer, any solvent which dissolves the material of the second organic compound layer well and does not take into consideration the dissolution of the first organic compound layer and is excellent in coatability is optional. It can be selected and used. Specific examples of the solvent include those exemplified as those used for forming the first organic compound layer.

  As a 2nd organic compound layer, although it changes also with structures of the organic light emitting element of this invention, a positive hole transport layer and a light emitting layer are mentioned, for example. When the second organic compound layer is not a light emitting layer, the organic light emitting device of the present invention has a light emitting layer as another layer.

[Hole transport layer]
When the second organic compound layer is used as a hole transport layer, materials known as a hole transport material can be used. 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 weight triphenylamine derivatives such as-(1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4, 4 ′, 4 ′ ′-tris (3-methylphenylphenylamino) triphenylamine); Polyvinyl carbazole; a polymer compound obtained by introducing a polymerizable substituent into the triphenylamine derivative and polymerizing the same. In particular, it is desirable to include a polymer compound because the organic compound layer is formed by coating film formation. The hole transport materials may be used alone or in combination of two or more. In addition, hole transport layers formed of different hole transport materials may be stacked. The thickness of the hole transport layer depends on the conductivity of the hole transport layer and the like, and can not 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.

[Emitting layer]
When using a 2nd organic compound layer as a light emitting layer, a well-known material can be used as a material for forming a light emitting layer.

  As an organic compound for forming the light emitting layer of the organic light emitting device of the present invention, there is a light emitting low molecular weight compound described in Hiroshi Omori: Applied Physics, Vol. 70, No. 12, pp. 1419-1425 (2001). A compound, a luminescent high molecular compound, etc. can be illustrated. In addition, the light emitting compound is preferably a phosphorescent compound in that the light emitting efficiency is high. As the phosphorescent compound, known transition metal complexes including ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, platinum and gold can be exemplified. Among them, iridium complexes and platinum complexes are preferable.

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

（一般式（１１）中、Ｍはイリジウムまたは白金を表し、Ａで表される環はＭに結合した窒素原子を含む含窒素ヘテロ芳香環を表し、Ｂで表される環はＭに結合した炭素原子を含む芳香環またはヘテロ芳香環を表し、環Ａと環Ｂは互いに結合しており、Ｌは二座配位子を表し、ｓは１〜３の整数を表し、ｔは０〜２の整数を表し、ｓ＋ｔは２または３である。）
本発明の方法により製造される有機ＥＬ素子における発光層は、好ましくは前記燐光発光性化合物を含む層であるが、発光層の塗布成膜時に発光性化合物の結晶化を抑制したり発光層の電荷輸送性を補う目的で正孔輸送性化合物や電子輸送性化合物、またはこれらを重合させた高分子化合物が含まれていてもよい。これらの目的で用いられる正孔輸送性化合物としては、例えば、ＴＰＤ（Ｎ，Ｎ'−ジフェニル−Ｎ，Ｎ'−ジ（３−メチルフェニル）−１，１'−ビフェニル−４，４'ジアミン）、α−ＮＰＤ（４，４'−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル）、ｍ−ＭＴＤＡＴＡ（４、４'，４''−トリス（３−メチルフェニルフェニルアミノ）トリフェニルアミン）などの低分子トリフェニルアミン誘導体や、ポリビニルカルバゾール、前記トリフェニルアミン誘導体に重合性官能基を導入して高分子化したもの、例えば特開平８−１５７５７５号公報に開示されているトリフェニルアミン骨格の高分子化合物、ポリパラフェニレンビニレン、ポリジアルキルフルオレンなどが挙げられ、また、電子輸送性化合物としては、例えば、Ａｌｑ３（トリス（８−ヒドロキシキノリナート）アルミニウム（ＩＩＩ））などのキノリノール誘導体金属錯体、オキサジアゾール誘導体、トリアゾール誘導体、イミダゾール誘導体、トリアジン誘導体、トリアリールボラン誘導体などの低分子材料や、上記の低分子電子輸送性化合物に重合性官能基を導入して高分子化したもの、例えば特開平１０−１６６５号公報に開示されているポリＰＢＤなどの既知の電子輸送性化合物が使用できる。

