WO2012070575A1

WO2012070575A1 - Light emitting device and method for producing light emitting device

Info

Publication number: WO2012070575A1
Application number: PCT/JP2011/076913
Authority: WO
Inventors: 祥司美馬
Original assignee: 住友化学株式会社
Priority date: 2010-11-24
Filing date: 2011-11-22
Publication date: 2012-05-31
Also published as: JP2012114188A; TW201232865A

Abstract

Provided is a light emitting device having a structure that does not need to undergo a step for removing ink applied in unwanted locations when forming a light emitting layer according to a coating method, and provided with multiple organic EL elements having an easily-formed electron injection layer. One embodiment of this light emitting device is provided with a support substrate, and multiple organic EL elements disposed on the support substrate along a prescribed array direction and connected in series. A light emitting layer straddles the multiple organic EL elements and extends along the prescribed array direction. Pairs of electrodes each have, as viewed from one of thickness directions of the support substrate, an extended section that extends in such a manner as to protrude from the light emitting layer in the width direction. One of the electrodes of the pair of electrodes extends from the extended section in the array direction to the other electrode of the adjacent organic EL element in the array direction, and also has a connection section that is connected to the other electrode. The electron injection layer contains an ionic polymer.

Description

LIGHT EMITTING DEVICE AND LIGHT EMITTING DEVICE MANUFACTURING METHOD

The present invention relates to a light emitting device and a manufacturing method thereof.

An organic electroluminescence element (hereinafter, “electroluminescence” may be referred to as “EL”) is a type of light-emitting element that emits light when a voltage is applied. And a light emitting layer disposed between the electrodes. When a voltage is applied to the organic EL element, holes are injected from the anode and electrons are injected from the cathode. Light emission occurs when these holes and electrons are combined in the light emitting layer.

In addition, in an organic EL element having a configuration in which only a light emitting layer is provided between an anode and a cathode, it is difficult to obtain the desired light emitting characteristics. Therefore, a predetermined layer other than the light emitting layer is usually provided between the anode and the cathode. Is further provided. As such a layer, for example, an electron injection layer that facilitates electron injection from the cathode may be provided.

Furthermore, in order to obtain the desired light emission characteristics, a light emitting device in which a plurality of organic EL elements are connected in series has been proposed (see, for example, Patent Document 1).

FIG. 9 is a diagram schematically showing a light emitting device 2 in which a plurality (three in FIG. 9) of organic EL elements 1 are connected in series. FIG. 9A is a plan view of the light-emitting device 2, and FIG. 9B is a cross-sectional view of the light-emitting device 2.

The light emitting device 2 shown in FIG. 9 includes three organic EL elements 1. These three organic EL elements 1 are arranged along a predetermined arrangement direction X on the support substrate 3 and are connected in series.

Each organic EL element 1 shown in FIG. 9 includes a pair of

electrodes

4 and 5, and a light emitting layer 6 and an electron injection layer 7 provided between the electrodes. Hereinafter, of the pair of

electrodes

4 and 5, an electrode disposed near the support substrate 3 is referred to as a first electrode 4, and an electrode disposed farther from the support substrate 2 than the first electrode 4 is a second electrode. This is referred to as an electrode 5. One of the first and

second electrodes

4 and 5 functions as an anode, and the other functions as a cathode.

FIG. 9 shows the organic EL element 1 having a configuration in which the first electrode 4 functions as an anode and the second electrode 5 functions as a cathode. In this case, the organic EL element 1 is configured by laminating the first electrode 4, the light emitting layer 6, the electron injection layer 7, and the second electrode 5 on the support substrate 2 in this order. In consideration of element characteristics and process simplicity, not only the light emitting layer 6 and the electron injection layer 7 but also a predetermined layer different from these layers is provided between the first and

second electrodes

4 and 5. Sometimes.

As shown in FIG. 9, the first electrodes 4 of the organic EL elements 1 are discretely arranged at a predetermined interval in the arrangement direction X and are not electrically connected to each other. Similarly, the second electrodes 5 of the respective organic EL elements 1 are not electrically connected to each other because they are arranged at a predetermined interval in the arrangement direction X. Thus, the first electrodes 4 and the second electrodes 5 of the plurality of organic EL elements are not electrically connected to each other.

On the other hand, the first electrode 4 and the second electrode 5 of the organic EL element 1 adjacent in the arrangement direction X are physically connected and electrically connected to each other. Thus, the plurality of organic EL elements 1 constitutes a series connection. Specifically, the first electrode 4 is one of the arrangement directions X (hereinafter, “one of the arrangement directions X” may be referred to as “left”, and “the other of the arrangement directions X” may be referred to as right). Up to a position where the end (hereinafter also referred to as the left end) overlaps the right end (hereinafter also referred to as the right end) of the second electrode 5 of the organic EL element 1 adjacent to the left. It is formed so as to extend and is physically connected to the second electrode 5 of the organic EL element 1 adjacent to the left. Thus, the 1st electrode 4 and the 2nd electrode 5 of the organic EL element 1 which adjoin the arrangement direction X are physically connected, The some organic EL element 1 comprises a serial connection.

Next, a method for manufacturing the light emitting device shown in FIG. 9 will be described with reference to FIG.

First, the first electrode 4 is formed on the support substrate 3. Specifically, three first electrodes 4 are discretely formed on the support substrate 3 at predetermined intervals in the arrangement direction X (see FIG. 10A).

Next, an ink containing a material that becomes the light emitting layer 6 is applied onto the support substrate 3 by a predetermined application method. In general, it is difficult for the coating method to selectively apply ink (ink) in a pattern only to an intended portion, and ink is also applied to unnecessary portions such as between the first electrodes 4 (see FIG. 10 (2)). . Therefore, after applying the ink, a step of removing the ink applied to unnecessary portions is required (see FIG. 10 (3)). This ink can be removed by, for example, a method of wiping the ink using a cloth or cotton swab containing a solvent in which the ink is soluble, a laser ablation method, or the like.

Next, a pattern of the electron injection layer 7 is formed on the light emitting layer 6 (see FIG. 10 (4)). The electron injection layer 7 is generally made of an electron injection material that is unstable in the atmosphere. In general, the electron injection layer is made of Ba, BaO, LiF, NaF, or the like, and is usually formed in a vacuum atmosphere. Thereafter, the second electrode 5 is patterned (see FIG. 10 (5)). As a result, a light emitting device 2 including three organic EL elements 1 connected in series can be manufactured.

JP 2010-183116 A

The above-described conventional technique has a problem that the number of steps increases because a step of removing ink applied to unnecessary portions is required. Further, when removing the ink applied to unnecessary portions, there is a possibility that foreign matters may be mixed into the light emitting layer.

In general, since the electron injection material is unstable in the air atmosphere, the electron injection layer is formed in a vacuum atmosphere as described above. Therefore, there has been a demand for an electron injection material that can be formed by a simple process that does not require a vacuum atmosphere and that also functions as an electron injection layer.

Accordingly, an object of the present invention is to provide an electron injection layer that has a structure that does not require a step of removing ink applied to unnecessary portions when forming a light emitting layer by a coating method, and can be easily formed. A light emitting device including a plurality of organic EL elements and a method for manufacturing the same.

One embodiment of the present invention is a light-emitting device including a support substrate and a plurality of organic electroluminescence elements that are provided on the support substrate along a predetermined arrangement direction and connected in series.
Each organic electroluminescence element includes a pair of electrodes, a light emitting layer and an electron injection layer provided between the electrodes,
The light emitting layer extends along the predetermined arrangement direction across the plurality of organic electroluminescence elements,
Each of the pair of electrodes extends so as to protrude from the light emitting layer in a width direction perpendicular to both the thickness direction of the support substrate and the arrangement direction when viewed from one thickness direction of the support substrate. Part
One electrode of the pair of electrodes extends from the extension portion to the other electrode of the organic electroluminescence element adjacent in the arrangement direction, and is connected to the other electrode. Further comprising
The electron injection layer relates to a light emitting device including an ionic polymer.

One embodiment of the present invention further includes an auxiliary electrode provided in contact with the electrode,
The auxiliary electrode relates to a light emitting device having a sheet resistance lower than that of an electrode in contact with the auxiliary electrode.

Further, one embodiment of the present invention relates to a light emitting device in which the auxiliary electrode is provided in contact with an electrode having a higher sheet resistance among the pair of electrodes.

Further, one embodiment of the present invention relates to a light-emitting device in which only the electrode having the lower sheet resistance among the pair of electrodes has the connection portion.

Further, according to one aspect of the present invention, the extending portion includes a first extending portion that extends so as to protrude from the light emitting layer in one of the width directions when viewed from one of the thickness directions, and the other in the width direction. And a second extending portion extending so as to protrude from the light emitting layer.

One embodiment of the present invention is a light-emitting device including a support substrate and a plurality of organic electroluminescence elements that are provided on the support substrate along a predetermined arrangement direction and connected in series.
Each organic electroluminescence element includes a pair of electrodes, a light emitting layer and an electron injection layer provided between the electrodes,
The light emitting layer extends along the predetermined arrangement direction across the plurality of organic electroluminescence elements,
Each of the pair of electrodes has an extending portion that extends from the light emitting layer in the width direction perpendicular to the thickness direction of the support substrate and the arrangement direction when viewed from one thickness direction of the support substrate. And
One electrode of the pair of electrodes extends from the extending portion to the other electrode of the organic electroluminescence element adjacent in the arrangement direction and is connected to the other electrode. A method for manufacturing a light emitting device further comprising:
The ink containing the material to be the light emitting layer is continuously applied across the plurality of electrodes arranged on the support substrate along the predetermined arrangement direction, and light is emitted by solidifying the applied coating film. Forming a layer;
And a step of forming the electron injection layer by coating and forming an ink containing an ionic polymer.
In other words, in the step of forming the light emitting layer, the ink containing the material to be the light emitting layer is continuously applied along the predetermined arrangement direction across the region where the plurality of organic electroluminescent elements are arranged when completed. The light emitting layer is formed by solidifying the coated film.

Further, according to one embodiment of the present invention, a method of applying the ink including the material to be the light emitting layer is a cap coat method, a slit coat method, a spray coat method, or a printing method. The present invention relates to a method for manufacturing a light emitting device.

Further, one embodiment of the present invention relates to a method for manufacturing a light-emitting device in which ink is applied in an air atmosphere in the step of forming the electron injection layer.

According to the present invention, a plurality of electron injection layers having a structure that does not require a step of removing ink applied to unnecessary portions when forming a light emitting layer by a coating method and that can be easily formed. A light-emitting device including the organic EL element and a manufacturing method thereof can be realized.

It is a top view which shows the light-emitting device 11 of 1st Embodiment of this invention. 6 is a diagram for explaining a manufacturing process of the light emitting device 11. FIG. 6 is a diagram for explaining a manufacturing process of the light emitting device 11. FIG. 6 is a diagram for explaining a manufacturing process of the light emitting device 11. FIG. FIG. 5 is a diagram schematically showing the light emitting device 31 of the second embodiment. FIG. 6 is a diagram schematically showing a light emitting device 41 according to the third embodiment. FIG. 7 is a diagram schematically showing a light emitting device 51 of the fourth embodiment. FIG. 8 is a diagram showing a light emitting device 61 according to the fifth embodiment. FIG. 9 is a diagram schematically showing a light emitting device 2 in which a plurality of organic EL elements 1 are connected in series. FIG. 10 is a diagram for explaining a manufacturing process of the light emitting device 2.

1) Configuration of Light Emitting Device First, the configuration of the light emitting device will be described below with reference to the drawings. The light emitting device of this embodiment is used for a light source such as a lighting device, a liquid crystal display device, and a scanner. FIG. 1 is a plan view schematically showing a light emitting device 11 according to a first embodiment of the present invention. The light emitting device 11 includes a support substrate 12 and a plurality of organic EL elements 13 provided on the support substrate 12 and connected in series.

The predetermined arrangement direction X is set in a direction perpendicular to the thickness direction Z of the support substrate 12. That is, the arrangement direction X is set parallel to the main surface of the support substrate 12. In the present embodiment, as shown in FIG. 1, the plurality of organic EL elements 13 are arranged along a predetermined straight line, but may be arranged along a predetermined curve. When a plurality of organic EL elements 13 are arranged along a predetermined curve, the arrangement direction X corresponds to the tangential direction of the predetermined curve.

The number of organic EL elements 13 provided on the support substrate 12 is appropriately set according to the design. In the first embodiment, a light emitting device 11 provided with three organic EL elements 13 will be described below.

Each organic EL element 13 includes a pair of

electrodes

14 and 15, and a light emitting layer 16 and an electron injection layer 20 provided between the

electrodes

14 and 15.

Any one of the pair of

electrodes

14 and 15 functions as an anode of the organic EL element 13, and the other electrode functions as a cathode of the organic EL element 13. Hereinafter, of the pair of

electrodes

14 and 15, an electrode disposed near the support substrate 12 is referred to as a first electrode 14, and the other electrode disposed apart from the support substrate 12 is referred to as a second electrode 15. Hereinafter, as an example, an organic EL element in which the first electrode 14 functions as an anode and the second electrode 15 functions as a cathode will be described.

The electron injection layer 20 is provided between the light emitting layer 16 and the electrode functioning as the cathode of the pair of

electrodes

14 and 15. The electron injection layer 20 is preferably disposed at a position in contact with the cathode. As described above, in the present embodiment, the first electrode 14 functions as an anode and the second electrode 15 functions as a cathode. Therefore, the organic EL element includes the first electrode 14, the light emitting layer 20, the electron injection layer 16, the second electrode. The electrodes 15 are stacked in this order. As another embodiment, when the first electrode 14 functions as a cathode and the second electrode 15 functions as an anode, the organic EL element is supported by the first electrode, the electron injection layer, the light emitting layer, and the second electrode. The layers are stacked in this order from the substrate side.

A predetermined layer other than the light emitting layer 16 and the electron injection layer 20 may be further provided between the first and

second electrodes

14 and 15 as necessary.

The light emitting layer 16 extends along the arrangement direction X across the plurality of organic EL elements 13, and the plurality of organic EL elements 13 share one light emitting layer 16. That is, in this embodiment, in the plurality of organic EL elements 13 connected in series, from the light emitting layer 16 of the organic EL element 13 provided at one end in the arrangement direction X (left end in FIG. 1), the other end in the arrangement direction X (see FIG. The light emitting layer extending along the arrangement direction X is continuously and integrally formed up to the light emitting layer 16 of the organic EL element 13 provided at the right end in FIG.

The electron injection layer 20 preferably extends along the arrangement direction X across the plurality of organic EL elements 13, similarly to the light emitting layer 16. This is because, as will be described later, when the electron injection layer is formed by a coating method, a step of removing the electron injection layer formed at an unnecessary portion can be omitted.

When the electron injection layer 20 is formed so as to cover the light emitting layer 16, a site where the first electrode and the second electrode are connected only through the electron injection layer 20 is generated. In such a configuration, if the electron injection layer 20 exhibits conductivity, the first electrode and the second electrode may be electrically connected. Therefore, when the electron injection layer 20 exhibits conductivity, The electron injection layer 20 is preferably formed inside the light emitting layer 16 in plan view. When the electron injection layer 20 is formed in this way, a portion where the first electrode and the second electrode are connected only through the electron injection layer 20 does not occur, and there is no conductivity between the first electrode and the second electrode. Since a light emitting layer having a low thickness inevitably intervenes, leakage current can be prevented from occurring between the first electrode and the second electrode.

A predetermined layer different from the light emitting layer and the electron injection layer may be provided between the first and

second electrodes

14 and 15. The predetermined layer may extend along the arrangement direction X across the plurality of organic EL elements 13. Further, the predetermined layer may be formed so as to be separated for each organic EL element 13. In the case where a predetermined layer different from the light emitting layer 16 and the electron injection layer 20 is formed by a coating method, the predetermined layer is arranged in the arrangement direction across the plurality of organic EL elements 13 like the light emitting layer 16. It preferably extends along X. This is because a step of removing a layer formed at an unnecessary portion can be omitted as will be described later.

The first and second electrodes 14 and 15 (a pair of electrodes) have extending

portions

17 and 18, respectively. The extending

portions

17 and 18 extend so as to protrude from the light emitting layer 16 in the width direction Y when viewed from one side in the thickness direction Z of the support substrate 12 (hereinafter sometimes referred to as “in plan view”). Exists. The width direction Y is a direction perpendicular to the thickness direction Z of the support substrate and the arrangement direction X. The extending portion 17 of the first electrode 14 is formed integrally with the first electrode 14. The extending portion 18 of the second electrode 15 is formed integrally with the second electrode 15. The first electrode 14 and the second electrode 15 (a pair of electrodes) constituting each organic EL element 13 are not in contact with each other for each organic EL element 13. Moreover, in each organic EL element 13, it arrange | positions so that the extension part 17 of the 1st electrode 14 and the extension part 18 of the 2nd electrode 15 may not overlap by planar view. In the present embodiment, the extending portion 17 of the first electrode 14 extends in the width direction Y from the left end portion (hereinafter also referred to as the left end portion) of the portion facing the second electrode 15 in the first electrode 14. Extend. The extending portion 18 of the second electrode 15 extends in the width direction Y from the right end portion (hereinafter sometimes referred to as the right end portion) of the second electrode 15 facing the first electrode 14. Yes. Therefore, the extending portion 17 of the first electrode 14 and the extending portion 18 of the second electrode 15 do not overlap in plan view but are electrically insulated.

One electrode of the first and second electrodes 14 and 15 (a pair of electrodes) has a connection portion. The connecting portion extends in the arrangement direction X from the extending portion to the other electrode of the organic EL element adjacent in the arrangement direction X, and is connected to the other electrode. Note that not only one of the first and

second electrodes

14 and 15 but also the other electrode may have a connecting portion. That is, the other electrode of the pair of electrodes also extends in the arrangement direction X from the extension portion to one electrode of the organic EL element adjacent in the arrangement direction X, and is connected to the one electrode. You may have a connection part.

In the present embodiment, the first electrode 14 corresponding to one of the first and second electrodes 14 and 15 (a pair of electrodes) has a connection portion 19. That is, the first electrode 14 extends to the left from the extending portion 17 of the first electrode 14 to the extending portion 18 of the second electrode 15 (the other electrode) of the organic EL element disposed on the left. Connecting portion 19 is provided. As described above, the connection portion 19 of the first electrode 14 overlaps with the extension portion 18 of the second electrode 15 (the other electrode) of the organic EL element disposed on the left side in a plan view, and directly at the overlapping portion. It is connected to the second electrode 15 (the other electrode).

The extending portion 18 extending in the width direction Y from the light emitting layer 16 in plan view is provided in one or the other of the width directions Y, but is preferably provided in both the width directions Y. That is, the

extended portions

17 and 18 protrude from the light emitting layer 16 in the width direction Y and the first extending

portions

17a and 18a extending so as to protrude from the light emitting layer in one of the width directions in a plan view. It is preferable to include the second extending portions 17b and 18b extending so as to. Thus, by providing the

extension parts

17 and 18 extended in both the width directions Y from the light emitting layer 16 in planar view, the 1st electrode 14 and the 2nd electrode 15 of the adjacent organic EL element 13 are width direction. It will be connected at both ends of Y.

Further, among the plurality of organic EL elements 13 constituting the series connection, the first electrode 14 of the organic EL element 13 arranged on the leftmost side and the second electrode of the organic EL element 13 arranged on the rightmost side Are respectively connected to wirings electrically connected to a power supply unit (not shown). As a result, power is supplied from the power supply unit to the plurality of organic EL elements 13 constituting the series connection, and each organic EL element emits light.

Each organic EL element 13 is supplied with power from the connecting portion. In the present embodiment, the organic EL elements 13 are supplied with power from both ends in the width direction Y by providing the extending

portions

17 and 18 extending in the width direction Y from the light emitting layer 16 in plan view. As the organic EL element 13 is further away from the site to be fed, the luminance decreases due to a voltage drop. In this embodiment, as the distance from the extending

portions

17 and 18 in the width direction Y, that is, in the center portion in the width direction Y, the luminance decreases due to the voltage drop. Since power is supplied from the end portion, the influence of the voltage drop can be suppressed as compared with the element configuration that is supplied from one end portion in the width direction Y, and thus luminance unevenness (spots) can be suppressed.

2) Method for Manufacturing Light-Emitting Device The method for manufacturing a light-emitting device according to the present embodiment includes a support substrate and a plurality of organic electroluminescent elements provided on the support substrate along a predetermined arrangement direction and connected in series. Each organic electroluminescence element includes a pair of electrodes, a light emitting layer and an electron injection layer provided between the electrodes, and the light emitting layer spans the plurality of organic electroluminescence elements, Each of the pair of electrodes extends along a predetermined arrangement direction, and each of the pair of electrodes has a light emitting layer in a thickness direction of the support substrate and a width direction perpendicular to the arrangement direction when viewed from one thickness direction of the support substrate. An organic electroluminescence element having an extending portion extending so as to protrude from the first electrode, wherein one of the pair of electrodes is adjacent to the arrangement direction A method of manufacturing a light emitting device further including a connecting portion that extends in the arrangement direction from the extending portion to the other electrode and is connected to the other electrode, the ink including a material that becomes the light emitting layer A step of forming a light emitting layer by solidly applying the applied coating across the plurality of electrodes arranged on the support substrate along the predetermined arrangement direction, and solidifying the applied coating; Forming the electron injection layer by coating and forming an ink containing a polymer.

Hereinafter, a method for manufacturing a light emitting device will be described with reference to FIGS.

First, the support substrate 12 is prepared. In this step, a support substrate 12 on which a drive circuit (not shown) for driving the organic EL element 13 is formed in advance may be prepared.

Next, the first electrode 14 is patterned on the support substrate 12 (see FIG. 2). For example, a conductive film is formed on the support substrate 12 by sputtering or vapor deposition, and then the first electrode 14 is patterned by patterning the conductive film into a predetermined shape by photolithography. Note that the first electrode 14 may be pattern-formed only at a predetermined portion by a mask vapor deposition method or the like without performing a photolithography process. Moreover, you may form the 1st electrode 14 by apply | coating the ink containing an electroconductive material with the apply | coating method, and solidifying the apply | coated coating film. Alternatively, the first electrode 14 may be formed by transferring a conductive thin film by a laminating method. Furthermore, you may prepare the support substrate 12 in which the 1st electrode 14 was formed previously.

