TW201302838A - Organic EL element - Google Patents

Abstract

This invention provides an organic EL element comprising a first electrode, a second electrode, one or a plurality of draw-out electrodes arranged between the above first electrode and the above second electrode, and a plurality of luminent units having electrons injection layers and luminent layer arranged in interials between the above first electrode, the above draw-out electrode and the above second electrode being adjacent to each other, wherein the above electron injection layer comprises iononcrs.

Description

Organic electric field emitting (EL) element

The present invention relates to an organic electroluminescence (EL) device, a display device and an illumination device including the organic EL device, and a method of manufacturing an organic EL device.

An organic EL (Electro Luminescence) device includes a pair of electrodes formed of an anode and a cathode, and a light-emitting layer provided between the electrodes. When a voltage is applied to the organic EL element, electrons are injected from the cathode while the anode is injected into the hole, whereby the holes and the electrons are combined in the light-emitting layer to generate light.

The number of the light-emitting layer layers provided between the electrodes is not limited to one layer, but a so-called multiphoton type organic EL element in which a plurality of light-emitting layers are provided between the electrodes. In the organic EL device having the plurality of light-emitting layers, since each of the light-emitting layers emits light, the amount of light per unit current increases as compared with the organic EL element having only one layer of the light-emitting layer.

However, in the organic EL device having the above structure, since a specific voltage cannot be independently applied to each of the light-emitting layers, the intensity of light emitted from each of the light-emitting layers cannot be independently regulated.

For the organic EL device having such a structure, there has been proposed an organic EL device in which a draw out electrode (an electrode or a terminal for outputting or inputting a voltage, which is originally referred to herein as an extraction electrode) is provided between the light-emitting layers. Since the extraction electrode is electrically connected to an external power source, a predetermined voltage can be applied to the extraction electrode. Therefore, in each luminescent layer can Independently and with a predetermined voltage applied, the intensity of light emitted by each of the light-emitting layers can be independently regulated (for example, refer to Patent Document 1).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-92998

Between the electrodes, the predetermined layer can be further set without limiting the above-mentioned light-emitting layer or the extraction electrode. As such a layer, the above-described conventional technique has been provided with an electron injecting layer. Further, in Patent Document 1, the material of the electron injecting layer and the method of forming the same are not disclosed in detail, since the electron injecting layer is generally composed of a material which is unstable in the atmosphere by Ba, BaO, NaF, LiF or the like.

The organic EL element is produced by sequentially laminating the layers constituting the element. Therefore, among the formed electron injecting layers, a predetermined layer such as a light emitting layer or an extraction electrode is formed. In the formation of the electron injecting layer, a light-emitting layer or the like laminated on the electron injecting layer, for example, when formed in the atmosphere, is denatured into an unstable electron injecting layer in the atmosphere, and as a result, the produced organic EL element emits light. The feature has a so-called drop problem.

Therefore, an object of the present invention is to provide an organic EL device including an electron injecting layer capable of suppressing deterioration in the step of producing an organic EL element.

The present invention relates to an organic EL device including a first electrode and a second electrode, and is disposed between the first electrode 1 and the second electrode 2 1 or a plurality of extraction electrodes 3, and a light-emitting unit disposed between the adjacent electrodes of the first electrode, the front-removal electrode, and the second electrode, and the pre-recorded light-emitting unit has an electron injection layer and The light-emitting layer, the electron-injecting layer described above, contains an ionic polymer.

Further, according to the present invention, in the organic EL device, the light-emitting layer and the electron-injecting layer are stacked in the light-emitting unit in which the first electrode is used as a reference in the light-emitting unit adjacent to the pair of extraction electrodes. In the foregoing light-emitting unit of the other side, the order of lamination of the light-emitting layer and the electron-injecting layer is different.

Moreover, the present invention relates to an organic EL device in which a pair of light-emitting layers are provided in mutually different light-emitting units, and light of different colors is emitted.

Moreover, the present invention relates to an organic EL device in which a pair of light-emitting layers are provided in mutually different light-emitting units, and light of the same color is emitted.

Moreover, the present invention relates to an illumination device comprising the above-described organic EL element.

Moreover, the present invention relates to a display device including the above-described organic EL element.

Moreover, the present invention relates to a method for producing an organic EL device, comprising: a first electrode, a second electrode, and 1 or a plurality of extraction electrodes disposed between the first electrode and the second electrode; a method for producing an organic EL device having a plurality of electron injection layers and light-emitting units of a light-emitting layer between adjacent electrodes of the extraction electrode and the second electrode, and a coating liquid containing an ionic polymer; The step of forming the electron injecting layer by film formation, and the step of forming the light emitting layer before forming the electron injecting layer or after forming the electron injecting layer.

In the step of forming the aforementioned electron injecting layer, the ionic polymerization is contained The coating liquid of the object can be applied in an atmosphere having a volume ratio of nitrogen of 90% or less and a volume ratio of oxygen of 10% or more and 30% or less.

According to the invention, it is possible to realize an organic EL device including an electron injecting layer capable of suppressing deterioration in the manufacturing process of the organic EL element.

The best form of invention implementation:

The organic EL device of the present invention includes a first electrode, a second electrode, and a plurality of extraction electrodes 3 disposed between the first electrode 1 and the second electrode 2 at intervals, and the first electrode A light-emitting unit including an electron injection layer and a light-emitting layer is disposed between the electrodes adjacent to each other and the second electrode. Further, the light-emitting unit has an electron injecting layer and a light-emitting layer, and the electron injecting layer contains an ionic polymer.