(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, the ring represented by B is bonded to M Represents an aromatic ring or heteroaromatic ring containing a carbon atom, 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 is 0 to 2 Represents an integer of, and s + t is 2 or 3.)
The light emitting layer in the organic EL device manufactured by the method of the present invention is preferably a layer containing the above-mentioned phosphorescent compound, but the crystallization of the light emitting compound is suppressed at the time of coating film formation of the light emitting layer. A hole transportable compound, an electron transportable compound, or a polymer compound obtained by polymerizing these may be included for the purpose of compensating the charge transportability. As a hole transportable compound used for these purposes, for example, TPD (N, N'-diphenyl-N, N'-di (3-methylphenyl) -1,1'-biphenyl-4,4 'diamine is used. ), Α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4,4 ′, 4 ′ ′-tris (3-methylphenylphenylamino) Low molecular weight triphenylamine derivatives such as triphenylamine), polyvinylcarbazole, those obtained by introducing a polymerizable functional group into the triphenylamine derivative and polymerizing it, as disclosed in, for example, JP-A-8-157575. Polymer compounds having a triphenylamine skeleton, polyparaphenylene vinylene, polydialkyl fluorene and the like, and examples of the electron transporting compound include Quinolinol derivative metal complexes such as Alq3 (tris (8-hydroxyquinolinate) aluminum (III)), oxadiazole derivatives, triazole derivatives, imidazole derivatives, imidazole derivatives, triazine derivatives, low molecular materials such as triarylborane derivatives, or the above It is possible to use one obtained by introducing a polymerizable functional group into a low molecular weight electron transporting compound and polymerizing it, for example, known electron transporting compounds such as polyPBD disclosed in JP-A-10-1665.

[cathode]
The material used for the cathode 15 is not particularly limited as long as it has electrical conductivity like the anode 12, but a material having a low work function and being chemically stable is preferable. Specifically, materials such as an alloy of Al and an alkali metal such as Al, MgAg alloy and AlLi, and an alloy of an Al and an alkaline earth metal such as AlCa can be exemplified. However, when it is desired that the material of the cathode 15 extract light from the cathode 15 side of the organic light emitting element 10 (when the surface on the cathode 15 side is a light extraction surface, ie, a light emitting surface), for example, 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, 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 and the like as other layers. In addition, 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. Materials usable 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] Zinc, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole and the like can be mentioned.

(Hole blocking layer)
In addition, between the second organic compound layer 14 and the electron transport layer, the holes are prevented from passing through the light emitting layer, and the holes and the electrons are efficiently recombined in the light emitting layer. A block layer may be provided. In order to form the said hole block layer, well-known materials, such as a triazole derivative, an oxadiazole derivative, a phenanthroline derivative, are used.

(Electron injection layer)
Further, an electron injection layer may be provided adjacent to the cathode 15 in order to increase the injection efficiency of electrons from the cathode 15. For the electron injection layer, a metal material having a work function lower than that of the cathode 15 is suitably used. For example, alkali metals (Na, K, Rb, Cs), alkaline earth metals (Sr, Ba, Ca, Mg), rare earths Although metals (Pr, Sm, Eu, Yb) can be used, fluorides, chlorides and oxides of these metals are also suitably 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)
In the organic light emitting element 10, it is preferable to use the organic light emitting element 10 stably for a long period of time and to attach a protective layer or a protective cover (not shown) for protecting the organic light emitting element 10 from the outside. As a material of the protective layer, a polymer compound, a metal oxide, a metal fluoride, a metal boride, a silicon compound such as silicon nitride, silicon oxide and the like can be used. Moreover, these laminated bodies can also be used.

  As the protective cover, a glass plate, a plastic plate whose surface has been subjected to a low water permeability treatment, metal or the like can be used. It is preferable that this protective cover adopt a method of bonding and sealing the element substrate with a thermosetting resin or a photocurable resin. At this time, 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. Then, if an inert gas such as nitrogen, argon or helium is sealed in this space, the oxidation of the upper cathode 16 can be easily prevented.

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

[Method of manufacturing organic light emitting device]
In the method of manufacturing an organic light emitting device of the present invention, an organic light emitting device is usually manufactured using the coating solution of the present invention.

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

  In the method of manufacturing an organic light emitting device of the present invention, a solution containing a first polymerizable compound capable of forming the non-crosslinked polymer and the crosslinked polymer and a solvent is applied on a first electrode to form a coated film. And 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, and adjacent to the first organic compound layer Forming a second organic compound layer by coating, and 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 charge transportability, and the non-crosslinked polymer and the crosslinked polymer both include a repeating unit including a structure having charge transportability. In the method of manufacturing an organic light emitting device according to 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 addition, in another method of manufacturing an organic light emitting device, at least one layer of the first organic compound layer and the second organic compound layer may be formed by a method other than coating.

  In the method of manufacturing an organic light-emitting device of the present invention, a first cross-linked polymer including a non-crosslinked polymer comprising a repeating unit including a structure having charge transportability and a cross-linked polymer including a structure having charge transportability may be formed on a first electrode. The solution containing the polymerizable compound is applied to form a coating, and the type and amount of each component contained in the solution are as described above. There is no particular limitation on the method of applying the solution on the first electrode, but usually, spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar, etc. Film formation can be performed using a coating method such as 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 forming a 1st organic compound layer by application | coating, after apply | coating a solution, before polymerizing a polymeric compound, the process of drying a coating film is included normally. The temperature for drying the coating film can be appropriately determined in the range in which the components in the coating film are not easily deteriorated by heat depending on the type of the solvent used for the solution, and is usually 50 to 300 ° C.