Next, the light emitting layer 16 is formed on the support substrate 12 (see FIG. 3). For example, ink containing a material that becomes the light emitting layer 16 is continuously applied across the plurality of first electrodes 14 arranged on the support substrate 12 along a predetermined arrangement direction, and the applied coating film is solidified. That is, by applying the ink including the material to be the light emitting layer 16 continuously along the arrangement direction X across the region where the plurality of organic EL elements 13 are arranged when completed, and solidifying the applied coating film The light emitting layer 16 can be formed.

Coating film can be solidified by natural drying, heat drying, vacuum drying, or the like. Moreover, when a coating film contains the material polymerized by applying energy, the coating film can be solidified by heating or light irradiation.

Next, the electron injection layer 20 is formed on the support substrate 12 (see FIG. 4). For example, the electron injection layer 20 can be formed by continuously applying an ink containing an ionic polymer along the arrangement direction X onto the light emitting layer 16 and solidifying the applied coating film. That is, the ink containing the ionic polymer is continuously applied along the arrangement direction X across the region where the plurality of organic EL elements 13 are arranged, and the applied coating film is solidified to solidify the electron injection layer 20. Can be formed. Ionic polymers are relatively stable in the atmosphere and can facilitate electron injection from the cathode. Details of the ionic polymer that can be applied to the present invention will be described later.

Since the ionic polymer is relatively stable in the air, the ink can be applied in an air atmosphere. Thus, since it is not necessary to introduce a vacuum atmosphere as in the conventional technique, the step of forming the electron injection layer can be simplified as compared with the conventional technique. Furthermore, the step of solidifying the film when applied is also preferably performed in an air atmosphere.

As described above, when the electron injection layer 20 exhibits conductivity, the electron injection layer 20 is preferably formed inside the light emitting layer 16 in plan view.

Next, the second electrode 15 is formed on the support substrate 12. The film formation method of the second electrode 15 includes a vapor deposition method. For example, the second electrode 15 can be patterned by using a metal mask or the like. In addition, since the electron injection layer 20 containing the ionic polymer is stable in the air atmosphere, the second electrode 15 can be formed using a coating method or a laminating method in the air atmosphere. When the second electrode 15 is formed by a coating method, the second electrode 14 is formed by applying ink containing a conductive material by a predetermined coating method and solidifying the coated film. In the laminating method, the second electrode 14 is formed by transferring a conductive thin film.

As described above, a predetermined layer different from the light emitting layer 16 and the electron injection layer 20 may be provided between the first and

second electrodes

14 and 15. The predetermined layer is preferably formed by a coating method as in the case of the light emitting layer. That is, an ink containing a material that becomes a predetermined layer different from the light emitting layer and the electron injection layer is continuously applied along the arrangement direction X across a region where the plurality of organic EL elements 13 are arranged at the time of completion. The predetermined layer is preferably formed by solidifying the coated film. When a predetermined layer different from the light emitting layer and the electron injection layer is formed by a dry method such as vapor deposition, the predetermined layer may be selectively formed only on the first electrode 14.

Examples of the ink application method include a cap coating method, a slit coating method, a spray coating method, a printing method, an ink jet method, and a nozzle printing method. Among these methods, a large area can be efficiently applied. Possible cap coating methods, slit coating methods, spray coating methods and printing methods are preferred.

In the light emitting device 11 described above, the first electrode 14 and the second electrode 15 of the adjacent organic EL elements 13 are connected in the region protruding in the width direction Y from the region where the light emitting layer 16 is formed in plan view. Thereby, the adjacent organic EL elements 13 are connected in series. Therefore, it is not necessary to connect the first electrode 14 and the second electrode 15 of the adjacent organic EL elements 13 in the region between the organic EL elements 13. For this reason, a light emitting layer or the like may be formed in a region between adjacent organic EL elements 13, whereby a light emitting layer formed in a region between adjacent organic EL elements 13 when forming a light emitting layer by a coating method. The step of removing can be omitted. Therefore, even if it is a coating method such as a cap coat method that is relatively poor at applying a fine pattern, a plurality of organic EL elements 13 connected in series can be easily produced.

Also, for the same reason as described above, an electron injection layer can be easily formed using an ionic polymer.

Further, as described above, since the ionic polymer is relatively stable in the air, the electron injection layer can be applied and formed in an air atmosphere.

FIG. 5 is a diagram schematically showing a light emitting device 31 according to the second embodiment of the present invention. The light emitting device 31 of this embodiment is different from the light emitting device 11 of the first embodiment described above only in the shapes of the first electrode 14 and the second electrode 15. Hereinafter, only the first electrode 14 and the second electrode 15 of the second embodiment will be described. In the second embodiment, portions corresponding to those of the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

In this embodiment, in addition to the first electrode 14, the second electrode 15 also has a connection portion 32. That is, the second electrode 15 has a connecting portion 32 that extends from the extending portion to the first electrode 14 of the organic EL element adjacent in the arranging direction X in the arranging direction X and is connected to the first electrode 14. In the pair of organic EL elements 13 adjacent to each other in the arrangement direction X, the connection part 19 of the first electrode 14 of the organic EL element 13 arranged on the right side extends from the extension part 17 of the first electrode 14 to the left side. To do. The connection part 32 of the second electrode 15 of the organic EL element 13 arranged on the left side extends from the extension part 18 of the second electrode 15 to the right side. The connection part 19 of these 1st electrodes 14 and the connection part 32 of the 2nd electrode 15 overlap, and the 1st electrode 14 and 2nd electrode 15 of a pair of adjacent organic EL element 13 are connected.

FIG. 6 is a diagram schematically showing a light emitting device 41 according to a third embodiment of the present invention. The light emitting device 41 of this embodiment differs from the light emitting device 11 of the first embodiment described above only in the shapes of the first electrode 14 and the second electrode 15. Hereinafter, only the first electrode 14 and the second electrode 15 of the third embodiment will be described. In the third embodiment, portions corresponding to those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

In the present embodiment, the first electrode 14 does not have the connection portion 19, and conversely, the second electrode 15 has the connection portion 42. That is, the second electrode 15 extends in the arrangement direction X from the extension portion to the first electrode 14 of the organic EL element adjacent in the arrangement direction X, and is connected to the first electrode 15. Have

In the light emitting device 11 of the first embodiment shown in FIG. 1, only the first electrode 14 has the connection portion 19. Conversely, in the light emitting device 41 of the third embodiment shown in FIG. 6, only the second electrode 15 is connected. Part 42. In the case where only one of the first and

second electrodes

14 and 15 has a connection portion, which electrode has a connection portion may be appropriately selected according to the design. Of the first and second electrodes 14 and 15 (a pair of electrodes), it is preferable that only the electrode having the lower sheet resistance has a connection portion. That is, when the sheet resistance of the first electrode 14 is lower than the sheet resistance of the second electrode 15, it is preferable that only the first electrode 14 has the connection portion 19 as in the light emitting device 11 of the first embodiment shown in FIG. 1. . Conversely, when the sheet resistance of the second electrode 15 is lower than the sheet resistance of the first electrode 14, only the second electrode 15 may have the connection portion 42 as in the light emitting device 41 of the third embodiment shown in FIG. 7. preferable.

Any one of the first and

second electrodes

14 and 15 is configured by a member that exhibits light transmittance in order to emit light emitted from the light emitting layer 16 to the outside. In general, a member exhibiting light transmittance has a higher sheet resistance than a conductive member exhibiting opaqueness. For this reason, one of the first and

second electrodes

14 and 15 that exhibits optical transparency usually has a higher sheet resistance. Therefore, it is usually preferable that only the other electrode, which is not one electrode exhibiting optical transparency, has a connection portion.

When driving the light-emitting device, a voltage drop also occurs in the connection part constituted by the conductor, but by providing the connection part only on the electrode constituted by a member having a low sheet resistance, the voltage generated in the connection part Lowering can be suppressed, and as a result, power consumption can be reduced.

FIG. 7 is a diagram schematically showing a light emitting device 51 according to a fourth embodiment of the present invention. The light emitting device 51 of the present embodiment further includes an auxiliary electrode provided in contact with the electrode. The light emitting device 51 of this embodiment differs from the light emitting devices of the above-described embodiments only in the presence or absence of an auxiliary electrode. Below, only the auxiliary electrode of 4th Embodiment is demonstrated. In the fourth embodiment, portions corresponding to those of the above-described embodiments are denoted by the same reference numerals, and redundant description is omitted. In FIG. 7, the region indicating the auxiliary electrode is hatched.

The auxiliary electrode is provided in contact with at least one of the first electrode 14 and the second electrode 15 (a pair of electrodes). For example, when the auxiliary electrode is provided in contact with the first electrode 14 and the second electrode 15, two of the auxiliary electrode provided in contact with the first electrode 14 and the auxiliary electrode provided in contact with the second electrode 15. Two auxiliary electrodes are provided.

The auxiliary electrode is composed of a member having a sheet resistance lower than that of the electrode in contact with the auxiliary electrode. The auxiliary electrode 52 is preferably provided in contact with the electrode having the higher sheet resistance among the first electrode 14 and the second electrode 15 (a pair of electrodes). As described above, any one of the first and

second electrodes

14 and 15 is configured by a member that exhibits light transmittance in order to emit light emitted from the light emitting layer 16 to the outside. One electrode exhibiting light transmittance usually has a higher sheet resistance than the other electrode. Therefore, it is usually preferable that the auxiliary electrode 52 is provided in contact with the light transmissive electrode of the first and

second electrodes

14 and 15. In the light emitting device 51 of the present embodiment shown in FIG. 8, the auxiliary electrode 52 is provided in contact with the first electrode 14 provided as an electrode exhibiting light transmittance.

The auxiliary electrode 52 is usually opaque because the sheet resistance is lower than the electrode with which the auxiliary electrode 52 is in contact. When the opaque auxiliary electrode 52 is provided in contact with the electrode through which light is transmitted, the auxiliary electrode 52 may block the light. Therefore, the auxiliary electrode 52 is preferably provided in a region where the light emitting layer 16 does not emit light in principle in a plan view.

The light emitting layer 16 can emit light in principle in a region where the first electrode 14 and the second electrode 15 are opposed to each other in plan view (hereinafter sometimes referred to as a facing region). For this reason, the region that does not emit light in principle corresponds to a region excluding the opposing region of the first electrode 14 and the second electrode 15 in plan view. Therefore, it is preferable that the auxiliary electrode 52 be provided in a region excluding a region where the first electrode 14 and the second electrode 15 are opposed in plan view.

The auxiliary electrode may be formed in the opposing region of the first electrode 14 and the second electrode 15 in a plan view in consideration of the light emission amount and the voltage drop. For example, the auxiliary electrode may be provided in the periphery of the opposing region and the opposing region. An electrode may be formed. For example, the auxiliary electrode may be formed in a lattice shape, a stripe shape, or a linear shape in the opposing region in plan view, and the auxiliary electrode formed in the opposing region may be connected to the auxiliary electrode formed in the periphery of the opposing region.

As the material of the auxiliary electrode, a material having high electrical conductivity is preferably used, and examples thereof include Al, Ag, Cu, Au, and W. An alloy such as Al—Nd, Ag—Pd—Cu may be used for the auxiliary electrode. The thickness of the auxiliary electrode is appropriately set depending on the required sheet resistance, and is, for example, 50 nm to 2000 nm. The auxiliary electrode may be constituted by a single layer, or may be a laminate in which a plurality of layers are laminated. For example, a predetermined function is exhibited for the purpose of improving the adhesion with the support substrate 12 (glass substrate or the like) or the first electrode 14 (ITO thin film or the like) and protecting the metal surface from oxygen or moisture. The layer may be laminated on a thin film made of a material having high electrical conductivity. For example, a laminated body composed of a thin film made of Mo, Mo—Nb, Cr, or the like and sandwiching a thin film made of a material having high electrical conductivity can be used as the auxiliary electrode.

In addition, although each embodiment mentioned above has shown the light-emitting device by which one series connection was comprised by the some organic EL element, even if it is a light-emitting device by which the some series connection was comprised by the some organic EL element, this book The invention can be suitably applied. Further, the present invention can be suitably applied even to a light-emitting device configured by using both serial connection and parallel connection.

FIG. 8 is a diagram showing a light emitting device 61 according to a fifth embodiment of the present invention. The light emitting device 61 of the present embodiment is a light emitting device having a configuration in which two rows of serial connections are connected in parallel. Each series connection is composed of three organic EL elements. In the two columns in series connection, one end and the other end of the electrodes of each organic EL element are electrically connected and connected in parallel.

In a light-emitting device in which one series connection is configured by a plurality of organic EL elements, the voltage of a drive source that drives the elements increases as the number of organic EL elements increases. The supply voltage required for the source can be moderately suppressed.

Hereinafter, the configurations of the support substrate 12 and the organic EL element 13 will be described in more detail.

As described above, not only the light emitting layer 16 and the electron injection layer 20 but also a predetermined layer different from the light emitting layer 16 and the electron injection layer 20 may be further provided between the first and

second electrodes

14 and 15. Examples of the layer provided between the cathode and the light emitting layer include an electron transport layer and a hole blocking layer.

The hole blocking layer has a function of blocking hole transport. In the case where the electron injection layer and / or the electron transport layer have a function of blocking hole transport, these layers may also serve as the hole blocking layer.

Examples of the layer provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer. When both the hole injection layer and the hole transport layer are provided between the anode and the light-emitting layer, the layer in contact with the anode is called a hole injection layer, and the layers other than the hole injection layer are positive. It is called a hole transport layer.

The hole injection layer has a function of improving the hole injection efficiency from the anode. The hole transport layer has a function of improving hole injection from a layer in contact with the surface on the anode side. The electron blocking layer has a function of blocking electron transport. When the hole injection layer and / or the hole transport layer has a function of blocking electron transport, these layers may also serve as an electron blocking layer.

Note that the electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer.

An example of a layer structure that can be taken by the organic EL element of the present embodiment is shown below.
a) Anode / hole injection layer / light emitting layer / electron injection layer / cathode b) Anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode c) Anode / hole injection layer / hole transport Layer / light emitting layer / electron injection layer / cathode d) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode e) anode / light emitting layer / electron injection layer / cathode f) Anode / light-emitting layer / electron transport layer / electron injection layer / cathode (Here, the symbol “/” indicates that the layers sandwiching the symbol “/” are stacked adjacent to each other. The same applies hereinafter.)

The organic EL element of this embodiment may have two or more light emitting layers. In any one of the layer configurations of a) to f) above, when the laminate sandwiched between the anode and the cathode is referred to as “structural unit A”, the configuration of an organic EL element having two light emitting layers is obtained. The layer structure shown in the following g) can be given. Note that the two (structural unit A) layer configurations may be the same or different.
g) Anode / (constituent unit A) / charge generation layer / (constituent unit A) / cathode

Further, when “(constituent unit A) / charge generation layer” is “constituent unit B”, examples of the constitution of the organic EL element having three or more light emitting layers include the layer constitution shown in the following h).
h) Anode / (Structural unit B) x / (Structural unit A) / Cathode

Note that the symbol “x” represents an integer of 2 or more, and (Structural unit B) x represents a stacked body in which the structural unit B is stacked in x stages. A plurality of (the structural unit B) may have the same or different layer structure.

Here, the charge generation layer is a layer that generates holes and electrons by applying an electric field. Examples of the charge generation layer include a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide, or the like.

Note that the organic EL element may be covered with a sealing member such as a sealing film and a sealing plate for hermetically sealing the element.

The organic EL elements are laminated on the support substrate in order from the left layer in the layer configurations of a) to h) given as an example, or are laminated on the support substrate in order from the right layer. In the layer configurations of a) to h) given as examples, the first electrode 14 corresponds to the anode when stacked on the support substrate sequentially from the left layer, that is, when stacked on the support substrate sequentially from the anode. The second electrode 15 corresponds to the cathode. Conversely, in the layer configurations of a) to h) given as an example, when the layers are stacked on the support substrate sequentially from the right layer, that is, when the layers are stacked on the support substrate sequentially from the cathode, the first electrode 14 is the cathode. The second electrode 15 corresponds to the anode.

Organic EL elements include (1) a bottom emission type, (2) a top emission type, and (3) a dual emission type. The bottom emission type organic EL element emits light to the outside through a support substrate. The top emission type organic EL element emits light to the outside from the side opposite to the support substrate. The double-sided light emitting organic EL element emits light to the outside from both the support substrate side and the opposite side of the support substrate. The present invention can be applied to any of bottom emission type, top emission type, and double-sided emission type organic EL elements. In the bottom emission type organic EL element, since light is emitted through the first electrode 14, the first electrode 14 is composed of an electrode exhibiting light transmittance, and conversely, the second electrode is composed of an electrode reflecting normal light. The In the top emission type organic EL element, since light is emitted through the second electrode, the second electrode 15 is constituted by an electrode exhibiting light transmittance, and conversely, the first electrode 14 is constituted by an electrode reflecting normal light. The In the double-sided light emitting organic EL element, both the first and

second electrodes

14 and 15 are composed of electrodes exhibiting light transmittance.

<Support substrate>
As the support substrate, one that is not chemically changed in the process of manufacturing the organic EL element is suitably used. For example, glass, plastic, a polymer film, a silicon plate, and a laminate of these are used. A drive substrate in which a drive circuit for driving the organic EL element is formed in advance may be used as the support substrate. In the case where a bottom emission type or double-sided light emitting type organic EL element configured to emit light through a support substrate is mounted on the support substrate, a substrate exhibiting light transmittance is used as the support substrate.

<Anode>
In the case of an organic EL element configured to emit light emitted from the light emitting layer through the anode, an electrode exhibiting optical transparency is used for the anode. As the electrode exhibiting light transmittance, a thin film of metal oxide, metal sulfide, metal or the like can be used, and an electrode having high electrical conductivity and light transmittance is preferably used. Specifically, a thin film made of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, or the like is used. Among these, ITO, IZO Or a thin film made of tin oxide is preferably used. Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. The organic transparent conductive film can be produced by applying an organic conductive material such as polythiophene.

The film thickness of the anode is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

<Hole injection layer>
As the hole injection material constituting the hole injection layer, metal oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanines, amorphous carbon, Examples thereof include polyaniline and polythiophene derivatives.

Examples of the method for forming the hole injection layer include film formation from a solution containing a hole injection material. For example, a hole injection layer can be formed by coating a film containing a hole injection material by a predetermined coating method and solidifying the solution.

Solvents used for film formation from solution include chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, and ketones such as acetone and methyl ethyl ketone. Examples thereof include solvents, ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate, and water.

The film thickness of the hole injection layer is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

<Hole transport layer>
As the hole transport material constituting the hole transport layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, Triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylene vinylene) or Examples thereof include derivatives thereof.

Among these, hole transport materials include polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly Polymeric hole transport materials such as arylamine or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferred, and polyvinylcarbazole or derivatives thereof are more preferred. , Polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

Examples of the method for forming the hole transport layer include film formation from a solution containing a hole transport material. For example, a hole transport layer can be formed by coating a film containing a hole transport material by a predetermined coating method and solidifying the solution. When a low molecular hole transport material is used, the film may be formed using a solution in which a polymer binder is further mixed with the hole transport material.

Solvents used for film formation from solution include, for example, chlorine solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, and ketones such as acetone and methyl ethyl ketone. Examples thereof include ester solvents such as system solvents, ethyl acetate, butyl acetate, and ethyl cellosolve acetate.

As the polymer binder to be mixed, those that do not extremely inhibit charge transport are preferable, and those that weakly absorb visible light are preferably used. For example, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, poly Examples thereof include vinyl chloride and polysiloxane.

The film thickness of the hole transport layer is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. .

<Light emitting layer>
The light emitting layer is usually formed of an organic substance that mainly emits fluorescence and / or phosphorescence, or an organic substance and a dopant that assists the organic substance. For example, a dopant is added in order to improve luminous efficiency and change the emission wavelength. The organic substance contained in the light emitting layer may be a low molecular compound or a high molecular compound. Since a high molecular compound having a generally higher solubility in a solvent than a low molecular compound is preferably used in the coating method, the light-emitting layer preferably contains a high molecular compound, and the number average molecular weight in terms of polystyrene as the high molecular compound Preferably contain from 10 ³ to 10 ⁸ compounds. Examples of the light emitting material constituting the light emitting layer include the following dye materials, metal complex materials, polymer materials, and dopant materials.

(Dye material)
Examples of dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds. Pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, coumarin derivatives, and the like.

(Metal complex materials)
Examples of the metal complex material include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Ir, Pt, etc. as a central metal, and oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline. Examples include metal complexes having a structure as a ligand, such as metal complexes having light emission from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, and benzoxazolyl zinc. A complex, a benzothiazole zinc complex, an azomethylzinc complex, a porphyrin zinc complex, a phenanthroline europium complex, and the like can be given.

(Polymer material)
As polymer materials, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinyl carbazole derivatives, the above dye materials and metal complex light emitting materials are polymerized. Things can be mentioned.

Among the luminescent materials described above, materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.

In addition, examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.

In addition, examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Among these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.

(Dopant material)
Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like. Note that the thickness of such a light emitting layer is usually about 2 nm to 200 nm.

The light emitting layer is formed, for example, by film formation from a solution. The light emitting layer is formed, for example, by applying a solution containing a light emitting material by a predetermined application method and further solidifying the solution. Examples of the solvent used for film formation from a solution include the same solvents as those used for forming a hole injection layer from the above solution.

<Electron transport layer>
As an electron transport material constituting the electron transport layer, an oxadiazole derivative, anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, Fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like can be given.

Examples of the method for forming the electron transport layer include a vapor deposition method and a film formation method from a solution. In the case of forming a film from a solution, a polymer binder may be used in combination.

The film thickness of the electron transport layer is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

<Electron injection layer>
The electron injection layer includes an ionic polymer. As an ionic polymer constituting the electron injection layer, for example, a structural unit containing one or more groups selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) The polymer which has is mentioned. As one form of the ionic polymer, a structural unit containing one or more groups selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2) Examples thereof include a polymer having 15 to 100 mol%.

-(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 (1)
(In Formula (1), Q ¹ represents a divalent organic group, Y ¹ represents —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ^— or —PO ₃ ²⁻ , and M ¹ represents a metal cation. Or an ammonium cation with or without a substituent, and Z ¹ is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ^−. , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ^- , N1 represents an integer of 0 or more, a1 represents an integer of 1 or more, b1 represents an integer of 0 or more, provided that a1 and b1 are charges of the group represented by the formula (1) Selected to be 0 and R ^a is the number of carbon atoms with or without substituents Represents an alkyl group having 1 to 30 alkyl groups or an aryl group having 6 to 50 carbon atoms with or without substituents, and when there are a plurality of Q ¹ , M ¹ and Z ¹ , they may be the same or different Good.)