In other words, the organic EL device of the present embodiment is configured such that the first electrode, the first electrode, or the plurality of extraction electrodes are arranged at intervals in the order of the second electrode, and the first electrode, the first electrode, or the plural electrode The light-emitting unit including the electron injection layer and the light-emitting layer is disposed between the extraction electrode and the adjacent electrodes among the second electrodes, and the electron injection layer contains an ionic polymer.

Hereinafter, the structure of the organic EL element will be described with reference to Fig. 1 . In the first embodiment, an organic EL element including three extraction electrodes 3 and four light-emitting units 4 is shown as an example. However, the number of the extraction electrodes 3 and the number of the light-emitting units 4 (the number of extracted electrodes + 1) are shown. It is not limited to the form shown in Fig. 1.

The first electrode 1 and the second electrode 2 function as an anode or a cathode in accordance with the configuration of the light-emitting unit 4 to be described later. Since at least one of the first electrode 1 and the second electrode 2 is emitted to the outside by the light emitted from the light-emitting layer, at least one of the first electrode 1 and the second electrode 2 is displayed by light. It is composed of a transparent electrode (light extraction electrode).

Between the first electrode 1 and the second electrode 2, one or a plurality of extraction electrodes 3 are provided. As described below, the extraction electrode 3 is formed by a layer of electrodes or a plurality of layers of electrodes. For example, in the case of a one-layer structure, the take-out electrode 3 is composed of a conductive film of the same material as the anode or a conductive film of the same material as the cathode. Further, in the case of a structure in which a plurality of layers are laminated, the extraction electrode 3 is composed of a laminate of a conductive film of the same material as the anode and a conductive film of the same material as the cathode.

The electrode 3 is taken out, and is required to pass through the light which is transmitted through the light-emitting layer.

The extraction electrode 3 is connected to a predetermined electric wiring via a drive circuit 11 that drives the organic EL element. In the present embodiment, the extraction electrode 3 is not limited to a positive voltage, and may be connected to a DC power supply of the drive circuit 11 by applying a negative voltage. For example, the electrode 3 is different from the structure of the first embodiment, but it is formed by one of the thickness directions of the first electrode 1 (hereinafter, referred to as a "planar view"). The area extending is as prominent as the extension, and the end portion is connected to the electric wiring. In this case, the first electrode 1, the second electrode 2, and the respective extraction electrodes 3 are in an attempt to overlap each other in a region extending from the light-emitting region in the planar viewing angle. Formed by the way.

The light-emitting unit 4 is provided between the first electrode 1, 1 or a plurality of the extraction electrodes 3 and the adjacent electrodes of the second electrode 2, respectively. That is, the light-emitting unit 4 is between (1) the first electrode 1 and the extraction electrode 3 disposed closest to the first electrode 1, (2) between the electrodes 3 adjacent to each other, and (3) and The second electrode 2 is provided between the extraction electrodes 3 disposed closest to the second electrode 2. Therefore, the number of the light-emitting units 4 may be set to be one plus one of the number of the extraction electrodes 3 provided in the organic EL element. Further, since only one of the extraction electrodes 3 is provided (see FIGS. 2 to 5), since the presence of the extraction electrodes 3 is not adjacent to each other, no light-emitting unit is provided between the adjacent extraction electrodes 3 described above.

Each of the light-emitting units 4 includes at least an electron injection layer and a light-emitting layer. Further, in the light-emitting unit 4, the electron injecting layer and the light-emitting layer are not limited, and a predetermined layer may be provided as necessary. The predetermined layer is composed of, for example, a layer made of an organic substance, a layer made of an inorganic substance, a layer made of an organic substance and an inorganic substance, or the like. As such a predetermined layer, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, a hole blocking layer, and the like can be cited.

As the layer structure of the light-emitting unit 4, for example, the following a) to f) can be cited.

a) luminescent layer / electron injection layer

b) luminescent layer / electron transport layer / electron injection layer

c) hole injection layer / luminescent layer / electron injection layer

d) hole injection layer / luminescent layer / electron transport layer / electron injection layer

e) hole injection layer / hole transport layer / luminescent layer / electron injection layer

f) hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer (herein, the symbol "/" indicates that two layers drawn by the mark "/" are adjacent and laminated. ,the same.)

The plurality of light-emitting units 4 are provided in plural, and the layer structure may be the same or different from each other.

When the first electrode 1 is used as a reference, the order of lamination of the layer structures of the light-emitting units 4 of the respective configurations a) to f) is two. In other words, when the first layer is placed next to the first electrode 1 with respect to the electron injecting layer, the second layer is placed next to the first electrode 1 with respect to the light emitting layer. In the light-emitting unit 4 of each layer structure of the above a) to f), in the first layering order, the layers are sequentially stacked on the left side in the description of the above a) to f), and the second layer is in the order of the layers. In the description of a) to f), the layers are sequentially stacked on the right side. The layer structure of the light-emitting unit 4 of the present invention may also be any stacking order.

Further, the configurations of the first electrode 1, the second electrode 2, and the extraction electrode 3 are specified by the order of lamination of the layer structures of the light-emitting units 4 disposed in the respective electrodes.

The polarities of the first electrode 1 and the second electrode 2 are related to the order of lamination of the layer structure of the light-emitting unit 4 connected to the electrode.