  The method of 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 to polymerize can be suitably determined in the range which the component in a coating film does not deteriorate easily with the kind of polymeric group of a 1st polymeric compound. For example, when polymerizing radically polymerizable groups such as vinyl group, ethynyl group, butenyl group, acryloyl group, acryloylamino group, methacryloyl group, methacryloyl group, vinyloxy group and vinylamino group by heating, usually, nitrogen, etc. 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 above-mentioned drying step.

  Further, there is no particular limitation on the method of applying the second organic compound layer to the first compound layer, and the film formation is performed using the same method as the first organic compound layer. It can be performed.

  Moreover, when the organic light emitting element of this invention has another layer, a member, etc., it can laminate | stack and arrange by a well-known method.

[Use]
The organic light emitting device of the present invention is suitably used for an image display device as a pixel by a matrix system or a segment system. Moreover, the said organic light emitting element is suitably used also as illuminating devices, such as a surface emitting light source, without forming a pixel.

  Specifically, the organic light emitting device of the present invention is a display device in a computer, a television, a portable terminal, a mobile phone, a car navigation, a sign, a signboard, a view finder of a video camera, a backlight, an electronic photograph, illumination, resist exposure , A reader, interior lighting, an optical communication system, etc. It is used suitably for the light irradiation apparatus.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

[Evaluation method]
(1) <ionization potential>
The non-crosslinked polymer or polymerizable compound was dissolved in toluene to prepare a 2.0% by mass coating solution. Using this coating solution, a film was formed on a transparent support substrate by spin coating (2000 rpm, 30 seconds), and heat treatment was performed at 140 ° C. for 2 hours in a nitrogen atmosphere to form a film with 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 rate>
(Preparation of Laminates A and B)
Example to be described later on blue plate glass (25 mm square, plate thickness 1.1 mm) for evaluation of solvent resistance (calculation of maintenance rate) separately from the organic EL elements manufactured in the following Examples and Comparative Examples. Two laminates provided with only the first organic compound layer (50 nm thickness) containing a crosslinked polymer and a non-crosslinked polymer were prepared by the procedure described in Comparative Example, and were designated as a laminate A and a laminate B. .

(Thickness of organic compound layer)
A portion of the organic compound layer of the laminate A is cut with a needle to expose the substrate (hereinafter, the substrate surface thus exposed is also referred to as a “substrate exposed portion”), and a stylus type surface shape measuring apparatus (ULVAC Dektak) The organic compound layer side surface of the laminate A is observed to cross the substrate exposed portion as shown in FIG. 2 using 6) to obtain an organic compound layer (hereinafter referred to as “organic compound layer before dissolution test treatment The thickness of “is also measured”.

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

  After 0.10 ml of toluene was dropped onto the organic compound layer of the laminate B, it was rotated at 3000 rpm for 30 seconds. The rotation started within 5 seconds after the addition of toluene. The sample was then left at 140 ° C. for 1 hour 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 dissolution test treatment”) is measured by the same method as in the case of the laminate A, and is defined by the following formula The “maintenance rate (%)” of the thickness of the organic compound layer was calculated.

Maintenance ratio = Thickness of organic compound layer after dissolution test treatment / Thickness of organic compound layer before dissolution test treatment × 100
(3) <Method of measuring driving voltage, luminous efficiency, power efficiency>
Voltage was applied stepwise to the organic light emitting device using a constant voltage power supply (manufactured by Keithley, SM2400), and the light emission start voltage and the luminance of the organic light emitting device were quantified with a luminance meter (manufactured by Topcon, BM-9). The resulting luminous efficiency (ratio of the number of photons to the amount of current (number of electrons) at 100 cd / m ² lighting), power efficiency (ratio of luminous flux to input power) from the current density and the ratio of luminance to drive voltage Were determined.

  Synthesis Example 1

窒素雰囲気下において、５００ｍｌの３つ口フラスコに２，５−ジメチル−１，４−フェニレンジアミン（５．０ｇ、３７ｍｍｏｌ）、３−ヨードトルエン（３３．０ｇ、１５０ｍｍｏｌ）および脱水キシレン（２００ｍｌ）を入れ、５０℃で撹拌した。これに、カリウム−ｔｅｒｔ−ブトキシド（１７ｇ、１５０ｍｍｏｌ）、酢酸パラジウム（０．５０ｇ、２．２ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン（１．４ｇ、６．９ｍｍｏｌ）を順に加え、１２０℃で４時間撹拌した。得られた反応混合物を室温にまで冷却し、水（１００ｍｌ）を加えた後、酢酸エチルで有機層を抽出した。抽出液を硫酸マグネシウムで乾燥し、減圧下で濃縮した後、シリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル−ヘキサンの混合溶媒）で精製した。得られた粗生成物をメタノールを用いて再結晶して化合物（ａ）を得た（１２．２ｇ、２５ｍｍｏｌ）。

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

  Then, under 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 resulting reaction solution was poured 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 filtering off the solid, the solvent was evaporated and the obtained residue was purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a compound (b) (6.5 g, 12 mmol).