-(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) _b2 (2)
(In the formula (2),
Q ² represents a divalent organic group,
Y ² represents a carbo cation, an ammonium cation, a phosphonyl cation or a sulfonyl cation or an iodonium cation, and M ² represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ^- or PF ₆ ^- represents, ^{Z 2} represents an ammonium cation which does not have or have a metal cation or a substituent, n2 represents an integer of 0 or more, a2 represents an integer of 1 or more, b2 is It represents an integer of 0 or more, provided that, a2 and b2 are selected so that the charge of the group represented by the formula (2) is 0, R ^b is a carbon source that does not have or have a substituent Represents a number of 1 to 30 alkyl group or a substituted or without aryl group having a carbon number of 6 to 50, each of Q ^2, M ² and Z ² are when a plurality of, be the same or different Also good. )

As an embodiment of the ionic polymer used in the present invention, a polymer having a group represented by the following formula (3) can be mentioned. When the ionic polymer has a group represented by the formula (3), the group represented by the formula (3) may be contained in the structural unit of the ionic polymer, and is represented by the formula (1). And may be contained in the same structural unit as the structural unit containing one or more groups selected from the group consisting of the group represented by formula (2), or may be contained in another different structural unit. It may be. Furthermore, as one form of the ionic polymer, a structural unit containing at least one of a group represented by the formula (1), a group represented by the formula (2), and a group represented by the formula (3) Is a polymer having 15 to 100 mol% of all structural units.

-(Q ³ ) _n3 -Y ³ (3)
(In Formula (3),
Q ³ represents a divalent organic group, Y ³ represents —CN or a group represented by any one of formulas (4) to (12), and n3 represents an integer of 0 or more.
-O- (R'O) _a3 -R '' (4)

-S- (R'S) _a4 -R '' (6)
-C (= O)-(R'-C (= O)) _a4 -R '' (7)
-C (= S)-(R'-C (= S)) _a4 -R '' (8)
−N {(R ′) _a4 R ″} ₂ (9)
—C (═O) O— (R′—C (═O) O) _a4 —R ″ (10)
—C (═O) O— (R′O) _a4 —R ″ (11)
—NHC (═O) — (R′NHC (═O)) _a4 —R ″ (12)
(In the formulas (4) to (12), R ′ represents a divalent hydrocarbon group with or without a substituent, and R ″ represents a monovalent with or without a hydrogen atom or a substituent. A hydrocarbon group, —COOH, —SO ₃ H, —OH, —SH, —NR ^c ₂ , —CN or —C (═O) NR ^c ₂ , wherein R ′ ″ has a substituent, or Represents a trivalent hydrocarbon group not having, a3 represents an integer of 1 or more, a4 represents an integer of 0 or more, and R ^c is an alkyl having 1 to 30 carbon atoms with or without a substituent. An aryl group having 6 to 50 carbon atoms with or without a group or substituent, and when there are a plurality of R ′, R ″ and R ′ ″, they may be the same or different. )) The ionic polymer comprises a structural unit represented by formula (13), a structural unit represented by formula (15), a structural unit represented by formula (17), and One or more structural units selected from the group consisting of the structural units (20), in the total structural units, preferably contains 15 to 100 mol%.

(In Formula (13), R ¹ is a monovalent group including a group represented by Formula (14), and Ar ¹ has a (2 + n4) -valent fragrance with or without a substituent other than R ^1. Represents a group, n4 represents an integer of 1 or more, and when there are a plurality of R ^{1 s} , they may be the same or different.

(In Formula (14), R ² represents a (1 + m1 + m2) -valent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 have the same meanings as described above. M1 and m2 each independently represent an integer of 1 or more, and when Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are plural, May be the same or different.))

(In the formula (15), R ³ is a monovalent group containing a group represented by the formula (16), and Ar ² has a (2 + n5) -valent fragrance with or without a substituent other than R ^3. Represents a group, n5 represents an integer of 1 or more, and when there are a plurality of R ^{3 s} , they may be the same or different.

(In Formula (16), R ⁴ represents a (1 + m3 + m4) -valent organic group, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 have the same meaning as described above. M3 and m4 each independently represent an integer greater than or equal to 1. When there are a plurality of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3, May be the same or different.))

(In Formula (17), R ⁵ is a monovalent group containing a group represented by Formula (18), R ⁶ is a monovalent group containing a group represented by Formula (19), Ar ³ represents a (2 + n6 + n7) -valent aromatic group having or not having a substituent other than R ⁵ and R ⁶ , n6 and n7 each independently represents an integer of 1 or more, and each of R ⁵ and R ⁶ May be the same or different when there are multiple.

-R ⁷ -{(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 } _m5 (18)
(In the formula (18), R ⁷ represents a direct bond or a (1 + m5) -valent organic group, Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1 represent the same meaning as described above, and m5 represents Represents an integer of 1 or more, and when there are a plurality of Q ¹ , Y ¹ , M ¹ , Z ¹ , n ¹ , a 1 and b ¹ , they may be the same or different.

-R ⁸ -{(Q ³ ) _n3 -Y ³ } _m6 (19)
(In Formula (19), R ⁸ represents a single bond or a (1 + m6) -valent organic group, Y ³ and n3 represent the same meaning as described above, m6 represents an integer of 1 or more, provided that R ⁸ is a single group. M6 represents 1 when bonded, and when there are a plurality of Q ³ , Y ³ and n3, they may be the same or different.))

(In the formula (20), R ⁹ is a monovalent group containing a group represented by the formula (21), R ¹⁰ is a monovalent group containing a group represented by the formula (22), Ar ⁴ represents a (2 + n8 + n9) -valent aromatic group having or not having a substituent other than R ⁹ and R ¹⁰ , n8 and n9 each independently represents an integer of 1 or more, and each of R ⁹ and R ¹⁰ May be the same or different when there are multiple.

-R ¹¹ -{(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) _b2 } _m7 (21)
(In formula (21), R ¹¹ represents a single bond or a (1 + m7) valent organic group, Q ² , Y ² , M ² , Z ² , n ² , a 2 and b 2 represent the same meaning as described above, and m 7 represents Represents an integer of 1 or more, provided that when R ¹¹ is a single bond, m7 represents 1, and when there are a plurality of Q ² , Y ² , M ² , Z ² , n ² , a 2 and b ² , they are the same or different May be.)

-R ¹² -{(Q ³ ) _n3 -Y ³ } _m8 (22)
(In the formula (22), R ¹² represents a single bond or a (1 + m8) -valent organic group, Y ³ and n3 represent the same meaning as described above, m8 represents an integer of 1 or more, provided that R ¹² is a single group. When bonded, m8 represents 1, and when there are a plurality of Q ³ , Y ³ and n3, they may be the same or different.)

The structural unit in the ionic polymer may contain two or more groups represented by the formula (1), may contain two or more groups represented by the formula (2), Two or more groups represented by 3) may be included.

-Group represented by Formula (1)-
In the formula (1), the divalent organic group represented by Q ¹ includes a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, 1,3 -Butylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, at least one hydrogen in these groups A divalent saturated hydrocarbon group having 1 to 50 carbon atoms, which may or may not have a substituent, such as a group in which an atom is substituted with a substituent; an ethenylene group, a propenylene group, a 3-butenylene group, a 2-butenylene group , 2-pentenylene group, 2-hexenylene group, 2-nonenylene group, 2-dodecenylene group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, or the like. An alkenylene group having 2 to 50 carbon atoms, And a divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms, including or not having a substituent, including an ethynylene group; a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, 3 to 50 carbon atoms having or not having a substituent, such as a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. Divalent cyclic saturated hydrocarbon group; 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, biphenyl-4,4 An arylene group having 6 to 50 carbon atoms, which may or may not have a substituent, such as a '-diyl group, a group in which at least one hydrogen atom of these groups is substituted with a substituent; Echi Have a substituent such as a lenoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. An alkyleneoxy group having 1 to 50 carbon atoms; an imino group having a substituent containing a carbon atom; a silylene group having a substituent containing a carbon atom, and a monomer (hereinafter, “ From the viewpoint of ease of synthesis of the “raw material monomer”, a divalent saturated hydrocarbon group, an arylene group, and an alkyleneoxy group are preferable.

Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. Group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, hydroxy group, carboxyl group, substituted carboxyl group, cyano group and nitro Group, etc., and when a plurality of the substituents are present, they may be the same or different. Of these, substituents other than amino groups, silyl groups, halogen atoms, hydroxy groups, and nitro groups contain carbon atoms.

Hereinafter, the substituent will be described. The term “C _m -C _n ” (m, n is a positive integer satisfying m <n) indicates that the organic group described together with this term has m to n carbon atoms. . For example, a C _m -C _n alkyl group indicates that the alkyl group has m to n carbon atoms, and a C _m -C _n alkyl aryl group indicates that the alkyl group has m carbon atoms of m to n. n represents an aryl-C _m -C _n alkyl group, the alkyl group has m to n carbon atoms.

The alkyl group may be linear or branched, and may be a cycloalkyl group. The alkyl group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and nonyl group. Decyl group, lauryl group and the like. The hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the fluorine atom-substituted alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Examples of the C ₁ to C ₁₂ alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, an isoamyl group, and a hexyl group. Cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group and lauryl group.

The alkoxy group may be linear or branched, may be a cycloalkyloxy group, and may have a substituent. The alkoxy group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. Alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy Octyloxy group, nonyloxy group, decyloxy group, lauryloxy group and the like. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the fluorine atom-substituted alkoxy group include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group. The alkoxy group also includes a methoxymethyloxy group and a 2-methoxyethyloxy group. Examples of the C ₁ -C ₁₂ alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group. Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group.

The alkylthio group may be linear or branched, may be a cycloalkylthio group, and may have a substituent. The alkylthio group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group , Nonylthio group, decylthio group, laurylthio group and the like. A hydrogen atom in the alkylthio group may be substituted with a fluorine atom. Examples of the fluorine atom-substituted alkylthio group include a trifluoromethylthio group.

An aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, a group having a benzene ring, a group having a condensed ring, an independent benzene ring or A group in which two or more condensed rings are bonded through a single bond or a divalent organic group, for example, an alkenylene group such as a vinylene group is also included. The aryl group usually has 6 to 60 carbon atoms, and preferably 7 to 48 carbon atoms. The aryl group includes a phenyl group, a C ₁ -C ₁₂ alkoxyphenyl group, a C ₁ -C ₁₂ alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and a 9-anthracenyl group. Etc. A hydrogen atom in the aryl group may be substituted with a fluorine atom. Examples of the fluorine atom-substituted aryl group include a pentafluorophenyl group. Among the aryl groups, a C ₁ to C ₁₂ alkoxyphenyl group and a C ₁ to C ₁₂ alkylphenyl group are preferable.

Among the aryl groups, C ₁ -C ₁₂ alkoxyphenyl groups include methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, s-butoxyphenyl group, t-butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3, Examples include 7-dimethyloctyloxyphenyl group, lauryloxyphenyl group, and the like.

Among the aryl groups, the C ₁ -C ₁₂ alkylphenyl group includes methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutyl group. Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group usually has 6 to 60 carbon atoms, and preferably 7 to 48 carbon atoms. Examples of the aryloxy group include a phenoxy group, a C ₁ to C ₁₂ alkoxyphenoxy group, a C ₁ to C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group. Among the aryloxy groups, a C ₁ -C ₁₂ alkoxyphenoxy group and a C ₁ -C ₁₂ alkylphenoxy group are preferable.

Among the aryloxy groups, the C ₁ -C ₁₂ alkoxyphenoxy group includes a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an isopropyloxyphenoxy group, a butoxyphenoxy group, an isobutoxyphenoxy group, and an s-butoxyphenoxy group. T-butoxyphenoxy group, pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3 , 7-dimethyloctyloxyphenoxy group, lauryloxyphenoxy group and the like.

Among the aryloxy groups, the C ₁ -C ₁₂ alkylphenoxy group includes methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, isopropyl Phenoxy group, butylphenoxy group, isobutylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group And dodecylphenoxy group.

The arylthio group is, for example, a group in which a sulfur element is bonded to the aforementioned aryl group. The arylthio group may have a substituent on the aromatic ring of the aryl group. The arylthio group usually has 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms. Examples of the arylthio group include a phenylthio group, a C ₁ to C ₁₂ alkoxyphenylthio group, a C ₁ to C ₁₂ alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

The arylalkyl group is, for example, a group in which the above alkyl group is bonded to the above aryl group. The arylalkyl group may have a substituent. The arylalkyl group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. The arylalkyl group includes a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group, 1- naphthyl _-C 1 _{~ C 12} alkyl group, 2-naphthyl _-C 1 _{~ C 12} alkyl group and the like.

The arylalkoxy group is, for example, a group in which the above alkoxy group is bonded to the above aryl group. The arylalkoxy group may have a substituent. The arylalkoxy group usually has 7 to 60 carbon atoms, and preferably 7 to 30 carbon atoms. The arylalkoxy group includes a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, 1- naphthyl _-C 1 _{~ C 12} alkoxy groups, 2-naphthyl _-C 1 _{~ C 12} alkoxy groups and the like.

The arylalkylthio group is, for example, a group in which the aforementioned alkylthio group is bonded to the aforementioned aryl group. The arylalkylthio group may have a substituent. The arylalkylthio group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. The arylalkylthio group includes phenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylthio group, 1- naphthyl _-C 1 _{~ C 12} alkylthio groups, 2-naphthyl _-C 1 _{~ C 12} alkylthio groups and the like.

The arylalkenyl group is, for example, a group in which an alkenyl group is bonded to the aforementioned aryl group. The arylalkenyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms. The arylalkenyl group includes a phenyl-C ₂ -C ₁₂ alkenyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, a C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl group, 1- And naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl-C ₂ -C ₁₂ alkenyl group, and the like. C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl- C ₂ -C ₁₂ alkenyl groups are preferred. Examples of the C ₂ -C ₁₂ alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, and 1-hexenyl. Group, 2-hexenyl group and 1-octenyl group.

The arylalkynyl group is, for example, a group in which an alkynyl group is bonded to the aforementioned aryl group. The arylalkynyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms. The arylalkynyl group includes phenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl group, 1- And naphthyl-C ₂ -C ₁₂ alkynyl group, 2-naphthyl-C ₂ -C ₁₂ alkynyl group, and the like. C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl- C ₂ -C ₁₂ alkynyl groups are preferred. The C ₂ -C ₁₂ alkynyl group includes, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group. Group, 2-hexynyl group and 1-octynyl group.

As the substituted amino group, at least one hydrogen atom in the amino group is substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The amino group formed is preferred. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amino group is usually 1 to 60 excluding the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have, 2 to 48 are preferred. Examples of substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, and s-butylamino group. Group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, lauryl amino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, (C 1 _~ C ₁₂ alkoxyphenyl) amino Group, di _{_(C} 1 _~ C ₁₂ alkoxyphenyl) amino group, di _{_(C} 1 _~ C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dazinylamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, (phenyl-C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ ~ _{C 12} alkyl) amino groups, 1-naphthyl _-C 1 _{~ C 12} alkylamino groups, 2-naphthyl -C Include ~ _{C 12} alkylamino groups and the like.

As the substituted silyl group, at least one hydrogen atom in the silyl group is substituted with 1 to 3 groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group Silyl group formed. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted silyl group is usually 1 to 60 without including the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have, 3 to 48 are preferred. The substituted silyl group includes trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group. Group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group, lauryldimethylsilyl group, (phenyl-C _1- (C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) silyl group, (1-naphthyl- C ₁ C ₁₂ alkyl) silyl group, (2-naphthyl _-C 1 _{~ C 12} alkyl) silyl group, (phenyl _-C 1 _{~ C 12} alkyl) dimethyl silyl group, a triphenylsilyl group, tri (p- xylyl) silyl group, Examples thereof include a tribenzylsilyl group, a diphenylmethylsilyl group, a t-butyldiphenylsilyl group, and a dimethylphenylsilyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The acyl group usually has 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The acyloxy group usually has 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The imine residue means a residue obtained by removing one hydrogen atom in this structure from an imine compound having a structure represented by at least one of the formula: HN═C <and the formula: —N═CH—. To do. Examples of such imine compounds include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, and aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like. It is done. The number of carbon atoms in the imine residue is usually 2-20, and preferably 2-18. Examples of the imine residue include a general formula: —CR ^β ═N—R ^γ or a general formula: —N═C (R ^γ ) ₂ (where R ^β is a hydrogen atom, an alkyl group, an aryl group, an arylalkyl) A group, an arylalkenyl group, or an arylalkynyl group, and R ^γ independently represents an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group, provided that two R ^γ are present. Two ^Rγ are bonded to each other to form a divalent group, for example, an alkylene group having 2 to 18 carbon atoms such as an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc. As a ring may be formed.). Examples of the imine residue include the following groups.

(In the formula, Me represents a methyl group, and the same shall apply hereinafter.)

The amide group usually has 1 to 20 carbon atoms and preferably 2 to 18 carbon atoms. As the amide group, formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoro Examples include an acetamide group and a dipentafluorobenzamide group.

The acid imide group is a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has 4 to 20 carbon atoms and preferably 4 to 18 carbon atoms. Examples of the acid imide group include the following groups.

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. Here, the heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom as an element constituting a ring among organic compounds having a cyclic structure. , An organic compound containing a heteroatom such as a selenium atom, a tellurium atom or an arsenic atom. The monovalent heterocyclic group may have a substituent. The monovalent heterocyclic group usually has 3 to 60 carbon atoms, and preferably 3 to 20 carbon atoms. The number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent. Examples of such a monovalent heterocyclic group include a thienyl group, a C ₁ to C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ to C ₁₂ alkyl pyridyl group, a pyridazinyl group, a pyrimidyl group, Examples include a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group, and among them, a thienyl group, a C ₁ to C ₁₂ alkylthienyl group, a pyridyl group, and a C ₁ to C ₁₂ alkylpyridyl group are preferable. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.

The substituted carboxyl group is a group in which a hydrogen atom in a carboxyl group is substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, that is, a formula: —C (═O) OR ^* (formula R ^* is a group represented by an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted oxycarbonyl group usually has 2 to 60 carbon atoms, and preferably 2 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Note that the number of carbon atoms does not include the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group may have. Examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyl group. Siloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group Perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

In Formula (1), Y ¹ represents a monovalent group such as —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ⁻ , or —B (R ^a ) ₃ ^— , and Y ¹ the, _-CO ² from the viewpoint of the acidity of the ionic polymer _-, ^-SO 2 -, -PO ₃ ^- is more preferred, from the viewpoint of the stability of the ionic polymer, ^- preferably, -CO ₂ - CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ^— or —PO ₃ ^— is preferred.

In formula (1), M ¹ represents a metal cation or an ammonium cation with or without a substituent. As the metal cation, monovalent, divalent or trivalent ions are preferable, and Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, Fe, Ga, Mn, Pb, Examples thereof include ions such as Sn, Ti, V, W, Y, Yb, Zn, and Zr, and Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Ag ⁺ , Mg ²⁺ , and Ca ²⁺ are preferable. In addition, examples of the substituent that the ammonium ion may have include 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, i-butyl group, and t-butyl group. Of the alkyl group.

In the formula (1), Z ¹ represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ are represented.

In the formula (1), n1 represents an integer of 0 or more, and is preferably an integer of 0 to 8, more preferably an integer of 0 to 2, from the viewpoint of synthesis of raw material monomers.

In formula (1), a1 represents an integer of 1 or more, and b1 represents an integer of 0 or more.

a1 and b1 are selected such that the charge of the group represented by the formula (1) is zero. For example, Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ⁻ , or —B (R ^a ) ₃ ^— , and M ¹ has a monovalent metal cation or substituent. An ammonium cation with or without Z ¹ being F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , When ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ is selected, it is selected to satisfy a1 = b1 + 1. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ⁻ , or —B (R ^a ) ₃ ^—— , M ¹ is a divalent metal cation, and Z ¹ is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ , it is selected so as to satisfy b1 = 2 × a1-1. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ⁻ , or —B (R ^a ) ₃ ^— , M ¹ is a trivalent metal cation, and Z ¹ is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , In the case of HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ , it is selected so as to satisfy b1 = 3 × a1-1. Y ¹ is —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ⁻ , or —B (R ^a ) ₃ ^— , and M ¹ has a monovalent metal cation or substituent, or If it is an ammonium cation that does not have it and Z ¹ is SO ₄ ²⁻ or HPO ₄ ^2−, it is selected to satisfy a1 = 2 × b1 + 1. In any of the above mathematical expressions representing the relationship between a1 and b1, a1 is preferably an integer of 1 to 5, more preferably 1 or 2.

^Ra represents an alkyl group having 1 to 30 carbon atoms, which may or may not have a substituent, or an aryl group having 6 to 50 carbon atoms, which may or may not have a substituent. Examples of the substituent which may be included include the same substituents as those exemplified in the description regarding Q ¹ described above. When a plurality of substituents are present, they may be the same or different. As R ^a , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group Carbon number such as alkyl group having 1 to 20 carbon atoms such as decyl group, lauryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, etc. Examples thereof include 6 to 30 aryl groups.

Examples of the group represented by the formula (1) include the following groups.

-Group represented by Formula (2)-
In the formula (2), the divalent organic group represented by Q ^2, include the same groups as those exemplified for the divalent organic group represented by Q ¹ described above, the raw material monomers for synthesis From the viewpoint of ease, a divalent saturated hydrocarbon group, an arylene group, and an alkyleneoxy group are preferable.

The group exemplified as an example of the divalent organic group represented by Q ² may have a substituent, and the substituent is the same as the substituent exemplified in the description of Q ¹ described above. A substituent is mentioned. When a plurality of substituents are present, they may be the same or different.

In formula (2), Y ² represents a carbocation, an ammonium cation, a phosphonyl cation, a sulfonyl cation, or an iodonium cation.
As the carbocation, for example,
-C ⁺ R ₂
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
Examples of ammonium cations include:
-N ⁺ R ₃
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
Examples of phosphonyl cations include:
-P ⁺ R ₃
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
Examples of the sulfonyl cation include:
-S ⁺ R ₂
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
As an iodonium cation, for example,
-I ⁺ R ₂
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
In the formula (2), Y ² represents a carbocation, an ammonium cation, a phosphonyl cation, a sulfonyl cation from the viewpoint of ease of synthesis of the raw material monomer and stability of the raw material monomer and the ionic polymer against air, moisture or heat. Are preferred, and ammonium cations are more preferred.