When the layering order of the layer structure in which the first electrode 1 is connected and the light-emitting unit 4 is provided is the first layering order, the first electrode 1 serving as the anode function is provided. In other words, only the first electrode 1 and the laminated body formed by the light-emitting unit 4 provided in the first electrode are considered, and the first function as the anode function is considered. The order of the electrode, the light-emitting layer, and the electron injecting layer is laminated to each layer. On the other hand, in the case where the layering order of the layer structure of the light-emitting unit 4 provided in the first electrode 1 is the second layering order, the first electrode 1 serving as a cathode function is provided. In other words, when only the first electrode and the laminated body connected to the light-emitting unit provided in the first electrode are considered, the layers are laminated in the order of the first electrode, the electron injecting layer, and the light-emitting layer serving as the cathode function.

When the layered order of the layer structure in which the second electrode 2 is connected and the light-emitting unit 4 is provided is the first layering order, the second electrode 2 serving as the cathode function is provided. In other words, when only the laminated body formed by the light-emitting unit 4 and the second electrode 2 provided in the second electrode 2 is connected, the layers are laminated in the order of the light-emitting layer, the electron injecting layer, and the second electrode serving as the cathode function. On the other hand, in the case where the layering order of the layer structure of the light-emitting unit 4 provided in the second electrode 2 is the second layering order, the second electrode 2 serving as the anode function is provided. In other words, when only the laminated body formed by the light-emitting unit 4 and the second electrode 2 provided in the second electrode 2 is connected, the layers are laminated in the order of the electron injection layer, the light-emitting layer, and the second electrode as the anode function.

The extraction electrode 3 is in the order of lamination of the layer structure of the pair of light-emitting units 4 that hold the extraction electrode 3, and has a different structure.

The stacking order of the layer structures is the take-out electrode 3 held by the different light-emitting units 4, and is composed of one layer of electrodes. For example, it can be constituted by any one of a conductive film of the same material as the cathode and a conductive film of the same material as the anode.

Specifically, in the light-emitting unit 4 of the first build-up order, and the take-out electrode 3 held by the light-emitting unit 4 of the second build-up sequence, the extraction electrode 3 can be used by It is composed of a conductive film of the same material. In other words, only the light-emitting unit 4 in the first layering order and the light-emitting unit 4 in the second layering order and the layered body formed by the extraction electrode 3 may be considered, and the light-emitting layer and the electron injection layer may be used. Each layer is laminated in the order of the conductive thin film, the electron injecting layer, and the light emitting layer of the same material as the cathode.

Further, in the light-emitting unit 4 of the second build-up order, the take-out electrode 3 held by the light-emitting unit 4 of the first build-up order can be constituted by a conductive film of the same material as the anode. In other words, it is also possible to consider only the light-emitting unit 4 in the second layering order, the light-emitting unit 4 in the first layering order, and the layered body formed by the extraction electrode 3, or the electron-injecting layer or the light-emitting layer. Each layer is laminated in the order of the conductive thin film, the light-emitting layer, and the electron injecting layer of the same material as the anode.

Further, in the layered structure, the extraction electrode 3 held by the same light-emitting unit 4 can be constituted by a laminate of a conductive film of the same material as the cathode and a conductive film of the same material as the anode.

Specifically, in the light-emitting unit 4 of the first build-up order, the take-out electrode 3 held by the light-emitting unit 4 of the first build-up order can be made of a conductive film of the same material as the cathode in the order of the first electrode 1 The conductive film of the same material of the anode is formed by laminating the layers in this order. In other words, only the light-emitting unit 4 in the first build-up order, the light-emitting unit 4 in the first build-up order, and the laminate formed by the take-out electrode 3 held therein may be considered, and the light-emitting layer and the electron injection layer may be used. The layers of the conductive film of the same material as the cathode, the conductive film of the same material as the anode, the light-emitting layer, and the electron injecting layer are laminated.

Further, in the light-emitting unit 4 of the second build-up order, the take-out electrode 3 held by the light-emitting unit 4 of the second build-up order may be a conductive film of the same material as the anode in the order of approaching the first electrode 1. And a structure in which the conductive film of the same material as the cathode is laminated in this order. In other words, only the light-emitting unit 4 in the second build-up order and the light-emitting unit 4 in the second build-up order may be used in the laminated body formed by the extraction electrode 3, or the electron injection layer or the light-emitting layer. The layers of the conductive film of the same material as the anode, the conductive film of the same material as the cathode, the electron injecting layer, and the light-emitting layer are laminated.

Further, in the case where three or more light-emitting units are provided, the layering order of the layer structures of the respective light-emitting units may be different from each other, and the light-emitting units may be laminated via the extraction electrodes, and the layering order of the layer structures of the respective light-emitting units may be interactive. In contrast, the light-emitting unit may be laminated in a plurality of layers by the extraction electrode, or a layer 1 or a plurality of light-emitting units may be laminated in an attempt to form the same layering order. In other words, in the case where three or more light-emitting units are provided, the layering order of the layer structures of the respective light-emitting units may be alternately attempted to be different, and the light-emitting unit may be mixed with the extraction electrode via the laminated portion, and in the layering order. The laminated part of the same way.

As described above, in the adjacent light-emitting units of the pair of extraction electrodes, the first electrode is used as a reference, and the order of lamination of the light-emitting layer and the electron injection layer is reversed, that is, adjacent to the extraction electrode In a pair of light-emitting units, in the case of one of the light-emitting units, the order of the light-emitting layer and the electron-injecting layer is based on the first electrode, and the order of the light-emitting layer and the electron-injecting layer is the same in the other light-emitting unit. Is a different situation, take The electrode can be formed by one layer of a structural electrode (a conductive film of the same material as the cathode and a conductive film of the same material as the anode). Therefore, the number of the extraction electrodes 3 can be reduced as compared with the extraction electrode 3 held by the light-emitting unit 4 having the same laminated order of the layer structure, and the step of forming the extraction electrode can be simplified.