  Next, under a nitrogen atmosphere, methyltriphenylphosphonium bromide (5.0 g, 14 mmol) and dehydrated tetrahydrofuran (THF) (100 ml) are placed in a 200 ml three-necked flask, and potassium tert-butoxide (1 .7 g, 15 mmol) were 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 the mixture was stirred at room temperature for 3 hours. Water (200 ml) was added to the resulting reaction mixture and 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 solvent was evaporated and the obtained residue was purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a compound (c) (5.1 g, 9.8 mmol).

  The identification data of the compound (c) are 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 spectrometry (FAB +): 522 (M +).
Next, Compound (c) (500 mg) is placed in a closed container, dehydrated toluene (9.9 mL) is added, and then a solution of azobisisobutyronitrile (AIBN) in dehydrated toluene (0.1 M, 198 μL) is added. The This solution was sealed under vacuum after repeated freeze degassing operation 5 times, and reacted by stirring at 60 ° C. for 60 hours. The reaction solution was dropped into 500 mL of acetone to obtain a precipitate. Furthermore, after repeating reprecipitation purification with toluene-acetone twice, the precipitate was vacuum dried overnight at 50 ° C. to obtain a non-crosslinked polymer (A). The weight average molecular weight of the obtained non-crosslinked polymer (A) was 34000, and the molecular weight distribution index (Mw / Mn) was 2.31.

  Synthesis Example 2

窒素雰囲気下において、５００ｍｌの３つ口フラスコに２，５−ジメチル−１，４−フェニレンジアミン（５．０ｇ、３７ｍｍｏｌ）、３−ヨードトルエン（１７．０ｇ、７８ｍｍｏｌ）および脱水キシレン（２００ｍｌ）を入れ、５０℃で撹拌した。これに、カリウム−ｔｅｒｔ−ブトキシド（８．７ｇ、７８ｍｍｏｌ）、酢酸パラジウム（０．３０ｇ、１．３ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン（１．０ｇ、４．９ｍｍｏｌ）を順に加え、１２０℃で４時間撹拌した。得られた反応混合物を室温にまで冷却し、水（１００ｍｌ）を加えた後、酢酸エチルで有機層を抽出した。抽出液を硫酸マグネシウムで乾燥し、減圧下で濃縮した後、シリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル−ヘキサンの混合溶媒）で精製して化合物（ｄ）を得た（９．５ｇ、３０ｍｍｏｌ）。

In a 500 ml three-necked flask under 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) Charge and stir at 50.degree. 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) are added in this order, and Stir for 4 hours. The resulting reaction mixture was cooled to room temperature, water (100 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated under reduced pressure, and then 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, the compound (d) (9.5 g, 30 mmol), 4-bromo-2-methylphenol (12.0 g, 64 mmol) and dehydrated xylene (200 ml) are 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), tri-tert-butyl phosphine (1.4 g, 6.9 mmol) are added in order, and it is kept at 120 ° C for 4 hours It stirred. The resulting reaction mixture was cooled to room temperature, 1 M 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 give compound (e) (10 g, 19 mmol).

  Next, under a nitrogen atmosphere, the compound (e) (10 g, 19 mmol), potassium tert-butoxide (4.7 g, 42 mmol) and dehydrated DMF (100 ml) are put in a 300 ml three-necked flask and stirred at room temperature for 1 hour did. 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) was added dropwise to the reaction mixture obtained, and it was kept for 5 hours at room temperature. It stirred. Next, 500 ml of water was added to the reaction solution, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a polymerizable compound B (1.5 g) , 1.0 mmol).

  The identification data of the polymerizable compound B are 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 spectrometry (FAB +): 1472 (M +).
Example 1
Indium tin oxide (ITO) was formed into a film of 120 nm thick by sputtering on a glass substrate and used as a transparent conductive support substrate. This was ultrasonically washed successively with acetone and isopropyl alcohol (IPA), and then washed by boiling with IPA and dried. Furthermore, the one subjected to UV / ozone cleaning 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 at a mass ratio of 50:50 was dissolved in toluene to prepare a 2.0% by mass coating solution. . Using this coating solution, a film is formed on the surface of the transparent support substrate on which ITO is formed by spin coating (2000 rpm, 30 seconds), and heat treatment is performed for 2 hours at 140 ° C. in a nitrogen atmosphere to obtain a film thickness of 50 nm. A cured film of the above was produced, and a hole injection layer (first organic compound layer) was formed.