In formula (2), Z ² represents a metal cation or an ammonium cation with or without a substituent. As the metal cation, monovalent, divalent or trivalent ions are preferable, and Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, Fe, Ga, Mn, Pb, Examples thereof include ions such as Sn, Ti, V, W, Y, Yb, Zn, and Zr. Examples of the substituent that the ammonium cation may have include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. Groups.

In the formula (2), M ² represents F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ are represented.

In formula (2), n2 represents an integer of 0 or more, preferably an integer of 0 to 6, and more preferably an integer of 0 to 2.

In the formula (2), a2 represents an integer of 1 or more, and b2 represents an integer of 0 or more.

a2 and b2 are selected such that the charge of the group represented by the formula (2) is zero. For example, M ² is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ^{_{^{_{^{-, nO 3 -, HSO 4}}}}} -, H 2 PO 4 -, BF 4 - or PF ₆ ^- if it is, if an ammonium ^{ion Z 2} has no or have a monovalent metal ion or a substituent , are selected so as to satisfy a2 = b2 + 1, if ^{Z 2} is a divalent metal ion, it is selected so as to satisfy a2 = 2 × b2 + 1, if ^{Z 2} is a trivalent metal ion, a2 = 3 Xb2 + 1 is selected to satisfy. When M ² is SO ₄ ²⁻ or HPO ₄ ²⁻ , if Z ² is a monovalent metal ion or an ammonium ion with or without a substituent, b2 = 2 × a2-1 is satisfied. If Z ² is a trivalent metal ion, it is selected so as to satisfy the relationship of 2 × a2 = 3 × b2 + 1. In any of the above formulas representing the relationship between a2 and b2, a2 is preferably an integer from 1 to 3, more preferably 1 or 2.

R ^b represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or an aryl group having 6 to 50 carbon atoms with or without a substituent, and these groups have Examples of the substituent which may be included include the same substituents as those exemplified in the description regarding Q ¹ described above. When a plurality of substituents are present, they may be the same or different. R ^b is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl Carbon number such as alkyl group having 1 to 20 carbon atoms such as decyl group, lauryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, etc. Examples thereof include 6 to 30 aryl groups.

Examples of the group represented by the formula (2) include the following groups.

-Group represented by Formula (3)-
In the formula (3), examples of the divalent organic group represented by Q ³ include the same groups as those exemplified for the divalent organic group represented by Q ¹ described above. From the viewpoint of ease, a divalent saturated hydrocarbon group, an arylene group, and an alkyleneoxy group are preferable.

The group mentioned as an example of the divalent organic group represented by Q ³ may have a substituent, and the substituent is the same as the substituent exemplified in the description of Q ¹ described above. A substituent is mentioned. When a plurality of substituents are present, they may be the same or different.

The divalent organic group represented by Q ³ is preferably a group represented by — (CH ₂ ) —.

N3 represents an integer of 0 or more, preferably an integer of 0 to 20, and more preferably an integer of 0 to 8.

In Formula (3), Y ³ represents —CN or a group represented by any one of Formulas (4) to (12).

In the formulas (4) to (12), the divalent hydrocarbon group represented by R ′ includes a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, and a 1,2-butylene. Group, 1,3-butylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, among these groups A divalent saturated hydrocarbon group having 1 to 50 carbon atoms, with or without a substituent, such as a group in which at least one hydrogen atom is substituted with a substituent; an ethenylene group, a propenylene group, a 3-butenylene group; Substituents such as 2-butenylene group, 2-pentenylene group, 2-hexenylene group, 2-nonenylene group, 2-dodecenylene group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, etc. 2 to 50 carbon atoms with or without A divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms, including or not having a substituent, including a lukenylene group and an ethynylene group; a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexane Number of carbon atoms with or without a substituent, such as a xylene group, cyclononylene group, cyclododecylene group, norbornylene group, adamantylene group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. 3 to 50 divalent cyclic saturated hydrocarbon groups; 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, biphenyl- An arylene group having 6 to 50 carbon atoms, which may or may not have a substituent, such as a 4,4′-diyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent; A substituent such as a nonoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. And an alkyleneoxy group having 1 to 50 carbon atoms which may or may not be included.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.

In the formulas (4) to (12), the monovalent hydrocarbon group represented by R ″ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t -Butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like, An alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, and these groups; And an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group in which at least one hydrogen atom is substituted with a substituent. From the viewpoint of solubility of the ionic polymer, a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group are preferable. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.

In the formula (5), the trivalent hydrocarbon group represented by R ′ ″ includes a methanetriyl group, an ethanetriyl group, a 1,2,3-propanetriyl group, a 1,2,4-butanetriyl group, 1 , 2,5-pentanetriyl group, 1,3,5-pentanetriyl group, 1,2,6-hexanetriyl group, 1,3,6-hexanetriyl group, at least of these groups An alkyltriyl group having 1 to 20 carbon atoms, with or without a substituent, such as a group in which one hydrogen atom is substituted with a substituent; 1,2,3-benzenetriyl group, 1,2 , 4-benzenetriyl group, 1,3,5-benzenetriyl group, or a group obtained by substituting at least one hydrogen atom of these groups with a substituent. Examples thereof include aryl groups having 6 to 30 carbon atoms. From the viewpoint of solubility of the ionic polymer, a methanetriyl group, an ethanetriyl group, a 1,2,4-benzenetriyl group, and a 1,3,5-benzenetriyl group are preferable. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.

In formulas (4) to (12), R ^c is preferably a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group or a 2-naphthyl group from the viewpoint of solubility of the ionic polymer.

In the formulas (4) and (5), a3 represents an integer of 1 or more, and an integer of 3 to 10 is preferable. In the formulas (6) to (12), a4 represents an integer of 0 or more. In the formula (6), a4 is preferably an integer of 0 to 30, and more preferably an integer of 3 to 20. In the formulas (7) to (10), a4 is preferably an integer of 0 to 10, and more preferably an integer of 0 to 5. In the formula (11), a4 is preferably an integer of 0 to 20, and more preferably an integer of 3 to 20. In the formula (12), a4 is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.

Y ³ represents —CN, a group represented by the formula (4), a group represented by the formula (6), a group represented by the formula (10), from the viewpoint of ease of synthesis of the raw material monomer. A group represented by the formula (11) is preferable, a group represented by the formula (4), a group represented by the formula (6), a group represented by the formula (11) are more preferable, and the following groups are particularly preferable: preferable.

-Structural units in ionic polymers-
The ionic polymer used in the present invention includes a structural unit represented by the formula (13), a structural unit represented by the formula (15), a structural unit represented by the formula (17), and the formula (20). ), And more preferably an ionic polymer having 15 to 100 mol% of the structural units in all the structural units.

Structural unit represented by formula (13) In formula (13), R ¹ is a monovalent group including a group represented by formula (14), and Ar ¹ has a substituent other than R ^1. Or it represents the (2 + n4) valent aromatic group which does not have, and n4 represents an integer greater than or equal to 1.

The group represented by the formula (14) may be directly bonded to Ar ^{1, and} includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a nonylene group, a dodecylene group, a cyclopropylene group, Substitution, such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent Alkylene group having 1 to 50 carbon atoms with or without a group; oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene group, oxynonylene group, oxiddecylene Group, cyclopropyleneoxy group, cyclobutyleneoxy group, cyclopentyleneoxy group, Chlohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. An oxyalkylene group having 1 to 50 carbon atoms with or without a substituent; an imino group with or without a substituent; a silylene group with or without a substituent; with a substituent An ethynylene group; an ethynylene group; a methanetriyl group with or without a substituent; and an Ar ¹ through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

Ar ¹ may have a substituent other than R ¹ . Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same or different.

The substituent other than R ¹ possessed by Ar ¹ is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, or a substituted carboxyl group from the viewpoint of ease of synthesis of the raw material monomer.

In the formula (13), n4 represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

Examples of the (2 + n4) -valent aromatic group represented by Ar ¹ in the formula (13) include a (2 + n4) -valent aromatic hydrocarbon group and a (2 + n4) -valent aromatic heterocyclic group. Or a (2 + n4) -valent aromatic group consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms. Examples of the (2 + n4) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, and a furan ring. , A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a monocyclic aromatic ring such as pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, azadiazole ring, etc .; selected from the group consisting of the monocyclic aromatic ring A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a condensed polycyclic aromatic ring in which two or more rings are condensed; from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from an aromatic ring assembly formed by connecting two or more selected aromatic rings with a single bond, an ethenylene group or an ethynylene group; the condensed polycyclic aromatic ring Or two adjacent aromatic ring assemblies A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a bridged polycyclic aromatic ring having a bridge in which the aromatic ring is bridged by a divalent group such as a methylene group, an ethylene group, or a carbonyl group. Can be mentioned.

Examples of the monocyclic aromatic ring include the following rings.

Examples of the condensed polycyclic aromatic ring include the following rings.

Examples of the aromatic ring assembly include the following rings.

Examples of the Aribashi polycyclic aromatic ring include the following rings.

The (2 + n4) -valent aromatic group includes (2 + n4) hydrogen atoms from the ring represented by the formulas 1 to 14, 26 to 29, 37 to 39, or 41 from the viewpoint of easy synthesis of the raw material monomer. A group obtained by removing (2 + n4) hydrogen atoms from the ring represented by the formulas 1 to 6, 8, 13, 26, 27, 37, or 41 is more preferred, and the group represented by the

formula

1, 37, or 41 is preferred. More preferred is a group in which (2 + n4) hydrogen atoms have been removed from the ring formed.

In the formula (14), examples of the (1 + m1 + m2) -valent organic group represented by R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m1 + m2) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl An aryl group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which (m1 + m2) hydrogen atoms are removed; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, A cyclopentyloxy group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like, A group obtained by removing (m1 + m2) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m1 + m2) hydrogen atoms from an amino group having a substituent containing a carbon atom Excluded group: a group obtained by removing (m1 + m2) hydrogen atoms from a silyl group having a substituent containing a carbon atom From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m1 + m2) hydrogen atoms are removed from an alkyl group, a group in which (m1 + m2) hydrogen atoms are removed from an aryl group, and an alkoxy group (m1 + m2) Groups in which one hydrogen atom has been removed are preferred.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same or different.

Structural unit represented by formula (15) In formula (15), R ³ is a monovalent group containing a group represented by formula (16), and Ar ² has a substituent other than R ^3. Alternatively, it represents a (2 + n5) -valent aromatic group not present, and n5 represents an integer of 1 or more.

The group represented by the formula (16) may be directly bonded to Ar ^{2, and} includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a nonylene group, a dodecylene group, a cyclopropylene group, Substitution, such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent Alkylene group having 1 to 50 carbon atoms with or without a group; oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene group, oxynonylene group, oxiddecylene Group, cyclopropyleneoxy group, cyclobutyleneoxy group, cyclopentyleneoxy group, Chlohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. An oxyalkylene group having 1 to 50 carbon atoms with or without a substituent; an imino group with or without a substituent; a silylene group with or without a substituent; with a substituent An ethynylene group; an ethynylene group; a methanetriyl group with or without a substituent; and an Ar ² through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

Ar ² may have a substituent other than R ³ . Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same or different.

The substituent other than R ³ possessed by Ar ² is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group from the viewpoint of ease of synthesis of the raw material monomer.

In the formula (15), n5 represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

Examples of the (2 + n5) -valent aromatic group represented by Ar ² in the formula (15) include a (2 + n5) -valent aromatic hydrocarbon group and a (2 + n5) -valent aromatic heterocyclic group. Or a (2 + n5) -valent aromatic group consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms. Examples of the (2 + n5) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, and a furan ring. , A (2 + n5) -valent group obtained by removing (2 + n5) hydrogen atoms from a monocyclic aromatic ring such as pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, azadiazole ring, etc .; selected from the group consisting of the monocyclic aromatic ring A (2 + n5) -valent group obtained by removing (2 + n5) hydrogen atoms from a condensed polycyclic aromatic ring in which two or more rings are condensed; from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring A (2 + n5) -valent group obtained by removing (2 + n5) hydrogen atoms from an aromatic ring assembly formed by connecting two or more selected aromatic rings with a single bond, an ethenylene group or an ethynylene group; the condensed polycyclic aromatic ring Or two adjacent aromatic ring assemblies A (2 + n5) -valent group obtained by removing (2 + n5) hydrogen atoms from a bridged polycyclic aromatic ring having a bridge in which the aromatic ring is bridged by a divalent group such as a methylene group, an ethylene group, or a carbonyl group. Can be mentioned.

Examples of the monocyclic aromatic ring include rings represented by formulas 1 to 12 exemplified in the description of the structural unit represented by formula (13).

Examples of the condensed polycyclic aromatic ring include rings represented by formulas 13 to 27 exemplified in the description of the structural unit represented by formula (13).

Examples of the aromatic ring assembly include rings represented by formulas 28 to 36 exemplified in the description of the structural unit represented by formula (13).

Examples of the bridged polycyclic aromatic ring include rings represented by Formulas 37 to 44 exemplified in the description of the structural unit represented by Formula (13).

The (2 + n5) -valent aromatic group includes (2 + n5) hydrogen atoms from the ring represented by the formulas 1 to 14, 26 to 29, 37 to 39, or 41 from the viewpoint of easy synthesis of the raw material monomer. A group obtained by removing (2 + n5) hydrogen atoms from the ring represented by formulas 1 to 6, 8, 13, 26, 27, 37, or 41 is more preferred, and a group represented by

formula

1, 37, or 41 is preferred. And more preferably a group in which (2 + n5) hydrogen atoms have been removed from the ring.

In formula (16), m3 and m4 each independently represent an integer of 1 or more.

In the formula (16), examples of the (1 + m3 + m4) -valent organic group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m3 + m4) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl An aryl group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which (m3 + m4) hydrogen atoms are removed; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, A cyclopentyloxy group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like, A group obtained by removing (m3 + m4) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m3 + m4) hydrogen atoms from an amino group having a substituent containing a carbon atom; Excluded group: a group obtained by removing (m3 + m4) hydrogen atoms from a silyl group having a substituent containing a carbon atom From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m3 + m4) hydrogen atoms are removed from an alkyl group, a group in which (m3 + m4) hydrogen atoms are removed from an aryl group, and an alkoxy group (m3 + m4) Groups in which one hydrogen atom has been removed are preferred.

Structural unit represented by formula (17) In formula (17), R ⁵ is a monovalent group including a group represented by formula (18), and R ⁶ is a group represented by formula (19). Ar ³ represents a (2 + n6 + n7) -valent aromatic group having or not having a substituent other than R ⁵ and R ⁶ , and n6 and n7 are each independently an integer of 1 or more Represents.

The group represented by the formula (18) and the group represented by the formula (19) may be directly bonded to Ar ^{3, and} include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, Nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group, adamantylene group, and at least one hydrogen atom in these groups An alkylene group having 1 to 50 carbon atoms, with or without a substituent, such as a group substituted with a substituent; an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group, an oxy Hexylene, oxynonylene, oxide decylene, cyclopropyleneoxy, cyclobutyleneoxy, Clopentyleneoxy group, cyclohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, and at least one hydrogen atom in these groups is substituted An oxyalkylene group having 1 to 50 carbon atoms with or without a substituent, such as a group substituted with a group; an imino group with or without a substituent; a silylene with or without a substituent An ethenylene group with or without a substituent; an ethynylene group; a methanetriyl group with or without a substituent; and bonded to Ar ³ through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. May be.

Ar ³ may have a substituent other than R ⁵ and R ⁶ . Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same or different.

The substituent other than R ⁵ and R ⁶ possessed by Ar ³ is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, or a substituted carboxyl group from the viewpoint of ease of synthesis of the raw material monomer. Is preferred.

In formula (17), n6 represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

In formula (17), n7 represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

Examples of the (2 + n6 + n7) -valent aromatic group represented by Ar ³ in the formula (17) include a (2 + n6 + n7) -valent aromatic hydrocarbon group and a (2 + n6 + n7) -valent aromatic heterocyclic group, and a carbon atom. Or a (2 + n6 + n7) -valent aromatic group consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms. Examples of the (2 + n6 + n7) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. A (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from a monocyclic aromatic ring such as an oxazole ring; a condensed polycycle in which two or more rings selected from the group consisting of the monocyclic aromatic rings are condensed A (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from the formula aromatic ring; two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring, , A (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from an aromatic ring assembly linked by an ethenylene group or an ethynylene group; the condensed polycyclic aromatic ring or two adjacent aromatic ring assemblies (2 + n6 + n7) -valent groups obtained by removing (2 + n6 + n7) hydrogen atoms from a bridged polycyclic aromatic ring having a bridge formed by bridging an aromatic ring with a divalent group such as a methylene group, an ethylene group, or a carbonyl group. It is done.

Examples of the monocyclic aromatic ring include rings represented by Formulas 1 to 5 and Formulas 7 to 10 exemplified in the description of the structural unit represented by Formula (13).

The (2 + n6 + n7) -valent aromatic group is a ring represented by the formula 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to 39 or 41 from the viewpoint of ease of synthesis of the raw material monomer. A group obtained by removing (2 + n6 + n7) hydrogen atoms from the ring is preferred, and a group obtained by removing (2 + n6 + n7) hydrogen atoms from the ring represented by

formula

1, 37 or 41 is more preferred, represented by formula 1, 38 or 42 A group obtained by removing (2 + n6 + n7) hydrogen atoms from the ring is more preferable.

In Formula (18), R ⁷ represents a single bond or a (1 + m5) -valent organic group, and is preferably a (1 + m5) -valent organic group.

In the formula (18), examples of the (1 + m5) -valent organic group represented by R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which an m5 hydrogen atom is removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, M5-hydrogen from an aryl group having 6 to 30 carbon atoms, which may or may not have a substituent, such as a 9-anthracenyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent. original Groups other than the above: methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group A group having a substituent, such as a group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing m5 hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms; a group obtained by removing m5 hydrogen atoms from an amino group having a substituent containing carbon atoms; a substituent containing carbon atoms; And a group obtained by removing m5 hydrogen atoms from the silyl group possessed, and from the viewpoint of ease of synthesis of the raw material monomer, an alkyl group Et m5 groups excluding the hydrogen atom, a group remaining after removing m5 hydrogen atoms from an aryl group, a group obtained by removing m5 hydrogen atoms from an amino group.

In formula (18), m5 represents an integer of 1 or more, provided that m5 represents 1 when R ⁷ is a single bond.

In Formula (19), R ⁸ represents a single bond or a (1 + m6) -valent organic group, and is preferably a (1 + m6) -valent organic group.

In the formula (19), examples of the (1 + m6) -valent organic group represented by R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which an m6 hydrogen atom is removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, M6-hydrogen from an aryl group having 6-30 carbon atoms, with or without a substituent, such as a 9-anthracenyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent original Groups other than the above: methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group A group having a substituent, such as a group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing m6 hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms; a group obtained by removing m6 hydrogen atoms from an amino group having a substituent containing carbon atoms; a substituent containing carbon atoms; And a group obtained by removing m6 hydrogen atoms from the silyl group possessed, and from the viewpoint of ease of synthesis of the raw material monomer, an alkyl group Et m6 groups excluding the hydrogen atom, a group remaining after removing m6 hydrogen atoms from an aryl group, a group obtained by removing m6 hydrogen atoms from an amino group.

In Formula (19), m6 represents an integer of 1 or more, provided that m6 represents 1 when R ⁸ is a single bond.

Structural unit represented by formula (20) In formula (20), R ⁹ is a monovalent group including a group represented by formula (21), and R ¹⁰ is a group represented by formula (22). Ar ⁴ represents a (2 + n8 + n9) -valent aromatic group having or not having a substituent other than R ⁹ and R ¹⁰ , and n8 and n9 are each independently an integer of 1 or more Represents.

The group represented by the formula (21) and the group represented by the formula (22) may be directly bonded to Ar ^{4, and} include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, Nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group, adamantylene group, and at least one hydrogen atom in these groups An alkylene group having 1 to 50 carbon atoms, with or without a substituent, such as a group substituted with a substituent; an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group, an oxy Hexylene, oxynonylene, oxide decylene, cyclopropyleneoxy, cyclobutyleneoxy, Clopentyleneoxy group, cyclohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, and at least one hydrogen atom in these groups is substituted An oxyalkylene group having 1 to 50 carbon atoms with or without a substituent, such as a group substituted with a group; an imino group with or without a substituent; a silylene with or without a substituent An ethenylene group with or without a substituent; an ethynylene group; a methanetriyl group with or without a substituent; and bonded to Ar ⁴ through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. May be.

Ar ⁴ may have a substituent other than R ⁹ and R ¹⁰ . Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same or different.

The substituent other than R ⁹ and R ^{10 of} Ar ⁴ is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group, or a substituted carboxyl group from the viewpoint of ease of synthesis of the raw material monomer. Is preferred.

In formula (20), n8 represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

In formula (20), n9 represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

Examples of the (2 + n8 + n9) -valent aromatic group represented by Ar ⁴ in the formula (20) include a (2 + n8 + n9) -valent aromatic hydrocarbon group and a (2 + n8 + n9) -valent aromatic heterocyclic group. Or a (2 + n8 + n9) -valent aromatic group consisting of carbon atoms and one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms and oxygen atoms. Examples of the (2 + n8 + n9) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. A (2 + n8 + n9) -valent group obtained by removing (2 + n8 + n9) hydrogen atoms from a monocyclic aromatic ring such as a condensed polycyclic aromatic ring in which two or more rings selected from the group consisting of the monocyclic aromatic rings are condensed A (2 + n8 + n9) -valent group obtained by removing (2 + n8 + n9) hydrogen atoms from the above; two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring are bonded to a single bond or an ethenylene group Or a (2 + n8 + n9) -valent group obtained by removing (2 + n8 + n9) hydrogen atoms from an aromatic ring assembly connected by an ethynylene group; the condensed polycyclic aromatic ring or two adjacent aromatic rings in the aromatic ring assembly are methylated. Group, an ethylene group, and a divalent hydrogen atoms from a bridged polycyclic aromatic ring having a bridged crosslinked with groups (2 + n8 + n9) pieces remaining after removing (2 + n8 + n9) valent group such as a carbonyl group.