The number of the light-emitting units 4 and the thickness of each layer are appropriately set in consideration of luminous efficiency or element life.

In the case where the number of the light-emitting units 4 is two, the specific examples in which the extraction electrodes 3 held by the light-emitting units 4 having the same layer structure are in the arrangement form are (1-1) and (1- In 2), a specific example in which the stacking order of the layer structure is different from that of the extraction electrode 3 held by the light-emitting unit 4 is shown in (2-1) and (2-2). Further, the drawings relating to the drive circuit are not shown in FIGS. 2 to 5.

(1-1) The stacking order of the layer structure is the same as that of the extraction electrode 3 held by the light-emitting unit 4 (see FIG. 2)

First electrode 1a (anode) / hole injection layer 5a / hole transport layer 6a / light-emitting layer 7a / electron injection layer 8a / take-out electrode 3a (conductive film 9a of the same material as the cathode / conductivity of the same material as the anode) Film 10a)/hole injection layer 5a/hole transport layer 6a/light-emitting layer 7a/electron injection layer 8a/second electrode 2a (cathode)

(1-2) The stacking order of the layer structure is the same as that of the extraction electrode 3 held by the light-emitting unit 4 (see FIG. 3)

First electrode 1b (cathode) / electron injection layer 8b / light-emitting layer 7b / hole transport layer 6b / hole injection layer 5b / take-out electrode 3b (guide of the same material as the anode Electroconductive film 10b / Conductive film 9b of the same material as the cathode) Electron injection layer 8b / Light-emitting layer 7b / Hole transport layer 6b / Hole injection layer 5b / Second electrode 2b (Anode)

(2-1) The stacking order of the layer structure is such that the extraction electrodes 3 held by the different light-emitting units 4 are in an installation form (see FIG. 4).

First electrode 1c (anode) / hole injection layer 5c / hole transport layer 6c / light-emitting layer 7c / electron injection layer 8c / take-out electrode 3c (conductive film 9c of the same material as the cathode) / electron injection layer 8c / light Layer 7c/hole transport layer 6c/hole injection layer 5c/second electrode 2c (anode)

(2-2) The stacking order of the layer structure is such that the extraction electrodes 3 held by the different light-emitting units 4 are in an installation form (see FIG. 5).

First electrode 1d (cathode) / electron injection layer 8d / light-emitting layer 7d / hole transport layer 6d / hole injection layer 5d / take-out electrode 3d (conductive film 10d of the same material as the anode) / hole injection layer 5d / Hole transport layer 6d / light-emitting layer 7d / electron injection layer 8d / second electrode 2d (cathode)

In the organic EL device having the above-described configuration, a predetermined voltage is applied to each of the first, first, second, and second electrodes 2, and a plurality of extraction electrodes 3, and a predetermined voltage can be independently applied to each of the light-emitting units 4. Thereby, the intensity of the light emitted by each of the light-emitting units 4 can be independently regulated.

Further, since the organic EL element includes a plurality of light-emitting units 4, it has a plurality of light-emitting layers. A pair of light-emitting layers provided in mutually different light-emitting units is formed by emitting light-emitting layers of different colors of light or emitting light-emitting layers of the same color.

(i) setting the case where a plurality of layers emit light of the same color

By independently controlling the intensity of light emitted from each of the light-emitting units, the color of the light emitted from the organic EL element is made almost the same, and the intensity of the light can be changed.

(ii) the case of illuminating a luminescent layer that emits light of different colors from each other

In order to emit light of various colors emitted by the respective light-emitting units, the organic EL element can adjust the intensity of light emitted from the organic light-emitting elements by independently controlling the intensity of light emitted from the respective light-emitting elements, and Light intensity.

The light-emitting layers that emit light of the same color may be formed by using the same light-emitting material. Further, the light-emitting layers that emit light of different colors may be formed by using mutually different light-emitting materials. In the case where a plurality of types of materials are mixed to form a light-emitting layer, light-emitting layers of mutually different color light are emitted, and this material may also be partially common.

In the case where three or more light-emitting units are provided, although the light-emitting layer is provided in three or more layers, for example, two of the light-emitting layers may be formed as light-emitting layers that emit light of the same color, and the remaining light-emitting layers may be radiated to each other. Light-emitting layers of different colors of light.

The above organic EL element is, for example, a light source used in a backlight or a pixel of a display device, or an illumination device. That is, a display device or an illumination device can be produced by forming one or a plurality of organic EL elements on a predetermined substrate.

Next, a method of manufacturing an organic EL element will be described.

In the method for producing an organic EL device of the present embodiment, the first electrode, the first electrode, the plurality of extraction electrodes, and the second electrode are spaced apart in this order. And a method of manufacturing an organic EL element comprising the light-emitting unit provided between each of the first electrode, the first electrode or the plurality of extraction electrodes, and the adjacent electrode of the second electrode, wherein the method includes forming a step of forming a first electrode, a step of forming a second electrode, a step of forming 1 or a plurality of extraction electrodes, and a step of forming a light-emitting unit, in the step of forming the light-emitting unit, coating a coating liquid containing an ionic polymer The film formation is performed by curing the electron injecting layer, and further, before the electron injecting layer is formed or after the electron injecting layer is formed, a light emitting layer is formed to form a light emitting unit including the electron injecting layer and the light emitting layer.

The organic EL device of the present embodiment can be formed, for example, by (1) sequentially stacking the respective constituent elements in the order of the first electrode, or (2) by lamination.