  Next, a mixture of compound X represented by the following formula and compound P represented by the following formula at a mass ratio of 10:90 is dissolved in toluene, and the total of compound X and compound P is 2.0 mass% The coating solution was adjusted. Compound X was synthesized by the method described in JP-A-2005-200638, and Compound P was synthesized by the method described in JP-A-2007-081392. Using this coating solution, a film is formed by spin coating (2000 rpm, 30 seconds) on the previously prepared film, and heat treatment is carried out at 140 ° C. for 1 hour in a nitrogen atmosphere to form a 50 nm film. The (second organic compound layer) was formed.

Furthermore, using a vapor deposition material consisting of aluminum and lithium (lithium concentration: 1 atomic%), a 150 nm-thick metal layer film is formed on the above-mentioned organic compound layer by vacuum evaporation, and the structure shown in FIG. A device was produced. The deposition was performed under the conditions of a degree of vacuum of 1.0 × 10 ⁻⁴ Pa and a deposition rate of 1.0 to 1.2 nm / sec. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

［合成例３］
１１−ブロモ−１−ウンデセンの代わりに５−ブロモ−１−ペンテンを用いた以外は、合成例２と同様の方法で行い、下式で表わされる重合性化合物Ｃを合成した。

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 are 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 +).

［実施例２］
実施例１の重合性化合物Ｂを合成例３で合成した重合性化合物Ｃに変えた他は実施例１の素子と全く同様にして実施例２の素子を作製した。この様にして得られた素子において、ＩＴＯ電極を正極、アルミニウム−リチウム電極を負極にして、真空中で直流電圧を印加して発光させた結果を表２に示す。

Example 2
A device of Example 2 was manufactured 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. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

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

  The identification data of the polymerizable compound D are 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 spectrometry (FAB +): 1528 (M +).

なお、化合物（ｇ）は以下の方法で合成した。

Compound (g) was synthesized by the following method.

  In a nitrogen atmosphere, a 500 ml three-necked flask is charged with 1,4-phenylenediamine (4.0 g, 37 mmol), 3-iodotoluene (17.0 g, 78 mmol) and dehydrated xylene (200 ml) 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) are added in this order, and Stir for 4 hours. The resulting reaction mixture was cooled to room temperature, water (100 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated under reduced pressure, and then 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, the compound (f) (8.7 g, 30 mmol), 4-bromo-2-methylphenol (12.0 g, 64 mmol) and dehydrated xylene (200 ml) are 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), tri-tert-butyl phosphine (1.4 g, 6.9 mmol) are added in order, and it is kept at 120 ° C for 4 hours It stirred. The resulting reaction mixture was cooled to room temperature, 1 M 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 give compound (g) (9.5 g, 19 mmol).

［実施例３］
実施例１の第１の重合性化合物Ｂを、合成例４で合成した重合性化合物Ｄに変えた他は実施例１の素子と全く同様にして実施例３の素子を作製した。この様にして得られた素子において、ＩＴＯ電極を正極、アルミニウム−リチウム電極を負極にして、真空中で直流電圧を印加して発光させた結果を表２に示す。

[Example 3]
A device of Example 3 was manufactured in the same manner as the device of Example 1 except that the first polymerizable compound B in Example 1 was changed to the polymerizable compound D synthesized in Synthesis Example 4. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

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 JP-A-2005-200638.

［合成例６］

Synthesis Example 6

窒素雰囲気下において、２００ｍｌの３つ口フラスコに化合物（ｉ）（特開２００５−９７５８９に記載された方法に従って合成した）（１．５ｇ、３．８ｍｍｏｌ）、化合物（ｊ）（１．３ｇ、３．９ｍｍｏｌ）および脱水キシレン（５０ｍｌ）を入れ、５０℃で撹拌した。これに、カリウム−ｔｅｒｔ−ブトキシド（０．４５ｇ、４．０ｍｍｏｌ）、酢酸パラジウム（０．１０ｇ、０．４５ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン（０．２５ｇ、１．２ｍｍｏｌ）を順に加え、１２０℃で４時間撹拌した。得られた反応混合物を室温にまで冷却し、水（５０ｍｌ）を加えた後、酢酸エチルで有機層を抽出した。抽出液を硫酸マグネシウムで乾燥し、減圧下で濃縮した後、シリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル−ヘキサンの混合溶媒）で精製して化合物（ｋ）を得た（２．０ｇ、３．１ｍｍｏｌ）。

Compound (i) (synthesized according to the method described in JP-A-2005-97589) (1.5 g, 3.8 mmol) in a 200 ml three-necked flask under a nitrogen atmosphere, 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) are sequentially added, and 120 Stir at 4 ° C for 4 hours. The resulting reaction mixture was cooled to room temperature, water (50 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated under reduced pressure, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a compound (k) (2.0 g, 3. 1 mmol).