The (2 + n8 + n9) -valent aromatic group is a ring represented by the formula 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to 39 or 41 from the viewpoint of ease of synthesis of the raw material monomer. Is preferably a group in which (2 + n8 + n9) hydrogen atoms are removed from, more preferably a group in which (2 + n8 + n9) hydrogen atoms are removed from the ring represented by the formulas 1 to 6, 8, 14, 27, 28, 38 or 42, A group obtained by removing (2 + n8 + n9) hydrogen atoms from the ring represented by

formula

1, 37 or 41 is more preferable.

In Formula (21), R ¹¹ represents a single bond or a (1 + m7) -valent organic group, and is preferably a (1 + m7) -valent organic group.

In the formula (21), examples of the (1 + m7) -valent organic group represented by R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which an m7 hydrogen atom is removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, M7 hydrogen from an aryl group having 6-30 carbon atoms, with or without a substituent, such as a 9-anthracenyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent Groups excluding atoms: methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group A group having a substituent, such as a group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing m7 hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms; a group obtained by removing m7 hydrogen atoms from an amino group having a substituent containing carbon atoms; a substituent containing carbon atoms; Examples include groups in which m7 hydrogen atoms are removed from the silyl group possessed. From the viewpoint of ease of synthesis of the raw material monomer, alkyl A group remaining after removing m7 hydrogen atoms from a group remaining after removing m7 hydrogen atoms from an aryl group, a group obtained by removing m7 hydrogen atoms from an amino group.

In formula (21), m7 represents an integer of 1 or more, provided that when R ¹¹ is a single bond, m7 represents 1.

In Formula (22), R ¹² represents a single bond or a (1 + m8) valent organic group, and is preferably a (1 + m8) valent organic group.

In the formula (22), examples of the (1 + m8) -valent organic group represented by R ¹² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which an m8 hydrogen atom is removed from an alkyl group having 1 to 20 carbon atoms, which may or may not have; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, M8 hydrogen from an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, or the like Groups excluding atoms: methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group A group having a substituent, such as a group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing m8 hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms; a group obtained by removing m8 hydrogen atoms from an amino group having a substituent containing carbon atoms; a substituent containing carbon atoms; And a group obtained by removing m8 hydrogen atoms from the silyl group possessed. From the viewpoint of ease of synthesis of the raw material monomer, alkyl A group remaining after removing m8 hydrogen atoms from a group remaining after removing m8 hydrogen atoms from an aryl group, a group obtained by removing m8 hydrogen atoms from an amino group.

In formula (22), m8 represents an integer of 1 or more, provided that m8 represents 1 when R ¹² is a single bond.

Examples of the structural unit represented by the formula (13) As the structural unit represented by the formula (13), from the viewpoint of the electron transport property of the obtained ionic polymer, the structural unit represented by the formula (23), The structural unit represented by Formula (24) is preferable, and the structural unit represented by Formula (24) is more preferable.

(In formula (23), R ¹³ represents a (1 + m9 + m10) -valent organic group, R ¹⁴ represents a monovalent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1 , A1, b1 and n3 represent the same meaning as described above, m9 and m10 each independently represent an integer of 1 or more, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, When there are a plurality of b1 and n3, they may be the same or different.)

In the formula (23), examples of the (1 + m9 + m10) -valent organic group represented by R ¹³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, and t-butyl. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m9 + m10) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl An aryl group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which (m9 + m10) hydrogen atoms have been removed from the group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy Groups, cyclopentyloxy groups, cyclohexyloxy groups, cyclononyloxy groups, cyclododecyloxy groups, norbornyloxy groups, adamantyloxy groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m9 + m10) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m9 + m10) hydrogens from an amino group having a substituent containing a carbon atom A group excluding atoms; (m9 + m10) hydrogen atoms from a silyl group having a substituent containing a carbon atom; From the viewpoint of ease of synthesis of the raw material monomer, a group obtained by removing (m9 + m10) hydrogen atoms from an alkyl group, a group obtained by removing (m9 + m10) hydrogen atoms from an aryl group, an alkoxy group To (m9 + m10) hydrogen atoms are preferred.

In the formula (23), examples of the monovalent organic group represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, It has a substituent such as a pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, or a group obtained by substituting at least one hydrogen atom of these groups with a substituent. Or a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, which is not present; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9- One hydrogen atom from an aryl group having 6 to 30 carbon atoms, which may or may not have a substituent, such as an anthracenyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent. Excluded group Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy Group, cyclododecyloxy group, norbornyloxy group, adamantyloxy group, or the number of carbon atoms having or not having a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which one hydrogen atom is removed from 1 to 50 alkoxy groups; a group in which one hydrogen atom is removed from an amino group having a substituent containing a carbon atom; a silyl group having a substituent containing a carbon atom; From the viewpoint of ease of synthesis of the raw material monomer, one hydrogen atom from the alkyl group is exemplified. Except groups, groups obtained by removing one hydrogen atom from an aryl group, a group derived by removing one hydrogen atom from an amino group.

Examples of the structural unit represented by the formula (23) include the following structural units.

(In the formula (24), R ¹³ represents a (1 + m11 + m12) -valent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 have the same meaning as described above. M11 and m12 each independently represents an integer of 1 or more, and R ¹³ , m11, m12, Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 (If there are several, each may be the same or different.)

In the formula (24), examples of the (1 + m11 + m12) -valent organic group represented by R ¹³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m11 + m12) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl A group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m11 + m12) hydrogen atoms from a reel group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy Groups, cyclopentyloxy groups, cyclohexyloxy groups, cyclononyloxy groups, cyclododecyloxy groups, norbornyloxy groups, adamantyloxy groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m11 + m12) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m11 + m12) hydrogens from an amino group having a substituent containing a carbon atom Groups excluding atoms; (m11 + m12) silyl groups having substituents containing carbon atoms From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m11 + m12) hydrogen atoms have been removed from the alkyl group, and (m11 + m12) hydrogen atoms have been removed from the aryl group. A group obtained by removing (m11 + m12) hydrogen atoms from a group or alkoxy group is preferred.

Examples of the structural unit represented by the formula (24) include the following structural units.

As the structural unit represented by the formula (13), the structural unit represented by the formula (25) is preferable from the viewpoint of durability of the obtained ionic polymer.

(In the formula (25), R ¹⁵ represents a (1 + m13 + m14) -valent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 have the same meaning as described above. M13, m14 and m15 each independently represents an integer of 1 or more, R ¹⁵ , m13, m14, Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and If there are multiple n3s, they may be the same or different.)

In the formula (25), examples of the (1 + m13 + m14) -valent organic group represented by R ¹⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m13 + m14) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl A group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m13 + m14) hydrogen atoms from a reel group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy A group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group obtained by substituting at least one hydrogen atom of these groups with a substituent, etc. A group obtained by removing (m13 + m14) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m13 + m14) hydrogens from an amino group having a substituent containing a carbon atom Groups excluding atoms; (m13 + m14) silyl groups having substituents containing carbon atoms From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m13 + m14) hydrogen atoms have been removed from the alkyl group, and (m13 + m14) hydrogen atoms have been removed from the aryl group. A group obtained by removing (m13 + m14) hydrogen atoms from an alkoxy group is preferred.

Examples of the structural unit represented by the formula (25) include the following structural units.

Examples of the structural unit represented by the formula (15) As the structural unit represented by the formula (15), from the viewpoint of the electron transport property of the obtained ionic polymer, the structural unit represented by the formula (26), The structural unit represented by Formula (27) is preferable, and the structural unit represented by Formula (27) is more preferable.

(In the formula (26), R ¹⁶ represents a (1 + m16 + m17) valent organic group, R ¹⁷ represents a monovalent organic group, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2 , a2, b2 and n3 represent the same as defined above, m16 and represent an integer of 1 or more, respectively m17 ^{^{^{^{independently, Q 2, Q 3, Y}}}} 2, M 2, Z 2, Y 3, n2, a2 , B2 and n3 may be the same or different when there is a plurality.

In the formula (26), examples of the (1 + m16 + m17) -valent organic group represented by R ¹⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m16 + m17) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl A group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m16 + m17) hydrogen atoms from a reel group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy Groups, cyclopentyloxy groups, cyclohexyloxy groups, cyclononyloxy groups, cyclododecyloxy groups, norbornyloxy groups, adamantyloxy groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m16 + m17) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m16 + m17) hydrogens from an amino group having a substituent containing a carbon atom Groups excluding atoms; (m16 + m17) silyl groups having substituents containing carbon atoms From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m16 + m17) hydrogen atoms have been removed from the alkyl group, and (m16 + m17) hydrogen atoms have been removed from the aryl group. A group obtained by removing (m16 + m17) hydrogen atoms from an alkoxy group is preferred.

In the formula (26), examples of the monovalent organic group represented by R ¹⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, It has a substituent such as a pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, or a group obtained by substituting at least one hydrogen atom of these groups with a substituent. Or a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, which is not present; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9- One hydrogen atom from an aryl group having 6 to 30 carbon atoms, which may or may not have a substituent, such as an anthracenyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent. Excluded group Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy Group, cyclododecyloxy group, norbornyloxy group, adamantyloxy group, or the number of carbon atoms having or not having a substituent, such as a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which one hydrogen atom is removed from 1 to 50 alkoxy groups; a group in which one hydrogen atom is removed from an amino group having a substituent containing a carbon atom; a silyl group having a substituent containing a carbon atom; From the viewpoint of ease of synthesis of the raw material monomer, one hydrogen atom from the alkyl group is exemplified. Except groups, groups obtained by removing one hydrogen atom from an aryl group, a group derived by removing one hydrogen atom from an amino group.

Examples of the structural unit represented by the formula (26) include the following structural units.

(In the formula (27), R ¹⁶ represents a (1 + m16 + m17) valent organic group, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 have the same meaning as described above. the stands, m16 and represent an integer of 1 or more each independently ^{^{^{^{m17, R 16, m16, m17}}}} , Q 2, Q 3, Y 2, M 2, Z 2, Y 3, n2, a2, b2 , and n3 If there are multiple of each, they may be the same or different.)

In the formula (27), examples of the (1 + m16 + m17) -valent organic group represented by R ¹⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m16 + m17) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl A group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m16 + m17) hydrogen atoms from a reel group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy Groups, cyclopentyloxy groups, cyclohexyloxy groups, cyclononyloxy groups, cyclododecyloxy groups, norbornyloxy groups, adamantyloxy groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m16 + m17) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m16 + m17) hydrogens from an amino group having a substituent containing a carbon atom Groups excluding atoms; (m16 + m17) silyl groups having substituents containing carbon atoms From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m16 + m17) hydrogen atoms have been removed from the alkyl group, and (m16 + m17) hydrogen atoms have been removed from the aryl group. A group obtained by removing (m16 + m17) hydrogen atoms from an alkoxy group is preferred.

Examples of the structural unit represented by the formula (27) include the following structural units.

As the structural unit represented by the formula (15), the structural unit represented by the formula (28) is preferable from the viewpoint of durability of the obtained ionic polymer.

(In the formula (28), R ¹⁸ represents a (1 + m18 + m19) valent organic group, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 have the same meaning as described above. M18, m19 and m20 each independently represent an integer of 1 or more, and R ¹⁸ , m18, m19, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2 and If there are multiple n3s, they may be the same or different.)

In the formula (28), examples of the (1 + m18 + m19) -valent organic group represented by R ¹⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m18 + m19) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl A group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m18 + m19) hydrogen atoms from a reel group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy Groups, cyclopentyloxy groups, cyclohexyloxy groups, cyclononyloxy groups, cyclododecyloxy groups, norbornyloxy groups, adamantyloxy groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m18 + m19) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m18 + m19) hydrogens from an amino group having a substituent containing a carbon atom Groups excluding atoms; (m18 + m19) silyl groups having substituents containing carbon atoms From the viewpoint of ease of synthesis of the raw material monomer, a group in which (m18 + m19) hydrogen atoms have been removed from the alkyl group, and (m18 + m19) hydrogen atoms have been removed from the aryl group. A group obtained by removing (m18 + m19) hydrogen atoms from an alkoxy group is preferred.

Examples of the structural unit represented by the formula (28) include the following structural units.

Example of Structural Unit Represented by Formula (17) As the structural unit represented by Formula (17), from the viewpoint of electron transport properties of the obtained ionic polymer, the structural unit represented by Formula (29) is preferable.

(In Formula (29), R ¹⁹ represents a single bond or a (1 + m21) -valent organic group, R ²⁰ represents a single bond or a (1 + m22) -valent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ ^{^{, Z 1, Y 3, n1}} , a1, b1 and n3 represent the same as defined above, represents an integer of 1 or more, respectively m21 and m22 independently, provided ^that when ^{R 19} is a single bond m21 represents 1 , R ²⁰ is a single bond, m22 represents ¹ , and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 each have the same or different May be.)

In the formula (29), examples of the (1 + m21) -valent organic group represented by R ¹⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m21) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 21) Groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m21) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m21) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m21) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, (m21) hydrogen atoms are removed from the alkyl group, (m21) hydrogen atoms are removed from the aryl group, and (m21) hydrogen atoms are removed from the alkoxy group. The groups are preferred.

In the formula (29), examples of the (1 + m22) -valent organic group represented by R ²⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m22) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 22) Groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m22) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m22) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m22) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, a group obtained by removing (m22) hydrogen atoms from an alkyl group, a group obtained by removing (m22) hydrogen atoms from an aryl group, and (m22) hydrogen atoms from an alkoxy group Are preferred.
Examples of the structural unit represented by the formula (29) include the following structural units.

The structural unit represented by the formula (17) is preferably the structural unit represented by the formula (30) from the viewpoint of durability of the obtained ionic polymer.

(In formula (30), R ²¹ represents a single bond or a (1 + m23) -valent organic group, R ²² represents a single bond or a (1 + m24) -valent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ ^{^{, Z 1, Y 3, n1}} , a1, b1 and n3 represent the same as defined above, represents an integer of 1 or more, respectively m23 and m24 independently, provided ^that when ^{R 21} is a single bond m23 represents 1 , R ²² is a single bond, m24 represents 1, m25 and m26 each independently represents an integer of 1 or more, and m23, m24, R ²¹ , R ²² , Q ¹ , Q ³ , Y ¹ , M ¹ , When there are a plurality of Z ¹ , Y ³ , n1, a1, b1, and n3, they may be the same or different.)

In the formula (30), examples of the (1 + m23) -valent organic group represented by R ²¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, and t-butyl. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m23) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 23) Groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m23) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m23) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m23) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, a group in which (m23) hydrogen atoms have been removed from an alkyl group, a group in which (m23) hydrogen atoms have been removed from an aryl group, and (m23) hydrogen atoms have been removed from an alkoxy group The groups are preferred.

In the formula (30), examples of the (1 + m24) -valent organic group represented by R ²² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m24) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 24) Groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m24) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m24) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m24) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, (m24) hydrogen atoms are removed from the alkyl group, (m24) hydrogen atoms are removed from the aryl group, and (m24) hydrogen atoms are removed from the alkoxy group. The groups are preferred.

Examples of the structural unit represented by the formula (30) include the following structural units.

Example of Structural Unit Represented by Formula (20) As the structural unit represented by Formula (20), the structural unit represented by Formula (31) is preferable from the viewpoint of the obtained electron transport property.

(In formula (31), R ²³ represents a single bond or a (1 + m27) -valent organic group, R ²⁴ represents a single bond or a (1 + m28) -valent organic group, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 represent the same meaning as described above, m 27 and m 28 each independently represent an integer of 1 or more, provided that m 27 represents 1 when R ²³ is a single bond. , When R ²⁴ is a single bond, m28 represents 1, and when Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 are plural, they are the same or different May be.)

In the formula (31), examples of the (1 + m27) -valent organic group represented by R ²³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m27) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 27) Groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m27) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m27) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m27) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, a group in which (m27) hydrogen atoms have been removed from an alkyl group, a group in which (m27) hydrogen atoms have been removed from an aryl group, and (m27) hydrogen atoms have been removed from an alkoxy group The groups are preferred.

In the formula (31), examples of the (1 + m28) -valent organic group represented by R ²⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m28) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 28) Groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m28) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m28) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m28) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, (m28) hydrogen atoms are removed from the alkyl group, (m28) hydrogen atoms are removed from the aryl group, and (m28) hydrogen atoms are removed from the alkoxy group. Are preferred.

Examples of the structural unit represented by the formula (31) include the following structural units.

As the structural unit represented by the formula (20), the structural unit represented by the formula (32) is preferable from the viewpoint of durability of the obtained ionic polymer.

(In Formula (32), R ²⁵ represents a single bond or a (1 + m29) -valent organic group, R ²⁶ represents a single bond or a (1 + m30) -valent organic group, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 represent the same meaning as described above, m 29 and m 30 each independently represent an integer of 1 or more, provided that m 29 represents 1 when R ²⁵ is a single bond. , R ²⁶ is a single bond, m30 represents 1, m31 and m32 each independently represents an integer of 1 or more, m29, m30, R ²⁵ , R ²⁶ , Q ² , Q ³ , Y ² , M ² , When there are a plurality of Z ² , Y ³ , n 2, a 2, b 2 and n 3, they may be the same or different.)

In the formula (32), examples of the (1 + m29) -valent organic group represented by R ²⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m29) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 29) groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m29) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m29) hydrogen atoms removed from an amino group having a substituent containing a carbon atom Group: a group obtained by removing (m29) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, a group in which (m29) hydrogen atoms are removed from an alkyl group, a group in which (m29) hydrogen atoms are removed from an aryl group, and (m29) hydrogen atoms are removed from an alkoxy group Are preferred.

In the formula (32), examples of the (1 + m30) -valent organic group represented by R ²⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m30) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl From an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group, a 9-anthracenyl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent (m 30) groups excluding one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy Substituents such as a group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like A group obtained by removing (m30) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without having; and (m30) hydrogen atoms removed from an amino group having a substituent containing carbon atoms Group: a group obtained by removing (m30) hydrogen atoms from a silyl group having a substituent containing a carbon atom. From the viewpoint of easiness, a group in which (m30) hydrogen atoms are removed from an alkyl group, a group in which (m30) hydrogen atoms are removed from an aryl group, and (m30) hydrogen atoms are removed from an alkoxy group Are preferred.

Examples of the structural unit represented by the formula (32) include the following structural units.

-Other structural unit The ionic polymer used for this invention may have 1 or more types of structural units further represented by Formula (33).

(In Formula (33), Ar ⁵ represents a divalent aromatic group having or not having a substituent, or a divalent aromatic amine residue having or not having a substituent, and X ′ represents a substituted group. Represents an imino group with or without a group, a silylene group with or without a substituent, an ethenylene group with or without a substituent, or an ethynylene group, and m33 and m34 are each independently 0 or 1 And at least one of m33 and m34 is 1.)

Examples of the divalent aromatic group represented by Ar ⁵ in formula (33) include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. Examples of the divalent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, a furan ring, and a pyrrole. A divalent group obtained by removing two hydrogen atoms from a monocyclic aromatic ring such as a ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, oxadiazole ring, azadiazole ring; the group consisting of the monocyclic aromatic ring A divalent group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic ring condensed with two or more selected from: two selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring A divalent group obtained by removing two hydrogen atoms from an aromatic ring assembly formed by connecting the above aromatic rings with a single bond, an ethenylene group or an ethynylene group; the condensed polycyclic aromatic ring or the aromatic ring assembly adjacent to each other. Two aromatic rings are methylene, ethylene and cal Group, and a divalent group in which two hydrogen atoms are removed from a bridged polycyclic aromatic ring having a bridged crosslinked with divalent group such as an imino group.

In the condensed polycyclic aromatic ring, the number of monocyclic aromatic rings to be condensed is preferably 2 to 4, more preferably 2 to 3, and further preferably 2 from the viewpoint of solubility of the ionic polymer. In the aromatic ring assembly, the number of aromatic rings to be connected is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2 from the viewpoint of solubility. In the bridged polycyclic aromatic ring, the number of aromatic rings to be bridged is preferably 2 to 4, more preferably 2 to 3, and further preferably 2 from the viewpoint of solubility of the ionic polymer.

Examples of the monocyclic aromatic ring include the following rings.

Examples of the condensed polycyclic aromatic ring include the following rings.

Examples of the aromatic ring assembly include the following rings.

Examples of the Aribashi polycyclic aromatic ring include the following rings.

From the viewpoint of either or both of the electron accepting property and the hole accepting property of the ionic polymer, the divalent aromatic group represented by Ar ⁵ is represented by the formulas 45 to 60, 61 to 71, 77 to 80, A divalent group obtained by removing two hydrogen atoms from the ring represented by 91, 92, 93 or 96 is preferred, and the ring represented by the formulas 45 to 50, 59, 60, 77, 80, 91, 92 or 96 A divalent group in which two hydrogen atoms are removed from is more preferable.

The above divalent aromatic group may have a substituent. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above.

Examples of the divalent aromatic amine residue represented by Ar ⁵ in Formula (33) include a group represented by Formula (34).

(In the formula (34), Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ are each independently an arylene group with or without a substituent or a divalent heterocyclic ring with or without a substituent. Ar ¹⁰ , Ar ¹¹ and Ar ¹² each independently represent an aryl group with or without a substituent or a monovalent heterocyclic group with or without a substituent, and n10 and m35 independently represents 0 or 1.)

Examples of the substituent that the arylene group, aryl group, divalent heterocyclic group, and monovalent heterocyclic group may have include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, and an aryloxy group. Group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substitution Amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl Group, arylalkyloxycarbonyl group, Lower aryloxy carbonyl group and a carboxyl group and the like. The substituent is vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, small ring (cyclopropyl group) , A group having a cyclobutyl group, an epoxy group, an oxetane group, a diketene group, an episulfide group, etc.), a lactone group, a lactam group, or a group containing a structure of a siloxane derivative.

When n10 is 0, the carbon atom in Ar ⁶ and the carbon atom in Ar ⁸ may be directly bonded, or may be bonded through a divalent group such as —O— or —S—. .

The aryl group and monovalent heterocyclic group represented by Ar ¹⁰ , Ar ¹¹ , and Ar ¹² are the same as the aryl group and monovalent heterocyclic group described and exemplified above as the substituent.