(1) The case of sequentially arranging each structural element

In the case where the two light-emitting units 4 are provided, the organic EL element can be formed by laminating the first electrode 1, the light-emitting unit 4, the extraction electrode 3, the light-emitting unit 4, and the second electrode 2 in this order on a support substrate or the like.

In the case where three or more light-emitting units 4 are provided, the first electrode 1 and the light-emitting unit 4 are sequentially laminated on a support substrate or the like, and the step of sequentially laminating the extraction electrode 3 and the light-emitting unit 4 is performed once or repeatedly. Several times, finally, the organic EL element can be formed by laminating the second electrode 2.

(2) Layered situation

When the organic EL element is cut in a vertical plane in the thickness direction, the first member to be formed by the layer of the first electrode cut surface is prepared, and the second electrode is formed in advance by the layer of the cut surface. member, The organic EL element can be formed by adhering the first member and the second member cut surface.

The first electrode 1 and the second electrode 2 are provided to correspond to an electrode serving as an anode or a cathode. The method of forming the anode and the cathode and the material thereof will be described later.

The extraction electrode 3 can be formed in the same manner as the anode or the cathode described later. In the case of the first layer, the extraction electrode 3 is made of the same material as the anode or the cathode, and is formed by the same formation method. In the case of two layers, the same material as one of the anode and the cathode is formed, and one layer is formed by the same formation method, and the other material is formed in the same manner as the other of the anode and the cathode, and the other layer is formed by the same formation method. These layers are formed by lamination. Further, the electrode 3 may be taken out, or may be formed of the same material as the anode or the cathode described later, or may be formed of a material different from that of the first electrode 1 or the second electrode 2.

When the extraction electrode 3 is too thick, it becomes opaque. On the other hand, when the extraction electrode 3 is too thin, the electric resistance becomes high. Therefore, the thickness is appropriately set in consideration of light transmittance, electric resistance, and the like.

a step of forming a light-emitting unit, coating a coating liquid containing an ionic polymer into a film, forming an electron injecting layer by hardening, and further forming a light-emitting layer before forming an electron injecting layer or after forming an electron injecting layer, A light emitting unit including an electron injecting layer and a light emitting layer may be formed. For the light-emitting unit, for example, the layers of the above structures a) to f) are sequentially stacked in the first layering order or the second layering order, or by the layering according to the first layering order or the second layering order. form.

The form of each layer in the sequential layer, relative to the electron injecting layer, will emit light In the case where the layer is in the order of the first buildup layer disposed adjacent to the first electrode 1, the light-emitting layer is first formed before the formation of the electron-injecting layer, and thereafter, the electron-injecting layer is formed. Moreover, in the case where the electron injection layer is placed in the second buildup layer close to the first electrode 1 with respect to the light-emitting layer, after the electron injection layer is formed, the light-emitting layer is formed.

The electron injecting layer is formed by applying a coating liquid containing an ionic polymer to a film and curing it. Since the ionic polymer is relatively stable in the air as described later, it can be formed by a coating method using a coating liquid containing the ionic polymer.

The application of the coating liquid containing an ionic polymer can be carried out, for example, in an atmosphere of an inert gas such as nitrogen or argon, and the volume ratio of nitrogen is 90% or less from the viewpoint of simplifying the production steps. And it is desirable to carry out an environment in which the volume ratio of oxygen is 10% to 30%, so that the volume ratio of nitrogen is 60% to 90%, the volume ratio of oxygen is 10% to 30%, and the volume ratio of water vapor is 0.0001% to 0.01%, a pressure of 10 kPa to 1000 kPa, and a temperature of 5 ° C to 100 ° C are preferably carried out so that the volume ratio of nitrogen is 70% to 90%, and the volume ratio of oxygen is 10% to 30%. %, the volume ratio of water vapor is 0.002% to 0.005%, the pressure is 80 kPa to 120 kPa, and the temperature is preferably 20 ° C to 30 ° C, preferably in the atmosphere at a temperature of 20 ° C to 30 ° C. .

The coating method containing the ionic polymer coating liquid can be carried out by using this method by selecting the most appropriate known coating method as a coating method in consideration of the shape of the organic EL element, the ease of the steps, and the like. Examples of the coating method include a spin coating method, a mold method, a micro-image coating method, and a photo coating method. Method, bar coating method, roll coating method, wire-bar coating method, dip coating method, spray coating method, mesh screen printing method, soft printing method, lithography method, and inkjet printing method.

The film in which the coating liquid containing an ionic polymer is applied to form a film is cured by natural drying, heat drying, vacuum drying, or the like. Further, in the case of using a coating liquid containing a polymer material by heating or light irradiation, the film can be cured by heating or light irradiation.

The hardening of the film can also be carried out in a vacuum environment or in an inert gas atmosphere such as nitrogen or argon. From the viewpoint of simplifying the production steps, the volume ratio of nitrogen is 90% or less, and the volume ratio of oxygen is It is preferably carried out in an environment of 10% to 30%, wherein the volume ratio of nitrogen is 60% to 90%, the volume ratio of oxygen is 10% to 30%, the volume ratio of water vapor is 0.0001% to 0.01%, and the pressure is 10 kPa. It is preferably carried out in an environment of 1000 kPa and a temperature of 60 ° C to 200 ° C, wherein the volume ratio of nitrogen is 70% to 90%, the volume ratio of oxygen is 10% to 30%, and the volume ratio of water vapor is 0.002% to It is more preferably carried out in an environment of 0.005%, a pressure of 80 kPa to 120 kPa, and a temperature of 50 ° C to 250 ° C, and is preferably carried out at an atmospheric temperature of 20 ° C to 30 ° C.