  Then, under a nitrogen atmosphere, the compound (k) (2.0 g, 3.1 mmol), the compound (l) (0.87 g, 1.5 mmol) and dehydrated xylene (50 ml) are 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) are sequentially added, and 120 Stir at 4 ° C for 4 hours. The resulting reaction mixture was cooled to room temperature, water (50 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated under reduced pressure, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a polymerizable compound F (2.2 g, 3 mmol).

  The identification data of the polymerizable compound F are 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 spectrometry (FAB +): 1698 (M +).
Example 4
The device of Example 1 is used except that the non-crosslinked polymer A of Example 1 is changed to the non-crosslinked polymer E synthesized in Synthesis Example 5, and the first polymerizable compound B is changed to the polymerizable compound F synthesized in Synthesis Example 6. The element of Example 4 was produced in exactly the same manner. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

[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 in Example 4 was changed to the polymerizable compound D. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

[Example 6]
A device of Example 6 was manufactured in the same manner as the device of Example 1 except that the ratio of the non-crosslinked polymer A to the polymerizable compound B in Example 1 was changed to 5:95. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

[Example 7]
The device of Example 7 was manufactured in the same manner as the device of Example 1 except that F4TCNQ was added so as to be 50: 50: 1 non-crosslinked polymer A, polymerizable compound B, and F4TCNQ. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

  Synthesis Example 7

窒素雰囲気下において、２００ｍｌの３つ口フラスコに化合物（ｅ）（５．０ｇ、９．５ｍｍｏｌ）、カリウム−ｔｅｒｔ−ブトキシド（２．２ｇ、２０ｍｍｏｌ）および脱水ＤＭＦ（５０ｍｌ）を入れ、室温で１時間撹拌した。得られた反応混合物に１１−ブロモ−１−ウンデセン（４．７ｇ、２０ｍｍｏｌ）のＤＭＦ（１５ｍｌ）溶液を滴下し、室温で５時間攪拌した。次に反応液に２００ｍｌの水を加え、酢酸エチルで抽出した後、シリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル−ヘキサンの混合溶媒）にて精製し、重合性化合物Ｉを得た（６．６ｇ、７．９ｍｍｏｌ）。

Under a nitrogen atmosphere, a 200 ml three-necked flask is charged with compound (e) (5.0 g, 9.5 mmol), potassium tert-butoxide (2.2 g, 20 mmol) and dehydrated DMF (50 ml). Stir for hours. A solution of 11-bromo-1-undecene (4.7 g, 20 mmol) in DMF (15 ml) was added dropwise to the resulting reaction mixture, and stirred at room temperature for 5 hours. Next, 200 ml of water was added to the reaction solution, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a 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 spectrometry (FAB +): 833 (M +).
[Example 8]
The coating solution for forming the hole injection layer used in Example 1 is the non-crosslinked polymer A synthesized in Synthesis Example 1, the polymerizable compound I synthesized in Synthesis Example 7, the styrene as the second polymerizable compound 50 A device of Example 8 was produced in the same manner as the device of Example 1, except that the toluene solution was changed to a toluene solution having a solid content of 2.0% by mass, which was contained at a mass ratio of 50:20. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

  Synthesis Example 8

窒素雰囲気下において、５００ｍｌの３つ口フラスコにトリ（４−ブロモフェニル）アミン（６．０ｇ、１２ｍｍｏｌ）、Ｎ−（３−メチルフェニル）アニリン（２．２ｇ、１２ｍｍｏｌ）、Ｎ−（３−ヒドロキシフェニル）−ｍ−トルイジン（２．４ｇ、１２ｍｍｏｌ）、Ｎ−（４−ベンジルオキシフェニル）−ｍ−トルイジン（３．５ｇ、１２ｍｍｏｌ）および脱水キシレン（２００ｍｌ）を入れ、５０℃で撹拌した。これに、カリウム−ｔｅｒｔ−ブトキシド（５．６ｇ、５０ｍｍｏｌ）、酢酸パラジウム（０．５０ｇ、２．２ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン（１．４ｇ、６．９ｍｍｏｌ）を順に加え、１２０℃で４時間撹拌した。得られた反応混合物を室温にまで冷却し、水（２００ｍｌ）を加えた後、酢酸エチルで有機層を抽出した。抽出液を硫酸マグネシウムで乾燥し、減圧下で濃縮した後、シリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル−ヘキサンの混合溶媒）で精製して化合物（ｍ）を得た（１．３ｇ、１．４ｍｍｏｌ）。

Tri (4-bromophenyl) amine (6.0 g, 12 mmol), N- (3-methylphenyl) aniline (2.2 g, 12 mmol), N- (3- (3-bromophenyl) amine in a 500 ml three-necked flask under a nitrogen atmosphere. 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) are added in this order, and Stir for 4 hours. The resulting reaction mixture was cooled to room temperature, water (200 ml) was added, and the organic layer was extracted with ethyl acetate. The extract was dried over magnesium sulfate and concentrated under reduced pressure, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (m) (1.3 g, 4 mmol).