Examples of the arylene group represented by Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ include the remaining atomic groups obtained by removing two hydrogen atoms bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, Examples thereof include a group having a benzene ring, a group having a condensed ring, a group in which two or more independent benzene rings or condensed rings are bonded through a single bond or a divalent organic group, for example, an alkenylene group such as a vinylene group. . The arylene group usually has 6 to 60 carbon atoms, and preferably 7 to 48 carbon atoms. Specific examples of the arylene group include a phenylene group, a biphenylene group, a C ₁ to C ₁₇ alkoxyphenylene group, a C ₁ to C ₁₇ alkylphenylene group, a 1-naphthylene group, a 2-naphthylene group, a 1-anthracenylene group, and a 2-anthracenylene group. Group, 9-anthracenylene group. A hydrogen atom in the aryl group may be substituted with a fluorine atom. Examples of the fluorine atom-substituted aryl group include a tetrafluorophenylene group. Among the aryl groups, a phenylene group, a biphenylene group, a C ₁ to C ₁₂ alkoxyphenylene group, and a C ₁ to C ₁₂ alkylphenylene group are preferable.

Examples of the divalent heterocyclic group represented by Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ include the remaining atomic groups obtained by removing two hydrogen atoms from a heterocyclic compound. Here, the heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom as an element constituting a ring among organic compounds having a cyclic structure. , An organic compound containing a heteroatom such as a selenium atom, a tellurium atom or an arsenic atom. The divalent heterocyclic group may have a substituent. The divalent heterocyclic group usually has 4 to 60 carbon atoms, and preferably 4 to 20 carbon atoms. The number of carbon atoms of the divalent heterocyclic group does not include the number of carbon atoms of the substituent. Examples of such a divalent heterocyclic group include a thiophene diyl group, a C ₁ -C ₁₂ alkylthiophene diyl group, a pyrrole diyl group, a furandiyl group, a pyridinediyl group, a C ₁ -C ₁₂ alkylpyridine diyl group, and a pyridazine. diyl group, a pyrimidine-diyl group, a pyrazinediyl group, a triazine-diyl group, pyrrolidinediyl group, piperidine-diyl group, quinolinediyl group, and isoquinoline-diyl group, among others, a thiophene-diyl group, C 1 _~ C ₁₂ alkyl thiophenediyl group, pyridinediyl More preferred are groups and C ₁ -C ₁₂ alkylpyridinediyl groups.

The ionic polymer containing a divalent aromatic amine residue as a structural unit may further have another structural unit. Examples of other structural units include arylene groups such as a phenylene group and a fluorenediyl group. Of these ionic polymers, those containing a crosslinking group are preferred.

Further, examples of the divalent aromatic amine residue represented by the formula (34) include groups obtained by removing two hydrogen atoms from the aromatic amine represented by the following formulas 101 to 110.

The aromatic amines represented by the formulas 101 to 110 may have a substituent within a range capable of forming a divalent aromatic amine residue, and as the substituent, in the description of Q ¹ described above, Examples of the substituent are the same as the exemplified substituents, and when a plurality of substituents are present, they may be the same or different.

In formula (33), X ′ represents an imino group with or without a substituent, a silylene group with or without a substituent, an ethenylene group with or without a substituent, or an ethynylene group. Examples of the substituent that the imino group, silyl group or ethenylene group may have include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a pentyl group. Alkyl groups having 1 to 20 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group; phenyl group, 1 An aryl group having 6 to 30 carbon atoms such as -naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, etc., and when there are a plurality of substituents, They may be the same or different.

From the viewpoint of stability of the ionic polymer against air, moisture or heat, X ′ is preferably an imino group, an ethenylene group or an ethynylene group.

From the viewpoint of electron acceptability and hole acceptability of the ionic polymer, m33 is preferably 1 and m34 is preferably 0.

As the structural unit represented by the formula (33), the structural unit represented by the formula (35) is preferable from the viewpoint of electron acceptability of the ionic polymer.

(In the formula (35), Ar ¹³ is a pyridinediyl group with or without a substituent, a pyrazinediyl group with or without a substituent, a pyrimidinediyl group with or without a substituent, Represents a pyridazinediyl group with or without a group or a triazinediyl group with or without a substituent.

Examples of the substituent that the pyridinediyl group may have include the same substituents as the substituents exemplified in the description regarding Q ¹ described above. When a plurality of substituents are present, they may be the same or different.
Examples of the substituent that the pyrazinediyl group may have include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.
Examples of the substituent that the pyrimidinediyl group may have include the same substituents as the substituents exemplified in the description regarding Q ¹ described above. When a plurality of substituents are present, they may be the same or different.
Examples of the substituent that the pyridazinediyl group may have include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.
Examples of the substituent that the triazinediyl group may have include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.

-Ratio of structural unit Structural unit represented by formula (13), structural unit represented by formula (15), structural unit represented by formula (17), and ionic polymer used in the present invention, From the viewpoint of the luminous efficiency of the organic EL device, the total proportion of the structural units represented by the formula (20) is 30 to 100 mol% in all the structural units contained in the ionic polymer excluding the terminal structural unit. It is more preferable that

-Terminal structural unit The terminal structural unit (terminal group) of the ionic polymer used in the present invention includes a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s- Butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group , Isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7- Dimethyloctyloxy group, lauryloxy group, methylthio group, ethylthio O, propylthio, isopropylthio, butylthio, isobutylthio, s-butylthio, t-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, nonylthio, decylthio, laurylthio Group, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, s-butoxyphenyl group, t-butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group Cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloxy Tyloxyphenyl group, lauryloxyphenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t-butylphenyl Group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propyl Amino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, pentylamino group, hexylamino Cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group , Dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, Nyl-C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, Di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkyl group Amino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, t-butyldimethylsilyl group, Pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, Chi le dimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-dimethyl silyl group, lauryl dimethyl silyl group, (phenyl _-C 1 _{~ C 12} alkyl) silyl group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) silyl group, (1-naphthyl-C ₁ -C ₁₂ alkyl) Silyl group, (2-naphthyl-C ₁ -C ₁₂ alkyl) silyl group, (phenyl-C ₁ -C ₁₂ alkyl) dimethylsilyl group, triphenylsilyl group, tri (p-xylyl) silyl group, tribenzylsilyl group , Diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl Group, a thienyl _group, C 1 _{~ C 12} alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl _group, C 1 _{~ C 12} alkyl pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, Examples include quinolyl group, isoquinolyl group, hydroxy group, mercapto group, fluorine atom, chlorine atom, bromine atom and iodine atom. When a plurality of the terminal structural units are present, they may be the same or different.

-Characteristics of ionic polymers-
The ionic polymer used in the present invention is preferably a conjugated compound. The ionic polymer used in the present invention is a conjugated compound when the ionic polymer has a multiple bond (for example, double bond, triple bond) or a nitrogen atom, oxygen atom, etc. in the main chain. It means that the pair includes a region that is continuous with one single bond. When the ionic polymer is a conjugated compound, the ratio calculated by the following mathematical formula (A) is preferably 50% or more and more preferably 60% or more from the viewpoint of electron transport properties of the conjugated compound. Preferably, it is 70% or more, more preferably 80% or more, and further preferably 90% or more.
{(The number of atoms on the main chain contained in a region where multiple bonds or unshared electron pairs of nitrogen atoms, oxygen atoms, etc. are connected across one single bond) / (the number of all atoms on the main chain) )} × 100% Formula (A)

The ionic polymer used in the present invention is preferably a polymer compound, more preferably a conjugated polymer compound. Here, the polymer compound means a compound having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ or more. Moreover, the ionic polymer used in the present invention being a conjugated polymer compound means that the ionic polymer is a conjugated compound and a polymer compound.

From the viewpoint of film formability by application of the ionic polymer used in the present invention, the number average molecular weight in terms of polystyrene of the ionic polymer is preferably 1 × 10 ³ to 1 × 10 ⁸ , and preferably 2 × 10 ³ to 1 × 10 ⁷ is more preferable, 3 × 10 ³ to 1 × 10 ⁷ is more preferable, and 5 × 10 ³ to 1 × 10 ⁷ is even more preferable. From the viewpoint of the purity of the ionic polymer, the weight average molecular weight in terms of polystyrene is preferably 1 × 10 ³ to 5 × 10 ⁷ , more preferably 1 × 10 ³ to 1 × 10 ^7. More preferably, it is × 10 ³ to 5 × 10 ⁶ . Further, from the viewpoint of solubility of the ionic polymer, it is preferred that the number average molecular weight in terms of polystyrene is ^{1 × 10 3 ~ 5 × 10} 5, more preferably ^{1 × 10 3 ~ 5 × 10} 4, More preferably, it is 1 × 10 ³ to 3 × 10 ³ . The polystyrene-equivalent number average molecular weight and weight average molecular weight of the ionic polymer used in the present invention can be determined using, for example, gel permeation chromatography (GPC).

From the viewpoint of the purity of the ionic polymer used in the present invention, the number of all structural units (ie, the degree of polymerization) contained in the ionic polymer excluding the terminal structural unit is preferably 1 or more and 20 or less. It is more preferably 10 or less and more preferably 1 or more and 5 or less.

From the viewpoint of electron acceptability and hole acceptability of the ionic polymer used in the present invention, the orbital energy of the lowest unoccupied molecular orbital (LUMO) of the ionic polymer is −5.0 eV or more and −2.0 eV or less. It is preferable that it is -4.5 eV or more and -2.0 eV or less. From the same viewpoint, the orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer is preferably from -6.0 eV to -3.0 eV, more preferably from -5.5 eV to -3.0 eV. Is more preferable. However, the orbital energy of HOMO is lower than that of LUMO. The orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer is obtained by measuring the ionization potential of the ionic polymer and using the obtained ionization potential as the orbital energy. On the other hand, the orbital energy of the lowest unoccupied molecular orbital (LUMO) of the ionic polymer is obtained by calculating the energy difference between HOMO and LUMO and using the sum of the value and the ionization potential measured above as the orbital energy. . A photoelectron spectrometer is used to measure the ionization potential. Further, the energy difference between HOMO and LUMO is obtained from the absorption terminal by measuring the absorption spectrum of the ionic polymer using an ultraviolet / visible / near infrared spectrophotometer.

The polymer used in the present invention is preferably substantially non-luminescent when used in an electroluminescent device. Here, the fact that a certain polymer is substantially non-luminous means as follows. First, an electroluminescent element A having a layer containing a certain polymer is produced. On the other hand, the electroluminescent element 2 which does not have the layer containing a polymer is produced. Although the electroluminescent element A has a layer containing a polymer, the electroluminescent element 2 is different from the electroluminescent element 2 only in that it does not have a layer containing a polymer. Next, a forward voltage of 10 V is applied to the electroluminescent element A and the electroluminescent element 2 to measure an emission spectrum. The wavelength λ that gives the maximum peak in the emission spectrum obtained for the electroluminescent element 2 is obtained. The emission spectrum at the wavelength λ is set to 1, the emission spectrum obtained for the electroluminescent element 2 is normalized, and the normalized emission amount S ₀ is calculated by integrating with respect to the wavelength. On the other hand, assuming that the emission intensity at the wavelength λ is 1, the emission spectrum obtained for the electroluminescent element A is also normalized, and the normalized emission amount S is calculated by integrating the wavelength. When the value calculated by (S−S ₀ ) / S ₀ × 100% is 30% or less, that is, compared with the normalized luminescence amount of the electroluminescent device 2 having no polymer-containing layer, the polymer When the increase in the normalized luminescence amount of the electroluminescent element A having a layer containing is 30% or less, the polymer used is substantially non-luminous, and (S−S ₀ ) / S _The value calculated by ₀ × 100 is preferably 15% or less, and more preferably 10% or less.

As the ionic polymer containing the group represented by the formula (1) and the group represented by the formula (3), an ionic polymer consisting only of the group represented by the formula (23), a formula (23) One or more selected from the group consisting of groups represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110, wherein two hydrogen atoms are removed. An ionic polymer comprising only the group represented by formula (24), a group represented by formula (24) and the formulas 45 to 50, 59, 60, 77, 80, 91, 92 96, 101 to 110, an ionic polymer comprising one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms, an ion comprising only the group represented by formula (25) Polymer, group represented by formula (25) and formula 4 An ionic polymer comprising one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms from the groups represented by ˜50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 An ionic polymer consisting only of a group represented by formula (29), a group represented by formula (29) and formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 An ionic polymer comprising at least one group selected from the group consisting of groups obtained by removing two hydrogen atoms from the represented group, an ionic polymer comprising only the group represented by formula (30), formula (30) And one selected from the group consisting of groups represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110, in which two hydrogen atoms are removed. Examples include ionic polymers consisting of the above groups That.

Examples of the ionic polymer containing the group represented by the formula (1) and the group represented by the formula (3) include the following polymer compounds. Among these, in the polymer compound represented by the formula in which two types of structural units are separated by a slash “/”, the proportion of the structural unit on the left is p mol% and the proportion of the structural unit on the right is (100− p) mol%, and these structural units are randomly arranged. In the following formula, n represents the degree of polymerization.

(In the formula, p represents a number of 15 to 100.)

As an ionic polymer containing the group represented by the formula (2) and the group represented by the formula (3), an ionic polymer consisting only of the group represented by the formula (26), the formula (26) One or more selected from the group consisting of groups represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110, wherein two hydrogen atoms are removed. An ionic polymer comprising only the group represented by the formula (27), a group represented by the formula (27) and the formulas 45 to 50, 59, 60, 77, 80, 91, 92 96, 101 to 110, an ionic polymer comprising one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms, ions comprising only groups represented by formula (28) Polymer, group represented by formula (28) and formula 4 An ionic polymer comprising one or more groups selected from the group consisting of groups obtained by removing two hydrogen atoms from the groups represented by ˜50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 An ionic polymer comprising only a group represented by formula (31), a group represented by formula (31), and formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110 An ionic polymer comprising at least one group selected from the group consisting of groups obtained by removing two hydrogen atoms from the represented group, an ionic polymer comprising only the group represented by formula (32), formula (32) And one selected from the group consisting of groups represented by formulas 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110, in which two hydrogen atoms are removed. Examples include ionic polymers consisting of the above groups That.

Examples of the ionic polymer containing the group represented by the formula (2) and the group represented by the formula (3) include the following polymer compounds. Among these, in the polymer compound represented by the formula in which two types of structural units are separated by a slash “/”, the proportion of the structural unit on the left is p mol% and the proportion of the structural unit on the right is (100− p) mol%, and these structural units are randomly arranged. In the following formula, n represents the degree of polymerization.

(In the formula, p represents a number of 15 to 100.)

-Production method of ionic polymer-
Next, a method for producing the ionic polymer used in the present invention will be described. As a suitable method for producing the ionic polymer used in the present invention, for example, a compound represented by the following general formula (36) is selected and used as one of the raw materials. ) in -A _a - compound is a structural unit represented by the formula (13), said -A _a - compound is a structural unit represented by the formula (15), said -A _a - is the formula ( 17) A method in which at least one of a compound that is a structural unit represented by formula (17) and a compound in which -A _a -is a structural unit represented by formula (20) is contained as an essential raw material, and this is subjected to condensation polymerization Can be mentioned.

Y ⁴ -A _a -Y ⁵ (36)
(In formula (36), A _a is represented by one or more groups selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) and 1 represented by formula (3). A repeating unit containing a group of at least species is represented, and Y ⁴ and Y ⁵ each independently represent a group involved in condensation polymerization.)

When the ionic polymer used in the present invention contains a structural unit represented by -A _a- in the above formula (36) and another structural unit other than -A _a- , When a compound having two substituents involved in condensation polymerization, which is another structural unit other than —A _a —, is used together with the compound represented by the formula (36), the condensation polymerization is performed. Good.

Examples of the compound having two condensation-polymerizable substituents used to contain such other structural units include compounds represented by the formula (37). In this manner, in addition to the compound represented by Y ⁴ -A _a -Y ⁵ , the structural unit represented by -A _b- is obtained by condensation polymerization of the compound represented by Formula (37). Furthermore, the ionic polymer used in the present invention can be produced.

Y ⁶ -A _b -Y ⁷ (37)
(In the formula (37), _Ab is a structural unit represented by the general formula (33) or a structural unit represented by the general formula (35), and Y ⁶ and Y ⁷ are each independently a condensation polymerization. Represents a group involved in

Examples of groups (Y ⁴ , Y ⁵ , Y ⁶ and Y ⁷ ) involved in such condensation polymerization include a hydrogen atom, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, a borate ester residue, Examples thereof include a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, a monohalogenated methyl group, —B (OH) ₂ , a formyl group, a cyano group, and a vinyl group.

Examples of the halogen atom that can be selected as a group involved in such condensation polymerization include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl sulfonate group that can be selected as the group involved in the condensation polymerization include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Is exemplified.

Examples of the arylalkyl sulfonate group that can be selected as a group involved in the condensation polymerization include a benzyl sulfonate group.

Further, examples of the boric acid ester residue that can be selected as a group involved in the condensation polymerization include groups represented by the following formulae.

Furthermore, the sulfonium methyl group that can be selected as a group involved in the condensation polymerization includes the following formula:
—CH ₂ S ⁺ Me ₂ E ⁻ or —CH ₂ S ⁺ Ph ₂ E ⁻
(Wherein E represents a halogen atom, Ph represents a phenyl group, and the same shall apply hereinafter).

Examples of the phosphonium methyl group that can be selected as the group involved in the condensation polymerization include the following formula:
-CH ₂ P ⁺ Ph ₃ E ^-
(Wherein E represents a halogen atom).

The phosphonate methyl group that can be selected as the group involved in the condensation polymerization is represented by the following formula:
—CH ₂ PO (OR ^d ) ₂
(Wherein, R ^d represents an alkyl group, an aryl group, or an arylalkyl group).

Furthermore, examples of the monohalogenated methyl group that can be selected as the group involved in the condensation polymerization include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

Further, a group suitable as a group involved in condensation polymerization varies depending on the type of polymerization reaction. For example, when a zerovalent nickel complex such as a Yamamoto coupling reaction is used, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group And arylalkyl sulfonate groups. In the case of using a nickel catalyst or palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a borate ester residue, —B (OH) _{2 and the} like can be mentioned. In the case of oxidative polymerization, a hydrogen atom is exemplified.

When producing the ionic polymer used in the present invention, for example, if necessary, the compound (monomer) represented by the general formula (36) or (37) having a plurality of groups involved in condensation polymerization may be used. You may employ | adopt the polymerization method which melt | dissolves in an organic solvent, and makes it react at the temperature below the melting | fusing point of an organic solvent below a boiling point using an alkali and a suitable catalyst. Such polymerization methods include, for example, “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”. Syntheses ”, Collective Volume 6 (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review, Vol. 95, 2457 ( 1995), Journal of Organometallic Chemistry, Vol. 576, 147 (1999), Kuromorekyura Chemistry Macromolecular Symposium (Macromol.Chem., Macromol.Symp.), Vol. 12, it is possible to employ a known method described in page 229 (1987).

Moreover, when manufacturing the ionic polymer used for this invention, you may employ | adopt a known condensation polymerization reaction according to the group which participates in condensation polymerization. Examples of such a polymerization method include a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) complex, a method of polymerizing by an oxidizing agent such as FeCl ₃ , Examples thereof include a method of electrochemically oxidative polymerization and a method of decomposing an intermediate polymer having an appropriate leaving group. Among such polymerization reactions, a polymerization method using a Suzuki coupling reaction, a polymerization method using a Grignard reaction, and a polymerization method using a nickel zero-valent complex are preferable because the structure of the resulting ionic polymer can be easily controlled.

One aspect of a preferred method for producing the ionic polymer used in the present invention is a group selected from the group consisting of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an aryl alkyl sulfonate group as a group involved in condensation polymerization. This is a method for producing an ionic polymer by condensation polymerization in the presence of a nickel zero-valent complex using a starting material monomer. Examples of the raw material monomer used in such a method include dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, and halogen-aryl sulfonates. Compounds, halogen-aryl alkyl sulfonate compounds, alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds and aryl sulfonate-aryl alkyl sulfonate compounds.

In another aspect of the preferred production method of the ionic polymer, a group involved in condensation polymerization includes a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, —B (OH) ₂ , and a boric acid ester residue. The total number of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and arylalkyl sulfonate groups (J), and —B (OH) ₂ and Using a raw material monomer in which the ratio of the total number of moles of boric acid ester residues (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2), the nickel catalyst or palladium catalyst It is a method for producing an ionic polymer by condensation polymerization in the presence.

As the organic solvent, although it varies depending on the compound and reaction used, it is generally preferable to use an organic solvent that has been sufficiently deoxygenated to suppress side reactions. When manufacturing an ionic polymer, it is preferable to advance reaction in inert atmosphere using such an organic solvent. In the organic solvent, it is preferable to perform a dehydration process in the same manner as the deoxygenation process. However, this is not the case in the case of reaction in a two-phase system with water such as Suzuki coupling reaction.

Examples of such organic solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloro Halogenated saturated hydrocarbons such as pentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, alcohols such as t-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl ether, Ethers such as lahydrofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, amines such as N, N, N ′, N′-tetramethylethylenediamine, pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N And amides such as N-diethylacetamide and N-methylmorpholine oxide. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ethers are more preferable from the viewpoint of reactivity, tetrahydrofuran and diethyl ether are more preferable, and toluene and xylene are preferable from the viewpoint of reaction rate.

In producing the ionic polymer, it is preferable to add an alkali or a suitable catalyst in order to react the raw material monomers. What is necessary is just to select such an alkali or a catalyst according to the superposition | polymerization method etc. to employ | adopt. Such an alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. Further, as a method of mixing the alkali or catalyst, the alkali or catalyst solution is slowly added while stirring the reaction liquid under an inert atmosphere such as argon or nitrogen, or the reaction liquid is added to the alkali or catalyst solution. The method of adding slowly is illustrated.

In the ionic polymer used in the present invention, if the polymerization active group remains as it is in the terminal group, the light emitting characteristics and life characteristics of the resulting light emitting device may be deteriorated. Therefore, the terminal group is protected with a stable group. May be. When the terminal group is protected with such a stable group, when the ionic polymer used in the present invention is a conjugated compound, it has a conjugated bond continuous with the conjugated structure of the main chain of the ionic polymer. The structure is preferably, for example, a structure bonded to an aryl group or a heterocyclic group via a carbon-carbon bond. Examples of such a stable group for protecting the end group include substituents such as a monovalent aromatic compound group represented by the structural formula of Chemical Formula 10 in JP-A-9-45478.

As another preferable method for producing the ionic polymer containing the structural unit represented by the formula (1), an ionic polymer having no cation is polymerized in the first step, and then from the ionic polymer in the second step. The method of manufacturing the ionic polymer containing a cation is mentioned. As the method for polymerizing the ionic polymer having no cation in the first step, the above-mentioned condensation polymerization reaction may be mentioned. Examples of the reaction in the second step include a hydrolysis reaction with a metal hydroxide, an alkyl ammonium hydroxide, or the like.