The light-emitting layer and the hole injection layer, the hole transport layer, the electron blocking layer, the hole barrier layer, and the electron transport layer which are provided as necessary may be formed by a known method such as the above-described coating method or a vapor deposition method to be described later. . These may be formed in a vacuum atmosphere or an inert gas atmosphere such as nitrogen or argon. From the viewpoint of simplifying the production steps, at least one layer is coated with the ionic polymer described above. It is preferable to form the environment as an ideal environment at the time of the liquid or the hardened film.

As described above, since the ionic polymer to be described later is relatively stable in the atmosphere, for example, in the above-described environment, formation of a light-emitting layer or the like can suppress deterioration of the electron injection layer. As described above, the production step can be simplified by forming a light-emitting layer or the like in a vacuum environment or an environment in which an inert gas such as nitrogen or argon is not introduced.

Hereinafter, each component of the organic EL device will be described, and the material and the formation method will be described.

As described above, in the light-emitting unit, not only the light-emitting layer and the electron injection layer, but also a predetermined layer different from the light-emitting layer and the electron injection layer, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and a hole can be provided. Barrier layer, etc.

The electron injection layer has a function of improving the efficiency of electron injection from the cathode. The electron transport layer has a function of improving the electron injection efficiency of the layer connected to the cathode side surface. The hole barrier layer has a function of blocking the transport of the holes. Further, in the case where the electron injecting layer and/or the electron transporting layer have a function of blocking the transport of the holes, the layers also serve as a hole blocking layer.

The hole injection layer has a function of improving the efficiency of hole injection by the anode. The hole transport layer has a function of improving the efficiency of hole injection by the layer connected to the anode side surface. The electron blocking layer has a conveyor function that blocks electrons. Further, the hole injection layer and/or the hole transport layer have a function of blocking electron transport, and these layers also serve as an electron blocking layer.

Further, the electron injecting layer and the hole injecting layer may be collectively referred to as a charge injecting layer, and the electron transporting layer and the hole transporting layer may be collectively referred to as a charge transporting layer.

The organic EL element has (1) Bottom Emission knot. The constructor, (2) the top-emission type structure, and (3) the two-sided light-emitting type structure. The organic EL element is usually provided on a support substrate, and the bottom emission type organic EL element emits light through the support substrate to the outside, and the top emission type organic EL element emits light from the opposite side of the support substrate to the outside, and the two-sided organic type The EL element emits light to the outside from both sides of the support substrate side and the support substrate. In the present invention, any one of a bottom emission type, a top emission type, and a double-sided emission type organic EL element can be applied.

In the bottom emission type organic EL device, since the light passing through the first electrode is emitted to the outside, the first electrode can be formed by an electrode that exhibits light transmittance, but the second electrode disposed opposite to the spacer support substrate is It consists of an electrode that reflects normal light. Further, in the top-emission type organic EL device, since the light from the second electrode disposed on the support substrate is emitted to the outside of the first electrode, the second electrode can be formed by an electrode that exhibits light transmittance. Conversely, the first electrode disposed adjacent to the support substrate is configured by reflecting an electrode of normal light. Further, in the double-emitting type organic EL device, the both electrodes of the first and second electrodes are formed by electrodes that exhibit light transmittance.

<Support substrate>

The organic EL element as described above is usually formed on a support substrate. The support substrate is suitable for use in the step of manufacturing the organic EL element without chemical change, for example, using glass, plastic, polymer film, and ruthenium, and laminating. Further, the driving circuit for driving the organic EL element may be used as a supporting substrate for the driving substrate formed in advance. A bottom-emitting type or a two-sided type of organic light that passes through the support substrate as an emission structure When the EL element is mounted on a support substrate, the support substrate is a substrate that exhibits light transmittance.

<anode>

The light emitted from the light-emitting layer is an organic EL element having a structure that is emitted to the outside through the anode, and an electrode that exhibits light transmittance is used at the anode. As the electrode for exhibiting light transmittance, a film of a metal oxide, a metal sulfide, or a metal can be used, but it is suitable for use in a case where the electrical conductivity and the light transmittance are high. As the electrode, a film made of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (Indium Zinc Oxide: IZO), gold, platinum, silver, copper, or the like is specifically used. A film made of ITO, IZO, or tin oxide is suitably used. Examples of the 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 a coating method using an organic conductive material such as polythiophene.

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

<hole injection layer>

Examples of the hole injecting material constituting the hole injection layer include metal oxides such as vanadium oxide, molybdenum oxide, cerium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, and phthalocyanines. Compounds, amorphous carbons, polyanilines, and polythiophene derivatives.

As a film formation method of a hole injection layer, the film formation of the solution containing the hole injection material is mentioned, for example. For example, a solution containing a hole injecting material is applied to a film by a predetermined coating method, and further, a hole injection layer can be formed by hardening. The hardening of the coating film can be carried out by natural drying, heat drying, vacuum drying, or the like, or can be carried out by irradiating predetermined light.

Examples of the solvent to be used for the film formation from the solution include a chlorine solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran, an aromatic hydrocarbon solvent such as toluene or xylene, or acetone. A ketone solvent such as methyl ethyl ketone; an ester solvent such as ethyl acetate, butyl acetate or ethyl cellulose acetate; and water.

The film thickness of the hole injection layer is appropriately set in consideration of desired characteristics, ease of steps, and the like, and is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more desirably 5 nm to 200 nm.