  Then, under a nitrogen atmosphere, the 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 The mixture was 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 stirred at room temperature for 5 hours. Next, 100 ml of water was added to the reaction solution, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a compound (n) (1.4 g) , 0.72 mmol).

  Next, under a nitrogen atmosphere, the compound (n) (1.4 g, 0.72 mmol) and tetrakis (triphenylphosphine) palladium (0.050 g, 0.043 mmol) are placed in a 100 ml three-necked flask, and 50 ml of THF is added. Dissolved. Hydrazine monohydrate (3.0 g, 54 mmol) was added to this, and it heated and refluxed for 12 hours. The obtained reaction mixture was poured 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).

  Then, under a nitrogen atmosphere, 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. The mixture was stirred at room temperature for 1 hour. To the resulting reaction mixture was added dropwise a solution of 11-bromo-1-undecene (0.51 g, 2.2 mmol) in DMF (5 ml) and stirred at room temperature for 5 hours. Next, 200 ml of water was added to the reaction solution, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a polymerizable compound J (1.3 g , 0.63 mmol).

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

Calcd _{(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 spectrometry (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 in Example 1 was changed to the polymerizable compound J synthesized in Synthesis Example 7. In the device thus obtained, the ITO electrode was made a positive electrode, the aluminum-lithium electrode was made a negative electrode, and direct current voltage was applied in vacuum to emit light. The results are shown in Table 2.

  Synthesis Example 8

窒素雰囲気下において、３００ｍｌの３つ口フラスコに２，４−ジアミノメシチレン（３．０ｇ、２０ｍｍｏｌ）、３−ヨードトルエン（８．７ｇ、４０ｍｍｏｌ）および脱水キシレン（１５０ｍｌ）を入れ、５０℃で撹拌した。これに、カリウム−ｔｅｒｔ−ブトキシド（４．５ｇ、４０ｍｍｏｌ）、酢酸パラジウム（０．３０ｇ、１．３ｍｍｏｌ）、トリ−ｔｅｒｔ−ブチルホスフィン（１．０ｇ、４．９ｍｍｏｌ）を順に加え、１２０℃で４時間撹拌した。得られた反応混合物（ｐ）に４−ブロモ−２−メチルフェノール（７．５ｇ、４０ｍｍｏｌ）およびカリウム−ｔｅｒｔ−ブトキシド（９．０ｇ、８０ｍｍｏｌ）を加え、さらに１２０℃で４時間撹拌した。反応液を室温にまで冷却し、水（１５０ｍｌ）を加えた後、酢酸エチルで有機層を抽出した。抽出液を硫酸マグネシウムで乾燥し、減圧下で濃縮した後、シリカゲルカラムクロマトグラフィー（溶離液：酢酸エチル−ヘキサンの混合溶媒）で精製して化合物（ｑ）を得た（３．９ｇ、７．２ｍｍｏｌ）。

Under a nitrogen atmosphere, a 300 ml three-necked flask is charged with 2,4-diaminomesitylene (3.0 g, 20 mmol), 3-iodotoluene (8.7 g, 40 mmol) and dehydrated xylene (150 ml) and stirred at 50 ° C. did. To this, potassium tert-butoxide (4.5 g, 40 mmol), palladium acetate (0.30 g, 1.3 mmol), tri-tert-butyl phosphine (1.0 g, 4.9 mmol) are added in this order, and Stir for 4 hours. To the resulting reaction mixture (p) were added 4-bromo-2-methylphenol (7.5 g, 40 mmol) and potassium tert-butoxide (9.0 g, 80 mmol), and the mixture was further stirred at 120 ° C. for 4 hours. The reaction solution 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 and concentrated under reduced pressure, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain compound (q) (3.9 g, 2 mmol).

  Then, 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) are put in a 200 ml three-necked flask, The mixture was stirred 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, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent: mixed solvent of ethyl acetate-hexane) to obtain a polymerizable compound K (0.50 g) , 0.33 mmol).

  The identification data of the polymerizable compound K are 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 in Example 1 was changed to the polymerizable compound K synthesized in Synthesis Example 8. The element obtained in this manner was made to emit light by applying a DC voltage in vacuum using the ITO electrode as a positive electrode and the aluminum-lithium electrode as a negative electrode. The results are shown in Table 2.