As another preferred method for producing an ionic polymer containing a group represented by the formula (2), an ionic polymer having no ions is polymerized in the first step, and ions are generated from the ionic polymer in the second step. The method of manufacturing the ionic polymer containing this is mentioned. As a method for polymerizing an ionic polymer having no ions in the first step, the above-mentioned condensation polymerization reaction may be mentioned. Examples of the reaction in the second step include quaternary ammonium chlorination reaction of amine using alkyl halide, halogen abstraction reaction with SbF _{5 and the} like.

Since the ionic polymer used in the present invention is excellent in charge injection and transportability, an element that emits light with high brightness can be obtained.

Examples of a method for forming a layer containing an ionic polymer include a method of forming a film using a solution containing an ionic polymer.

Solvents used for film formation from such solutions include alcohols other than water, ethers, esters, nitrile compounds, nitro compounds, alkyl halides, aryl halides, thiols, sulfides Of the solvents such as sulfoxides, thioketones, amides and carboxylic acids, those having a solubility parameter of 9.3 or more are preferable. Examples of the solvent (values in parentheses represent solubility parameter values of each solvent) include methanol (12.9), ethanol (11.2), 2-propanol (11.5), 1- Butanol (9.9), t-butyl alcohol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7), N, N-dimethylformamide (11.5), dimethyl sulfoxide (12.8), acetic acid (12.4), nitrobenzene (11.1), nitromethane (11.0), 1,2-dichloroethane (9.7), dichloromethane (9.6), chlorobenzene (9.6) ), Bromobenzene (9.9), dioxane (9.8), propylene carbonate (13.3), pyridine (10.4), carbon disulfide (10.0), and a mixed solvent thereof. It is. Here, a mixed solvent formed by mixing two kinds of solvents (referred to as solvent 1 and solvent 2) will be described. The solubility parameter (δ _m ) of the mixed solvent is δ _m = δ ₁ × φ ₁ + δ ₂ × it that obtained by phi ₂ ([delta] ₁ is the solubility parameter of the solvent 1, phi ₁ is the volume fraction of solvent 1, [delta] ₂ is the solubility parameter, phi ₂ is the volume fraction of solvent 2 in the solvent 2.)

As the film thickness of the electron injection layer, the optimum value varies depending on the ionic polymer to be used, so that the drive voltage and the light emission efficiency may be selected to be appropriate values, and a thickness that does not cause pinholes is required. From the viewpoint of lowering the driving voltage of the element, the film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and even more preferably 2 nm to 200 nm. From the viewpoint of protecting the light emitting layer, the film thickness is preferably 5 nm to 1 μm.

<Cathode>
As a material for the cathode, a material having high electrical conductivity is preferable. Moreover, in the organic EL element of the structure which takes out light from an anode side, in order to reflect the light from a light emitting layer to an anode side with a cathode, the material with a high visible light reflectance is preferable as a material of a cathode. For the cathode, gold, silver, platinum, copper, aluminum, manganese, titanium, cobalt, nickel, tungsten, tin alone or an alloy containing one or more, graphite, or a graphite intercalation compound is used. As the cathode, a conductive metal oxide, a conductive resin, a mixture of a resin and a conductive filler, or the like can be used. Specifically, examples of the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO, and examples of the conductive resin include 3,4-polyethylenedioxythiophene / polystyrene sulfonic acid. Can do.
In the case of a thin film composed of a resin and a conductive filler, a conductive resin can be used as the resin. Further, as the conductive filler, metal fine particles, conductive wires, and the like can be used. As the conductive filler, Au, Ag, Al, or the like can be used. The cathode may be composed of a laminate in which two or more layers are laminated.

The film thickness of the cathode is appropriately designed in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded. As a method for manufacturing the cathode, a coating method can be used in the case of using ink in which a conductive filler and a resin are dispersed in a dispersion medium.

An ionic polymer was produced by the following method, and an organic EL device was produced using this ionic polymer for an electron injection layer.

[Reference Example 1]
Synthesis of 2,7-dibromo-9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (compound A) 2,7-dibromo -9-fluorenone (52.5 g), ethyl salicylate (154.8 g), and mercaptoacetic acid (1.4 g) were placed in a 300 mL flask and purged with nitrogen. Thereto was added methanesulfonic acid (630 mL) and the mixture was stirred at 75 ° C. overnight. The mixture was allowed to cool, added to ice water and stirred for 1 hour. The resulting solid was filtered off and washed with heated acetonitrile. The washed solid was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution and filtered. The resulting solid (62.7 g), 2- [2- (2-methoxyethoxy) ethoxy] -p-toluenesulfonate (86.3 g), potassium carbonate (62.6 g), and 18-crown-6 (7 2 g) was dissolved in N, N-dimethylformamide (DMF) (670 mL) and the solution was transferred to a flask and stirred at 105 ° C. overnight. The obtained mixture was allowed to cool to room temperature, added to ice water, and stirred for 1 hour. Chloroform (300 mL) was added to the reaction solution, liquid separation extraction was performed, and the solution was concentrated to give 2,7-dibromo-9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2 -Methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound A) (51.2 g) was obtained.

Compound A

[Reference Example 2]
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis [3-ethoxycarbonyl-4- [2- [2- ( Synthesis of 2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound B) Compound A (15 g), bis (pinacolato) diboron (8.9 g), [1,1′-bis (diphenylphos) under nitrogen atmosphere Fino) ferrocene] dichloropalladium (II) dichloromethane complex (0.8 g), 1,1′-bis (diphenylphosphino) ferrocene (0.5 g), potassium acetate (9.4 g), dioxane (400 mL) were mixed. , Heated to 110 ° C. and heated to reflux for 10 hours. The reaction liquid was filtered after standing_to_cool and the filtrate was concentrate | evaporated under reduced pressure. The reaction mixture was washed 3 times with methanol. The precipitate was dissolved in toluene, and activated carbon was added to the solution and stirred. Thereafter, filtration is performed, and the filtrate is concentrated under reduced pressure to give 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis. [3-Ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound B) (11.7 g) was obtained.

Compound B

[Reference Example 3]
Synthesis of poly [9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene] (Polymer A) Compound A under an inert atmosphere (0.55 g), Compound B (0.61 g), triphenylphosphine palladium (0.01 g), methyl trioctyl ammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene ( 10 mL) and heated to 105 ° C. To this reaction solution, 2M aqueous sodium carbonate solution (6 mL) was added dropwise and refluxed for 8 hours. 4-t-butylphenylboronic acid (0.01 g) was added to the reaction solution, and the mixture was refluxed for 6 hours. Then, a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g / mL) was added, and the mixture was stirred for 2 hours. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 mL of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran. The solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried. Yield of the obtained poly [9,9-bis [3-ethoxycarbonyl-4-bis [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene] (polymer A (BSAFEGGP)) Was 520 mg.

The number average molecular weight in terms of polystyrene of the polymer A was 5.2 × 10 ⁴ . The polymer A consists of a repeating unit represented by the formula (A).

[Experimental Example 1]
Synthesis of Polymer A Cesium Salt Polymer A (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (20 mL) and ethanol (20 mL) were added and the mixture was warmed to 55 ° C. An aqueous solution in which cesium hydroxide (200 mg) was dissolved in water (2 mL) was added thereto, and the mixture was stirred at 55 ° C. for 6 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (150 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer A completely disappeared. The obtained cesium salt of polymer A is referred to as conjugated polymer compound 1. Conjugated polymer compound 1 is composed of a repeating unit represented by formula (B) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) ”is 100 mol%.) The conjugated polymer compound 1 had an orbital energy of HOMO of −5.5 eV and an orbital energy of LUMO of −2.7 eV.

[Experiment 2]
Synthesis of Polymer A Potassium Salt Polymer A (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (20 mL) and methanol (10 mL) were mixed, an aqueous solution in which potassium hydroxide (400 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 1 hour. 50 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (131 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer A completely disappeared. The obtained potassium salt of polymer A is referred to as conjugated polymer compound 2. Conjugated polymer compound 2 is composed of a repeating unit represented by formula (C) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 100 mol%.) The conjugated polymer compound 2 had an orbital energy of HOMO of −5.5 eV and an orbital energy of LUMO of −2.7 eV.

[Experiment 3]
Synthesis of Polymer A Sodium Salt Polymer A (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (20 mL) and methanol (10 mL) were mixed, an aqueous solution in which sodium hydroxide (260 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 1 hr. 30 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (123 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer A completely disappeared. The resulting sodium salt of polymer A is referred to as conjugated polymer compound 3. Conjugated polymer compound 3 is composed of a repeating unit represented by formula (D) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 100 mol%.) The conjugated polymer compound 3 had a HOMO orbital energy of −5.6 eV and a LUMO orbital energy of −2.8 eV.

[Experimental Example 4]
Synthesis of Polymer A Ammonium Salt Polymer A (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (20 mL) and methanol (15 mL) were mixed, an aqueous solution in which tetramethylammonium hydroxide (50 mg) was dissolved in water (1 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 6 hours. An aqueous solution in which tetramethylammonium hydroxide (50 mg) was dissolved in water (1 mL) was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (150 mg). From the NMR spectrum, it was confirmed that 90% of the signal derived from the ethyl group at the ethyl ester site in the polymer A disappeared. The resulting ammonium salt of polymer A is referred to as conjugated polymer compound 4. The conjugated polymer compound 4 is composed of a repeating unit represented by the formula (E) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 90 mol%.) The conjugated polymer compound 4 had a HOMO orbital energy of −5.6 eV and a LUMO orbital energy of −2.8 eV.

[Reference Example 4]
2,7-bis [7- (4-methylphenyl) -9,9-dioctylfluoren-2-yl] -9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxy) Synthesis of ethoxy) ethoxy] ethoxy] phenyl] -fluorene (Polymer B) Compound A (0.52 g), 2,7-bis (1,3,2-dioxaborolan-2-yl) -9 under inert atmosphere , 9-dioctylfluorene (1.29 g), triphenylphosphine palladium (0.0087 g), methyl trioctyl ammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g), toluene (10 mL), and 2M aqueous sodium carbonate solution (10 mL) was mixed and heated to 80 ° C. The reaction was allowed to react for 3.5 hours. Thereafter, parabromotoluene (0.68 g) was added thereto, and the mixture was further reacted for 2.5 hours. After the reaction, the reaction solution was cooled to room temperature, 50 ml of ethyl acetate / 50 ml of distilled water were added, and the aqueous layer was removed. After adding 50 ml of distilled water again to remove the aqueous layer, magnesium sulfate was added as a desiccant, and the insoluble matter was filtered to remove the organic solvent. Thereafter, the obtained residue was dissolved again in 10 mL of THF, 2 mL of saturated aqueous sodium diethyldithiocarbamate was added and stirred for 30 minutes, and then the organic solvent was removed. Purification was performed through an alumina column (developing solvent hexane: ethyl acetate = 1: 1, v / v), and the deposited precipitate was filtered and dried under reduced pressure for 12 hours. As a result, 2,7-bis [7- (4-methyl Phenyl) -9,9-dioctylfluoren-2-yl] -9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (heavy 524 mg of union B) was obtained.

The number average molecular weight in terms of polystyrene of the polymer B was 2.0 × 10 ³ . The polymer B is represented by the formula (F).

[Experimental Example 5]
Synthesis of Polymer B Cesium Salt Polymer B (262 mg) was placed in a 100 mL flask and purged with argon. Tetrahydrofuran (10 mL) and methanol (15 mL) were added thereto, and the mixture was heated to 55 ° C. The aqueous solution which melt | dissolved cesium hydroxide (341 mg) in water (1 mL) was added there, and it stirred at 55 degreeC for 5 hours. After the resulting mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (250 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site had completely disappeared. The obtained polymer B cesium salt is referred to as a conjugated polymer compound 5. The conjugated polymer compound 5 is represented by the formula (G) (“one type selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2) in all repeating units). "Ratio of repeating units containing the above groups and one or more groups represented by formula (3)" and "in formulas (13), (15), (17), (20) in all repeating units" “The ratio of the repeating unit represented” is 33.3 mol% rounded off to the second decimal place.) The conjugated polymer compound 5 had a HOMO orbital energy of −5.6 eV and a LUMO orbital energy of −2.6 eV.

[Reference Example 5]
Synthesis of Polymer C Compound A (0.40 g), Compound B (0.49 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-) under an inert atmosphere Butyl-2,6-dimethylphenyl) 1,4-phenylenediamine (35 mg), triphenylphosphine palladium (8 mg), methyltrioctylammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g), And toluene (10 mL) were mixed and heated to 105 ° C. To this reaction solution, 2M aqueous sodium carbonate solution (6 mL) was added dropwise and refluxed for 8 hours. Phenylboronic acid (0.01 g) was added to the reaction solution and refluxed for 6 hours. Then, a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g / mL) was added, and the mixture was stirred for 2 hours. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 mL of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran. The solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer C was 526 mg.

The number average molecular weight in terms of polystyrene of the polymer C was 3.6 × 10 ⁴ . The polymer C consists of a repeating unit represented by the formula (H).

N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-butyl-2,6-dimethylphenyl) 1,4-phenylenediamine is disclosed in, for example, JP-A-2008-74017. It can be synthesized by the method described in the publication.

[Experimental Example 6]
Synthesis of Polymer C Cesium Salt Polymer C (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (20 mL) and methanol (20 mL) were added and mixed. An aqueous solution in which cesium hydroxide (200 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 1 hour. 30 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (150 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer C had completely disappeared. The obtained cesium salt of polymer C is referred to as conjugated polymer compound 6. The conjugated polymer compound 6 is composed of a repeating unit represented by the formula (I) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 95 mol%.). The conjugated polymer compound 6 had a HOMO orbital energy of −5.3 eV and a LUMO orbital energy of −2.6 eV.

[Reference Example 6]
Synthesis of Polymer D Compound A (0.55 g), Compound B (0.67 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-) under an inert atmosphere Butyl-2,6-dimethylphenyl) 1,4-phenylenediamine (0.038 g), 3,7-dibromo-N- (4-n-butylphenyl) phenoxazine 0.009 g, triphenylphosphine palladium (0. 01 g), methyltrioctylammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed and heated to 105 ° C. To this reaction solution, 2M aqueous sodium carbonate solution (6 mL) was added dropwise and refluxed for 2 hours. Phenylboronic acid (0.004 g) was added to the reaction solution and refluxed for 6 hours. Then, a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g / mL) was added, and the mixture was stirred for 2 hours. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 mL of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran. The solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer D was 590 mg.

The number average molecular weight in terms of polystyrene of the polymer D was 2.7 × 10 ⁴ . The polymer D consists of a repeating unit represented by the formula (J).
3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.

[Experimental Example 7]
Synthesis of Polymer D Cesium Salt Polymer D (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (15 mL) and methanol (10 mL) were mixed. An aqueous solution in which cesium hydroxide (360 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 3 hours. 10 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (210 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer D had completely disappeared. The resulting cesium salt of polymer D is referred to as conjugated polymer compound 7. The conjugated polymer compound 7 is composed of a repeating unit represented by the formula (K) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by the formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 90 mol%.) The conjugated polymer compound 7 had a HOMO orbital energy of −5.3 eV and a LUMO orbital energy of −2.4 eV.

[Reference Example 7]
Synthesis of Polymer E In an inert atmosphere, Compound A (0.37 g), Compound B (0.82 g), 1,3-dibromobenzene (0.09 g), triphenylphosphine palladium (0.01 g), methyltri Octyl ammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL) were mixed and heated to 105 ° C. To this reaction solution, a 2M aqueous sodium carbonate solution (6 mL) was added dropwise and refluxed for 7 hours. Phenylboronic acid (0.002 g) was added to the reaction solution and refluxed for 10 hours. Next, an aqueous sodium diethyldithiacarbamate solution (10 mL, concentration: 0.05 g / mL) was added and stirred for 1 hour. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 mL of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran. The solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer E was 293 mg.

The number average molecular weight in terms of polystyrene of the polymer E was 1.8 × 10 ⁴ . The polymer E consists of a repeating unit represented by the formula (L).

[Experimental Example 8]
Synthesis of Polymer E Cesium Salt Polymer E (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (10 mL) and methanol (5 mL) were mixed. An aqueous solution in which cesium hydroxide (200 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 2 hours. 10 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 5 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (170 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer E completely disappeared. The resulting cesium salt of polymer E is referred to as conjugated polymer compound 8. Conjugated polymer compound 8 is composed of a repeating unit represented by formula (M) ("selected from the group consisting of a group represented by formula (1) and a group represented by formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 75 mol%.) The conjugated polymer compound 8 had a HOMO orbital energy of −5.6 eV and a LUMO orbital energy of −2.6 eV.

[Reference Example 8]
Synthesis of Polymer F Under an inert atmosphere, Compound B (1.01 g), 1,4-dibromo-2,3,5,6-tetrafluorobenzene (0.30 g), triphenylphosphine palladium (0.02 g) , Methyltrioctylammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed and heated to 105 ° C. To this reaction solution, 2M aqueous sodium carbonate solution (6 mL) was added dropwise and refluxed for 4 hours. Phenylboronic acid (0.002 g) was added to the reaction solution and refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution (10 mL, concentration: 0.05 g / mL) was added and stirred for 1 hour. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was dropped into a mixed solvent of 120 ml of methanol and 50 mL of 3% by weight acetic acid aqueous solution and stirred for 1 hour, and then the deposited precipitate was filtered and dissolved in 20 ml of tetrahydrofuran. The solution thus obtained was dropped into 200 ml of methanol and stirred for 30 minutes, and then the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in a mixed solvent of tetrahydrofuran / ethyl acetate (1/1 (volume ratio)) and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution collected from the column was concentrated and then added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer E was 343 mg.

The polystyrene equivalent number average molecular weight of the polymer F was 6.0 × 10 ⁴ . The polymer F consists of a repeating unit represented by the formula (N).

[Experimental Example 9]
Synthesis of Polymer F Cesium Salt Polymer F (150 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (10 mL) and methanol (5 mL) were mixed. An aqueous solution in which cesium hydroxide (260 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 2 hours. 10 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 5 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (130 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer E completely disappeared. The resulting cesium salt of polymer F is referred to as conjugated polymer compound 9. The conjugated polymer compound 9 is composed of a repeating unit represented by the formula (O) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by the formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 75 mol%.) The conjugated polymer compound 9 had a HOMO orbital energy of −5.9 eV and a LUMO orbital energy of −2.8 eV.

[Reference Example 9]
Under an inert atmosphere, 2- [2- (2-methoxyethoxy) ethoxy] -p-toluenesulfonate (11.0 g), triethylene glycol (30.0 g), and potassium hydroxide (3.3 g) were mixed. The mixture was stirred with heating at 100 ° C. for 18 hours. After allowing to cool, the reaction solution was added to water (100 mL), liquid separation extraction was performed with chloroform, and the solution was concentrated. The concentrated solution was subjected to Kugelrohr distillation (10 mm Torr, 180 ° C.) to give 2- (2- (2- (2- (2- (2-methoxyethoxy) -ethoxy) -ethoxy) -ethoxy) -ethoxy). Ethanol (6.1 g) was obtained.

[Reference Example 10]
Under an inert atmosphere, 2- (2- (2- (2- (2- (2-methoxyethoxy) -ethoxy) -ethoxy) -ethoxy) -ethoxy) ethanol (8.0 g), sodium hydroxide (1. 4 g), distilled water (2 mL) and tetrahydrofuran (2 mL) were mixed and ice-cooled. To the mixed solution, a solution of p-tosyl chloride (5.5 g) in tetrahydrofuran (6.4 mL) was added dropwise over 30 minutes. After the addition, the reaction solution was raised to room temperature and stirred for 15 hours. Distilled water (50 mL) was added to the reaction solution, and the reaction solution was neutralized with 6M sulfuric acid, followed by liquid separation extraction with chloroform. The solution was concentrated to give 2- (2- (2- (2- (2- (2-methoxyethoxy) -ethoxy) -ethoxy) -ethoxy) -ethoxy) p-toluenesulfonate (11.8 g). It was.

[Reference Example 11]
2,7-dibromo-9,9-bis [3-ethoxycarbonyl-4- [2- (2- (2- (2- (2- (2-methoxyethoxy) -ethoxy) -ethoxy) -ethoxy)- Synthesis of Ethoxy) Ethoxy] phenyl] -fluorene (Compound C) 2,7-dibromo-9-fluorenone (127.2 g), ethyl salicylate (375.2 g), and mercaptoacetic acid (3.5 g) were placed in a 300 mL flask. And replaced with nitrogen. Thereto was added methanesulfonic acid (1420 mL) and the mixture was stirred at 75 ° C. overnight. The mixture was allowed to cool, added to ice water and stirred for 1 hour. The resulting solid was filtered off and washed with heated acetonitrile. The washed solid was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution and filtered to obtain a solid (167.8 g). The resulting solid (5 g), 2- (2- (2- (2- (2- (2-methoxyethoxy) -ethoxy) -ethoxy) -ethoxy) -ethoxy) p-toluenesulfonate (10.4 g), Potassium carbonate (5.3 g) and 18-crown-6 (0.6 g) were dissolved in N, N-dimethylformamide (DMF) (100 mL), and the solution was transferred to a flask and stirred at 105 ° C. for 4 hours. . The obtained mixture was allowed to cool to room temperature, added to ice water, and stirred for 1 hour. Chloroform (300 mL) was added to the reaction solution, liquid separation extraction was performed, and the solution was concentrated. The concentrate was dissolved in ethyl acetate, passed through an alumina column, and the solution was concentrated to give 2,7-dibromo-9,9-bis [3-ethoxycarbonyl-4- [2- (2- (2- ( 2- (2- (2- (2- (2-methoxyethoxy) -ethoxy) -ethoxy) -ethoxy) -ethoxy) ethoxy] phenyl] -fluorene (compound C) (4.5 g) was obtained.