<hole transport layer>

As the hole transporting material constituting the hole transporting layer, for example, polyvinylcarbazole or a derivative thereof, polydecane or a derivative thereof, polyfluorene having an aromatic amine in a side chain or a main chain may be mentioned. Alkane derivative, pyrazoline derivative, aromatic amine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or a derivative, a polypyrrole or a derivative thereof, a poly(p-phenylenevinylene) or a derivative thereof, and a poly(2,5-thiophenylene extended ethylene) or a derivative thereof.

Among these, as a material for transporting holes, polyvinyl carbazole or a derivative thereof, polydecane or a derivative thereof, and a fragrance in a side chain or a main chain are used. a polyamine derivative-based polyoxane derivative, polyaniline or a derivative thereof, polythiophene or a derivative thereof, polyarylamine or a derivative thereof, poly(p-phenylenevinylene) or a derivative thereof, or It is preferably a polymer hole transporting material such as poly(2,5-thienylthiophene) or a derivative thereof, more preferably polyvinylcarbazole or a derivative thereof, polydecane or a derivative thereof, on the side A chain or a polyoxane derivative having an aromatic amine in the main chain. In the case of a low molecular hole transport material, it is preferred to use it in a polymer adhesive.

As a film forming method of a hole transport layer, for example, a film is formed from a solution containing a hole transporting material. The solution containing the hole transporting material is applied, for example, by a predetermined coating method, and the hole transporting layer can be further formed by hardening. In the low-molecular hole transporting material, a solution in which a polymer binder is further mixed may be used to form a film.

Examples of the solvent to be used for the film formation of the solution include a chlorine solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran, and an aromatic hydrocarbon solvent such as toluene or xylene. A ketone solvent such as acetone or methyl ethyl ketone; an ester solvent such as ethyl acetate, butyl acetate or ethyl cellulose acetate.

The polymer adhesive to be mixed in the low-molecular hole transporting material is preferably one which does not extremely inhibit the charge transport, and which is suitable for the weak visible light absorption. For example, polycarbonate or polyacrylate is exemplified. , polymethacrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride and polyoxyalkylene.

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

<Light Emitting Layer>

The luminescent layer is typically formed primarily of fluorescent and/or phosphorescent organic matter or by the organic compound and the dopant. For example, dopants added to increase luminous efficiency or to change the wavelength of light emission. Further, the organic substance contained in the light-emitting layer may be a low molecular compound or a high molecular compound. Since a polymer compound having a generally high solubility in a solvent is suitable for use in a coating method as compared with a low molecular compound, the light-emitting layer is preferably a polymer compound, and is a polystyrene-converted number average of a polymer compound. The molecular weight is preferably a compound containing from 10 ³ to 10 ⁸ . Examples of the light-emitting material constituting the light-emitting layer include the following pigment-based materials, metal-based compound materials, polymer-based materials, and dopant materials.

(pigmented material)

Examples of the pigment-based material include a cyclopentamine derivative, a tetraphenylbutadiene derivative compound, a triphenylamine derivative, an oxadiazole derivative, and a pyrazoloquinoline derivative. a distyrylbenzene derivative, a distyryl extended aromatic derivative, a pyrrole derivative, a thiophene ring compound, a pyridine ring compound, a perinone derivative, an anthracene derivative, an oligothiophene derivative, and a dioxin An azole dimer, a pyrazoline dimer, a quinacridone derivative, and a coumarin derivative.

(metal complex material)

Examples of the metal complex material include a rare earth metal such as Tb, Eu, or Dy, or Al, Zn, Be, Ir, Pt, or the like as a center metal, and have oxadiazole, thiadiazole, and benzene. Pyridine, phenyl benzimidazole, A metal complex of a ligand such as a quinoline structure. Specific examples thereof include a metal complex which emits light in a triplet state, such as a ruthenium complex, a platinum complex, an aluminum quinolinol complex, and a benzoquinolinol complex. , benzoxazolyl zinc complex, benzothiazole zinc complex, azomethyl zinc complex, zinc porphyrin complex, phenanthroline complex, and the like.

(polymer material)

Examples of the polymer material include polyparaphenylene ethylene derivative, polythiophene derivative, polyparaphenylene derivative, polydecane derivative, polyacetylene derivative, polyfluorene derivative, and polyvinyl anthracene. The azole derivative is obtained by polymerizing the above-mentioned dye-based material or metal-based luminescent material.

Among the above-mentioned luminescent materials, examples of the blue luminescent material include a stilbene-based aromatic derivative (Distyrylarylene) derivative, an oxadiazole derivative, and the like, a polyvinyl carbazole derivative, and a poly A benzene derivative, a polyfluorene derivative or the like. Among them, a polyvinylcarbazole derivative, a polyparaphenylene derivative or a polyfluorene derivative of a polymer material is preferable.

Further, among the above-mentioned luminescent materials, examples of the green luminescent material include quinacridone derivatives, coumarin derivatives, and the like, polyparaphenylene ethylene derivatives, and poly Deuterium derivatives and the like. Among them, it is desirable to use a polyethylene terephthalene derivative or a polyfluorene derivative of a polymer material.

Further, among the above-mentioned luminescent materials, examples of the red luminescent material include a coumarin derivative, a thiophene ring compound, and the like, a polyparaphenylene ethylene derivative, a polythiophene derivative, and a polyfluorene. Derivatives, etc. Among them, a polyethylene terephthalene derivative, a polythiophene derivative, a polyfluorene derivative or the like which is a polymer material is preferable.