Claims (13)

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;
And 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 both include a repeating unit including a structure having charge transportability,
And the ionization potential of the non-crosslinked polymer, Ri absolute value 0~0.2eV der of the difference between the ionization potential of the crosslinked polymer,
The crosslinked polymer is a polymer formed by polymerizing at least a first polymerizable compound,
The first polymerizable compound is a compound including a structure having charge transportability,
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 first polymerizable compound is a compound represented by the following general formula (3),
The first polymerizing compound and the second polymerizing compound in the range where the second polymerizing compound is 10 to 100 mass% with respect to 100 mass% of the first polymerizing compound as the crosslinked polymer der Ru organic light emitting device which is obtained by copolymerizing and.

(In the general formulas (1) to (3), each A independently represents a structure having charge transportability, and X ¹ and X ⁵ each independently represent -O-, -S-, or a substituent An alkylene group having 1 to 20 carbon atoms which may be substituted, provided that one or two or more non-adjacent methylene groups in the alkylene group may be substituted by -O- or -S- and be bonded to A not one or more methylene groups not adjacent to each _{-SO -, - SO 2 -,} - CO -, - COO -, - N (R Y) -, - CO-N (R Y) -, an arylene group And may be replaced by
Each of X ^{2 to} X ⁴ independently 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 two of the alkylene groups are not adjacent. Two or more methylene groups may be substituted by -O-, -S- and one or two non-adjacent methylene groups not bonded to A may be -SO-, -SO _2- , -CO- And -COO-, -N ( ^RY )-, -CO-N ( ^RY )-, which may be substituted with an arylene group; and R ^Y is 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. ) The organic light-emitting device according to claim 1 , wherein in the non-crosslinked polymer and the cross-linked polymer, the two structures having charge transportability contained in adjacent repeating units are linked by a linking group including a non-conjugated structure. . The organic light emitting device according to claim 1 or 2 , wherein the structure having charge transportability possessed by the repeating unit of the non-crosslinked polymer and the structure possessing charge transportability possessed by the repeating unit of the crosslinked polymer have the same structure. The organic light emitting device according to any one of claims 1 to 3 , wherein the charge transportable structure is a triphenylamine derivative. The organic light emitting device according to any one of claims 1 to 4, wherein A in the general formulas (1) to (3) is represented by the following general formula (4).

(In the 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) Bond to an atom,
The group represented by the general formula (5) and R ^{1 to} R ¹⁵ which are not the bond each independently represent a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or carbon It is a number 1-10 alkoxy group. )

(In the general formula (5), each of R ^{16 to} R ²⁹ which is not the bond is independently a hydrogen atom, a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms In the case where b is 0 or 1 and b is 1, Rs of linked aromatic rings may be bonded to each other to form a fused ring). The organic light emitting device according to any one of claims 1 to 5 , 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 1 to 6 , wherein the formula weight of the structure represented by A is 240 to 1000. Alkylene which X ³ and X ⁴ in the above-mentioned general formula (3) may have a substituent whose atom which constitutes the shortest chain which connects A and a vinyl group in general formula (3) is 10 or more Group, provided that one or more non-adjacent methylene groups in the alkylene group may be substituted by -O- or -S- and one or more non-adjacent methylene groups not bound to A Is optionally substituted by -SO-, -SO _2- , -CO-, -COO-, -N (R ^Y )-, -CO-N (R ^Y )-or an arylene group, and R ^Y is hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group or an aralkyl group.) an organic light-emitting device according to any one of claims 1 to 7. The organic compound according to any one of claims 1 to 8 , wherein the first organic compound layer contains an electron acceptor 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. Light emitting element. A coating solution used for producing an organic light emitting device, comprising:
A non-crosslinked polymer, a first polymerizable compound capable of forming a crosslinked polymer, and a solvent,
The non-crosslinked polymer is a compound containing a repeating unit containing a structure having charge transportability, and the first polymerizable compound containing a structure having charge transportability,
The coating solution whose absolute value of the difference of the ionization potential of the said non-crosslinked polymer and the ionization potential of the crosslinked polymer formed by superposing | polymerizing a said 1st polymeric 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 film;
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, and a second step adjacent to the first organic compound layer Forming a second electrode on the second organic compound layer, and forming the second organic compound layer on the second organic compound layer,
The first polymerizable compound is a compound including a structure having charge transportability, and the non-crosslinked polymer and the crosslinked polymer both include a repeating unit including a structure having charge transportability,
The manufacturing method of the organic light emitting element whose absolute value of the difference of the ionization potential of the said non-crosslinked polymer and the ionization potential of the said crosslinked polymer is 0.2 eV or less. Lighting device including the organic light-emitting device according to any one of claims 1-9. Display device having organic light-emitting device according to any one of claims 1-9.

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