Compound C

[Reference Example 12]
Synthesis of Polymer G In an inert atmosphere, 200 mL of Compound C (1.0 g), 4-t-butylphenyl bromide (0.9 mg), 2,2′-bipyridine (0.3 g), dehydrated tetrahydrofuran (50 mL) Mix in flask. The temperature of the mixture was raised to 55 ° C., bis (1,5-cyclooctadiene) nickel (0.6 g) was added, and the mixture was stirred at 55 ° C. for 5 hours. After the mixture was cooled to room temperature, the reaction solution was added dropwise to a mixture of methanol (200 mL) and 1N dilute hydrochloric acid (200 mL). The resulting precipitate was collected by filtration and redissolved in tetrahydrofuran. The solution was added dropwise to a mixture of methanol (200 mL) and 15% aqueous ammonia (100 mL), and the resulting precipitate was collected by filtration. The precipitate was redissolved in tetrahydrofuran, added dropwise to a mixture of methanol (200 mL) and water (100 mL), and the resulting precipitate was collected by filtration. The collected precipitate was dried under reduced pressure to obtain a polymer G (360 mg). The number average molecular weight in terms of polystyrene of the polymer G was 6.0 × 10 ⁴ . The polymer G consists of a repeating unit represented by the formula (P).

[Experimental Example 10]
Synthesis of Polymer G Cesium Salt Polymer G (150 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (15 mL) and methanol (5 mL) were mixed. An aqueous solution in which cesium hydroxide (170 mg) was dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 6 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (95 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer G had completely disappeared. The obtained cesium salt of polymer G is referred to as conjugated polymer compound 10. The conjugated polymer compound 10 is composed of a repeating unit represented by the formula (Q) (“selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by the formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 100 mol%.) The conjugated polymer compound 10 had a HOMO orbital energy of −5.7 eV and a LUMO orbital energy of −2.9 eV.

[Reference Example 13]
Synthesis of 1,3-dibromo-5-ethoxycarbonyl-6- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] benzene 3,5-dibromosalicylic acid (20 g), ethanol (17 mL) under inert atmosphere ), Concentrated sulfuric acid (1.5 mL) and toluene (7 mL) were mixed, and the mixture was stirred with heating at 130 ° C. for 20 hours. After allowing to cool, the reaction solution was added to ice water (100 mL), liquid separation extraction was performed with chloroform, and the solution was concentrated. The obtained solid was dissolved in isopropanol, and the solution was added dropwise to distilled water. The obtained precipitate was filtered off to obtain a solid (18 g). Under an inert atmosphere, the obtained solid (1 g), 2- [2- (2-methoxyethoxy) ethoxy] -p-toluenesulfonate (1.5 g), potassium carbonate (0.7 g), DMF (15 mL) were added. Mix and stir at 100 ° C. for 4 hours. After allowing to cool, chloroform was added to perform liquid separation and extraction, and the solution was concentrated. The concentrate was dissolved in chloroform and purified by passing through a silica gel column. The solution was concentrated to give 1,3-dibromo-5-ethoxycarbonyl-6- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] benzene (1.0 g).

[Reference Example 14]
Synthesis of Polymer H Compound A (0.2 g), Compound B (0.5 g), 1,3-dibromo-5-ethoxycarbonyl-6- [2- [2- (2-methoxyethoxy) under an inert atmosphere ) Ethoxy] ethoxy] benzene (0.1 g), triphenylphosphine palladium (30 mg), tetrabutylammonium bromide (4 mg), and toluene (19 mL) were mixed and heated to 105 ° C. To this reaction solution, 2M aqueous sodium carbonate solution (5 mL) was added dropwise and refluxed for 5 hours. Phenylboronic acid (6 mg) was added to the reaction solution and refluxed for 14 hours. Then, a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g / mL) was added, and the mixture was stirred for 2 hours. The aqueous layer was removed, the organic layer was washed with distilled water, and the solid obtained by concentration was dissolved in chloroform and purified by passing through an alumina column and a silica gel column. The eluate from the column was concentrated and dried. The yield of the obtained polymer H was 0.44 g.

The number average molecular weight in terms of polystyrene of the polymer H was 3.6 × 10 ⁴ . The polymer H consists of a repeating unit represented by the formula (R).

[Experimental Example 11]
Synthesis of Polymer H Cesium Salt Polymer H (200 mg) was placed in a 100 mL flask and purged with nitrogen. Tetrahydrofuran (14 mL) and methanol (7 mL) were added and mixed. An aqueous solution in which cesium hydroxide (90 mg) was dissolved in water (1 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C. for 1 hour. 5 mL of methanol was added to the reaction solution, and the mixture was further stirred at 65 ° C. for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (190 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site in the polymer H had completely disappeared. The resulting cesium salt of polymer H is referred to as conjugated polymer compound 11. The conjugated polymer compound 11 is composed of a repeating unit represented by the formula (S) ("selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). The ratio of the repeating unit containing one or more groups and one or more groups represented by the formula (3) "and" the formulas (13), (15), (17), ( The ratio of the repeating unit represented by 20) is 100 mol%.) The conjugated polymer compound 11 had a HOMO orbital energy of −5.6 eV and a LUMO orbital energy of −2.8 eV.

[Reference Example 15]
Synthesis of 2,7-dibromo-9,9-bis [3,4-bis [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] -5-methoxycarbonylphenyl] fluorene (Compound D) -Dibromo-9-fluorenone (34.1 g), methyl 2,3-dihydroxybenzoate (101.3 g), and mercaptoacetic acid (1.4 g) were placed in a 500 mL flask and purged with nitrogen. Thereto was added methanesulfonic acid (350 mL), and the mixture was stirred at 90 ° C. for 19 hours. The mixture was allowed to cool, added to ice water and stirred for 1 hour. The resulting solid was filtered off and washed with heated acetonitrile. The washed solid was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution and filtered. The resulting solid (16.3 g), 2- [2- (2-methoxyethoxy) ethoxy] -p-toluenesulfonate (60.3 g), potassium carbonate (48.6 g), and 18-crown-6 (2 4 g) was dissolved in N, N-dimethylformamide (DMF) (500 mL) and the solution was transferred to a flask and stirred at 110 ° C. for 15 hours. The obtained mixture was allowed to cool to room temperature, added to ice water, and stirred for 1 hour. Separation extraction was performed by adding ethyl acetate (300 mL) to the reaction solution, the solution was concentrated, dissolved in a mixed solvent of chloroform / methanol (50/1 (volume ratio)), and purified by passing through a silica gel column. By concentrating the solution passed through the column, 2,7-dibromo-9,9-bis [3,4-bis [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] -5-methoxycarbonyl Phenyl] fluorene (Compound D) (20.5 g) was obtained.

[Reference Example 16]
2,7-bis [7- (4-methylphenyl) -9,9-dioctylfluoren-2-yl] -9,9-bis [5-methoxycarbonyl-3,4-bis [2- [2- ( Synthesis of 2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Polymer I) Compound D (0.70 g), 2- (4,4,5,5-tetramethyl-1,2 under inert atmosphere , 3-Dioxaboran-2-yl) -9,9-dioctylfluorene (0.62 g), triphenylphosphine palladium (0.019 g), dioxane (40 mL), water (6 mL) and aqueous potassium carbonate (1.38 g) Were mixed and heated to 80 ° C. The reaction was allowed to react for 1 hour. After the reaction, 5 mL of saturated aqueous sodium diethyldithiocarbamate was added and stirred for 30 minutes, and then the organic solvent was removed. The obtained solid is purified through an alumina column (developing solvent hexane: ethyl acetate = 1: 1 (volume ratio)), and the solution is concentrated to give 2,7-bis [7- (4-methylphenyl)- 9,9-Dioctylfluoren-2-yl] -9,9-bis [3-ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Polymer I) 660 mg of was obtained.

The number average molecular weight in terms of polystyrene of the polymer I was 2.0 × 10 ³ . The polymer I is represented by the formula (T). 2- (4,4,5,5-tetramethyl-1,2,3-dioxaboran-2-yl) -9,9-dioctylfluorene is described in, for example, JP-A-2008-74017. It can be synthesized by the method.

[Experimental example 12]
Synthesis of Polymer I Cesium Salt Polymer I (236 mg) was placed in a 100 mL flask and purged with argon. Tetrahydrofuran (20 mL) and methanol (10 mL) were added thereto, and the mixture was heated to 65 ° C. Thereto was added an aqueous solution in which cesium hydroxide (240 mg) was dissolved in water (2 mL), and the mixture was stirred at 65 ° C. for 7 hours. After the resulting mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to obtain a pale yellow solid (190 mg). From the NMR spectrum, it was confirmed that the signal derived from the ethyl group at the ethyl ester site had completely disappeared. The obtained polymer I cesium salt is referred to as a conjugated polymer compound 12. The conjugated polymer compound 12 is represented by the formula (U) (“one type selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2) in all repeating units). "Ratio of repeating units containing the above groups and one or more groups represented by formula (3)" and "in formulas (13), (15), (17), (20) in all repeating units" The “ratio of repeating units represented” is 33.3 mol% rounded off to the second decimal place.) The conjugated polymer compound 12 had a HOMO orbital energy of −5.6 eV and a LUMO orbital energy of −2.8 eV.

[Experimental Example 13]
<Production of organic EL element>
A hole injection material solution was applied onto an ITO anode (film thickness: 45 nm) patterned on the surface of a glass substrate, and a hole injection layer was formed to a film thickness of 60 nm by spin coating. The glass substrate on which the hole injection layer is formed is heated in an inert atmosphere (nitrogen atmosphere) at 200 ° C. for 10 minutes to insolubilize the hole injection layer, and the substrate is naturally cooled to room temperature. A substrate on which was formed was obtained.

Here, PEDOT: PSS solution (poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid, product name: “Baytron”) manufactured by Starck Vitec Co., Ltd. was used as the hole injection material solution.

Next, a hole transporting polymer material and xylene were mixed to obtain a composition for forming a hole transporting layer containing 0.7 wt% of the hole transporting polymer material.

Here, the hole transporting polymer material was synthesized by the following method.
To a 1 liter three-necked round bottom flask equipped with a reflux condenser and an overhead stirrer was added 2,7-bis (1,3,2-dioxyborol) -9,9-di (1-octyl) fluorene (3.863 g). 7.283 mmol), N, N-di (p-bromophenyl) -N- (4- (butan-2-yl) phenyl) amine (3.177 g, 6.919 mmol) and di (4-bromophenyl) Benzocyclobutanamine (156.3 mg, 0.364 mmol) was added. Subsequently, methyl trioctyl ammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (2.29 g) was added, followed by 50 mL of toluene. After adding PdCl ₂ (PPh ₃ ) ₂ (4.9 mg), the mixture was stirred in an oil bath at 105 ° C. for 15 minutes. Aqueous sodium carbonate (2.0 M, 14 mL) was added and the resulting mixture was stirred in an oil bath at 105 ° C. for 16.5 hours. Phenylboronic acid (0.5 g) was then added and the resulting mixture was stirred for 7 hours. The aqueous layer was removed and the organic layer was washed with 50 mL of water. The organic layer was returned to the reaction flask and 0.75 g of sodium diethyldithiocarbamate and 50 mL of water were added. The resulting mixture was stirred in an 85 ° C. oil bath for 16 hours. The aqueous layer was removed and the organic layer was washed 3 times with 100 mL of water and then passed through a column of silica gel and basic alumina. Using toluene as an eluent, a toluene solution containing the eluted polymer was recovered. Next, the recovered toluene solution was poured into methanol to precipitate a polymer. The precipitated polymer was dissolved again in toluene, and the obtained toluene solution was poured into methanol to precipitate the polymer again. The precipitated polymer was vacuum-dried at 60 ° C. to obtain 4.2 g of a hole transporting polymer material. According to gel permeation chromatography, the obtained hole transporting polymer material had a polystyrene equivalent weight average molecular weight of 1.24 × 10 ⁵ and a molecular weight distribution index (Mw / Mn) of 2.8. It was.

On the hole injection layer of the substrate on which the hole injection layer obtained above was formed, the composition for forming a hole transport layer was applied by a spin coating method to obtain a coating film having a thickness of 20 nm. The substrate provided with this coating film was heated at 190 ° C. for 20 minutes in an inert atmosphere (in a nitrogen atmosphere) to insolubilize the coating film, and then naturally cooled to room temperature to form a substrate on which the hole transport layer was formed. Obtained.

Next, a light emitting polymer material (“Lumation BP361” manufactured by Summation Co., Ltd.) and xylene were mixed to obtain a composition for forming a light emitting layer containing 1.4% by weight of the light emitting polymer material. On the hole transport layer of the board | substrate with which the hole transport layer obtained above was formed, the composition for light emitting layer formation was apply | coated by the spin coat method, and the coating film with a film thickness of 80 nm was obtained. The substrate provided with this coating film was heated at 130 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a light emitting layer was formed.

Methanol and conjugated polymer compound 1 were mixed to obtain a composition containing 0.2% by weight of conjugated polymer compound 1. On the light emitting layer of the board | substrate with which the light emitting layer obtained above was formed, the said composition was apply | coated by the spin coat method, and the coating film with a film thickness of 10 nm was obtained. The substrate provided with this coating film is heated at 130 ° C. for 10 minutes under an inert atmosphere (nitrogen atmosphere) under normal pressure to evaporate the solvent, and then naturally cooled to room temperature, and the electrons containing the conjugated polymer compound 1 A substrate on which an injection layer was formed was obtained.

The substrate on which the layer containing the conjugated polymer compound 1 obtained above was formed was inserted into a vacuum apparatus, and an Al film was formed on the layer by vacuum vapor deposition to form a cathode, thereby forming a laminated structure. 1 was produced.

The laminated structure 1 obtained above was taken out from the vacuum apparatus and sealed with sealing glass and a two-component mixed epoxy resin in an inert atmosphere (in a nitrogen atmosphere) to obtain an organic EL element 1.

[Experimental Example 14]
An organic EL device 2 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 2 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experimental Example 15]
In Experimental Example 13, methanol and conjugated polymer compound 1 were mixed, and instead of obtaining a composition containing 0.2% by weight of conjugated polymer compound 1, methanol, water and conjugated polymer compound 3 were mixed (methanol). / Water volume ratio = 20/1), and the organic EL device 3 was obtained in the same manner as in Experimental Example 13 except that the composition containing 0.2% by weight of the conjugated polymer compound 3 was used.

[Experimental Example 16]
An organic EL device 4 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 4 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experimental Example 17]
An organic EL device 5 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 5 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experiment 18]
An organic EL device 6 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 6 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experimental Example 19]
An organic EL device 7 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 7 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experiment 20]
An organic EL device 8 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 8 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experiment 21]
An organic EL device 9 was obtained in the same manner as in Experimental Example 13 except that the conjugated polymer compound 9 was used instead of the conjugated polymer compound 1 in Experimental Example 13.

[Experimental example 22]
In the experimental example 13, an organic EL device 10 was obtained in the same manner as in the experimental example 13 except that the conjugated polymer compound 10 was used instead of the conjugated polymer compound 1.

[Experimental example 23]
In Experiment Example 13, an organic EL element 11 was obtained in the same manner as in Experiment Example 13 except that the conjugated polymer compound 11 was used instead of the conjugated polymer compound 1.

[Experimental example 24]
In Experiment Example 13, an organic EL device 12 was obtained in the same manner as in Experiment Example 13 except that the conjugated polymer compound 12 was used instead of the conjugated polymer compound 1.

[Experiment 25]
In Experimental Example 13, instead of mixing methanol and conjugated polymer compound 1 to obtain a composition containing 0.2% by weight of conjugated polymer compound 1, methanol, conjugated polymer compound 1, Al-doped ZnO nanoparticles ( An organic EL device 13 was obtained in the same manner as in Experimental Example 13 except that a composition mixed with Aldrich was used.

[Experiment 26]
In Experimental Example 13, instead of mixing methanol and conjugated polymer compound 1 to obtain a composition containing 0.2% by weight of conjugated polymer compound 1, methanol, conjugated polymer compound 1, low molecular compound (manufactured by Aldrich) , 3,5-bis (4-tert-butylphenyl) -4-phenyl-4H-1,2,4-triazole), 0.2% by weight of conjugated polymer compound 1 and 0.2% by weight The organic EL device 14 was obtained in the same manner as in Experimental Example 13 except that the composition containing the low molecular compound was obtained.

[Experiment 27]
In Experimental Example 13, an organic EL element 15 was obtained in the same manner as in Experimental Example 13 except that Ag was used instead of Al.

[Experiment 28]
In Example 13, except that Au was used instead of Al, the same operation as in Example 13 was performed to obtain an electroluminescent element 16.

[Measurement]
A forward voltage of 10 V was applied to the organic EL elements 1 to 16 obtained above, and the light emission luminance and the light emission efficiency were measured. The results are shown in Table 1.

[Experimental example 29]
Methanol and conjugated polymer compound 1 were mixed to obtain a composition containing 0.2% by weight of conjugated polymer compound 1. The composition was applied by spin coating in the air on an ITO cathode (film thickness: 45 nm) patterned on the surface of a glass substrate to obtain a coating film having a film thickness of 10 nm. The substrate provided with this coating film was heated in an inert atmosphere (nitrogen atmosphere) at 130 ° C. for 10 minutes to evaporate the solvent, and then naturally cooled to room temperature. A formed substrate was obtained.

Next, a light emitting polymer material (“Lumation BP361” manufactured by Summation Co., Ltd.) and xylene were mixed to obtain a composition for forming a light emitting layer containing 1.4% by weight of the light emitting polymer material. A composition for forming a light-emitting layer is applied in the air by a spin coating method on the layer containing the conjugated polymer compound 1 of the substrate on which the layer containing the conjugated polymer compound 1 obtained above is formed. Coating film was obtained. The substrate provided with this coating film was heated at 130 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a light emitting layer was formed.

Next, the hole injection material solution was applied in the air by a spin coating method on the light emitting layer of the substrate on which the light emitting layer obtained above was formed, to obtain a coating film having a film thickness of 60 nm. The substrate provided with this coating film was heated in an inert atmosphere (nitrogen atmosphere) at 130 ° C. for 15 minutes to evaporate the solvent and then naturally cooled to room temperature to obtain a substrate on which a hole injection layer was formed. It was. Here, PEDOT: PSS solution (poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid, product name: “Baytron”) manufactured by Starck Vitec Co., Ltd. was used as the hole injection material solution.

The substrate on which the hole injection layer formed above was formed was inserted into a vacuum apparatus, Au was deposited on the layer by 80 nm by a vacuum deposition method, and an anode was formed, whereby the laminated structure 1 was manufactured. .

The laminated structure 2 obtained above was taken out from the vacuum apparatus and sealed with sealing glass and a two-component mixed epoxy resin in an inert atmosphere (in a nitrogen atmosphere) to obtain an organic EL element 17.

A forward voltage of 10 V was applied to the organic EL element 17 obtained above, and the light emission luminance and the light emission efficiency were measured. The results are shown in Table 2.

[Experiment 30]
<Production of Double-sided Light Emitting Organic EL Device>
In Experimental Example 29, except that the film thickness of Au was set to 20 nm, the same operation as in Experimental Example 29 was performed to obtain a double-sided light emitting organic EL element 18.

A forward voltage of 15 V was applied to the double-sided light emitting organic EL element 18 obtained above, and the light emission luminance and the light emission efficiency were measured. The results are shown in Table 3.

As shown in Tables 2 and 3, it was confirmed that the reverse stacked organic EL device in which an ionic polymer was formed in the atmosphere by an application process and an electron injection layer was formed emitted light.

The light emitting device and the manufacturing method thereof according to the present invention can be used in technical fields such as a display and a lighting device.

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Light-emitting device 3 Support substrate 4 1st electrode 5 Second electrode 6 Light-emitting layer 7 Electron injection layer 11 Light-emitting device 12 Support substrate 13 Organic EL element 14 1st electrode 15 2nd electrode 16 Light-emitting layer 20

Electron injection layer

17, 18 Extension part 19 Connection part 31 Light-emitting device 32 Connection part 41 Light-emitting device 42 Connection part 51 Light-emitting device 52 Auxiliary electrode 61 Light-emitting device

Claims

A support substrate;
A plurality of organic electroluminescence elements provided on the support substrate along a predetermined arrangement direction and connected in series;
Each organic electroluminescence element includes a pair of electrodes, a light emitting layer and an electron injection layer provided between the electrodes,
The light emitting layer extends along the predetermined arrangement direction across the plurality of organic electroluminescence elements,
Each of the pair of electrodes extends so as to protrude from the light emitting layer in a width direction perpendicular to both the thickness direction of the support substrate and the arrangement direction when viewed from one thickness direction of the support substrate. Part
One electrode of the pair of electrodes extends from the extension portion to the other electrode of the organic electroluminescence element adjacent in the arrangement direction, and is connected to the other electrode. Further comprising
The electron injection layer is a light emitting device including an ionic polymer.
An auxiliary electrode provided in contact with the electrode;
The light emitting device according to claim 1, wherein the auxiliary electrode has a lower sheet resistance than an electrode in contact with the auxiliary electrode.
The light emitting device according to claim 2, wherein the auxiliary electrode is provided in contact with an electrode having a higher sheet resistance among the pair of electrodes.
The light-emitting device according to any one of claims 1 to 3, wherein only the electrode having the lower sheet resistance of the pair of electrodes has the connection portion.
The extension portion, as viewed from one side in the thickness direction, has a first extension portion that extends from the light emitting layer to one side in the width direction, and projects from the light emitting layer to the other side in the width direction. The light emitting device according to any one of claims 1 to 4, further comprising a second extending portion that extends.
A light-emitting device comprising a support substrate and a plurality of organic electroluminescence elements provided in series along a predetermined arrangement direction and connected in series;
Each organic electroluminescence element includes a pair of electrodes, a light emitting layer and an electron injection layer provided between the electrodes,
The light emitting layer extends along the predetermined arrangement direction across the plurality of organic electroluminescence elements,
Each of the pair of electrodes has an extending portion that extends from the light emitting layer in the width direction perpendicular to the thickness direction of the support substrate and the arrangement direction when viewed from one thickness direction of the support substrate. And
One electrode of the pair of electrodes extends from the extending portion to the other electrode of the organic electroluminescence element adjacent in the arrangement direction and is connected to the other electrode. A method for manufacturing a light emitting device further comprising:
The ink containing the material to be the light emitting layer is continuously applied across the plurality of electrodes arranged on the support substrate along the predetermined arrangement direction, and light is emitted by solidifying the applied coating film. Forming a layer;
And a step of forming the electron injection layer by coating and forming an ink containing an ionic polymer.
The method for manufacturing a light emitting device according to claim 6, wherein the method of applying the ink containing the material for the light emitting layer is a cap coating method, a slit coating method, a spray coating method or a printing method.
The method for manufacturing a light emitting device according to claim 6 or 7, wherein in the step of forming the electron injection layer, ink is applied in an air atmosphere.