(dopant material)

As the dopant material, for example, an anthracene derivative, a coumarin derivative, a red fluorene derivative, a quinacridone derivative, a squarylium derivative, a porphyrin derivative, and styrene may be mentioned. Base dye, naphthacene derivative, pyrazolone derivative, Decacyclene, phenoxazine.

The thickness of the luminescent layer is usually from about 2 nm to 200 nm.

The light-emitting layer can be formed, for example, by film formation from a solution. The light-emitting layer, for example, a solution containing a light-emitting material can be applied by a predetermined coating method, and further formed by hardening. The solvent used for film formation from a solution may be the same solvent as the solvent used when forming a hole injection layer from the solution described above.

<Electronic transport layer>

As the electron transporting material constituting the electron transporting layer, for example, an oxadiazole derivative, decyl dimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, hydrazine or the like a derivative, tetracyanodecyl dimethane or a derivative thereof, an anthracene derivative, diphenyldicyanoethylene or a derivative thereof, a diphenylguanidine derivative, or an 8-hydroxyquinoline or a derivative thereof Metal complex, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and the like.

Examples of the film formation method of the electron transport layer include a vapor deposition method and a film formation method from a solution. Moreover, in the case of film formation from a solution, it is also possible to use it in combination. Polymer adhesive.

The film thickness of the electron transport layer is appropriately set in consideration of desired characteristics, ease of steps, and the like, 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 injecting layer is a structure containing an ionic polymer. In the ionic polymer constituting the electron injecting layer, for example, one or more groups selected from the group represented by the following formula (1) and the group represented by the following formula (2) are selected. The polymer of the structural unit. In one form of the ionic polymer, a structural unit in which one or more groups are selected from the group represented by the formula (1) and the group represented by the formula (2) is contained, and in the entire structural unit, It can be exemplified that there are 15 to 100 mol% of the polymer.

-(Q ¹ ) _n1 -Y ¹ (m ¹ ) _a1 (Z ¹ ) _b1 (1)

In the formula (1), Q ¹ represents a divalent organic group, and Y ¹ represents -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^- , m ¹ An ammonium cation representing a metal cation or with or without a substituent, 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 ^- . N1 represents an integer of 0 or more, a1 represents an integer of 1 or more, and b1 represents an integer of 0 or more. However, a1 and b1 are selected such that the charge of the group represented by the formula (1) becomes 0, and R ^a represents an alkyl group having 1 to 30 carbon atoms with or without a substituent, or a carbon atom with or without a substituent. A number of 6 to 50 aryl groups. Q ¹ , M ¹ and Z ^{1 are} each a plurality of cases, and may be the same or different.

-(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 carbocation, an ammonium cation, a phosphonium cation or a phosphonium cation or a phosphonium 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 ^- , Z ² represents a metal cation or an ammonium cation with or without a substituent. N2 represents an integer of 0 or more, a2 represents an integer of 1 or more, and b2 represents an integer of 0 or more. However, a2 and b2 are selected such that the charge of the group represented by the formula (2) becomes 0, and R ^b represents an alkyl group having 1 to 30 carbon atoms with or without a substituent, or the number of carbon atoms with or without a substituent. 6 to 50 aryl groups. The case where each of Q ² , M ² and Z ² is plural may be the same or different.

As a form of using one of the ionic polymers in the present embodiment, a polymer having a group represented by the following formula (3) may be further mentioned. The ionic polymer may have a group represented by the formula (3), and the group represented by the formula (3) may be contained in the structural unit of the ionic polymer, or may be selected from the group consisting of 1) One or more base structural units in the group shown by the formula (2) are contained in the same structural unit, or may be contained in different other structural units. Further, as one of the ionic polymers, a structure containing at least one selected from the group represented by the formula (1), the group represented by the formula (2), and the group represented by the formula (3) may be mentioned. The unit, in the full structural unit, has from 15 to 100 mole % of polymer.

-(Q ³ ) _n3 -Y ³ (3)

In the formula (3), Q ³ represents a divalent organic group, Y ³ represents a group represented by -CN or any one of the formulae (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 formulae (4) to (12), R' represents a divalent hydrocarbon group with or without a substituent, and R" represents a monovalent hydrocarbon group with or without a substituent, -COOH, -SO ₃ H, -OH, -SH, _{^{-NR c 2, -CN, -C (}} = O) NR c 2 or a hydrogen atom, R '''represents a substituent group, with or without trivalent hydrocarbon .a3 represents an integer of 1, a4 represents an integer of 0 R ^c 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. R', R" and R''' are each plural. The situation can be the same or different.

The ionic polymer is one selected from the group consisting of 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 a structural unit represented by the formula (20). The above structural unit is preferably contained in the entire structural unit in an amount of 15 to 100 mol%.

In the formula (13), R ¹ represents a monovalent group having a group represented by the formula (14), and Ar ¹ represents an aromatic group having a (2+n4) valence other than R ¹ or having no substituent. N4 represents an integer of 1 or more. R ¹ is a plurality of cases, and may be the same or different.

In the formula (14), R ² represents an organic group having a (1+m1+m2) valence, and Q ¹ , Q ³ , Y ¹ , m ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 are the same as defined above. It is meant that m1 and m2 are independent of each other and represent an integer of 1 or more. Q ¹ , Q ³ , Y ¹ , m ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are each plural, and 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 represents a (2+n5)-valent aromatic group with or without a substituent other than R ³ . N5 represents an integer of 1 or more. R ³ is a plurality of cases, and may be the same or different.

In the formula (16), R ⁴ represents an organic group having a (1+m3+m4) valence, and Q ² , Q ³ , Y ² , m ² , Z ² , Y ³ , n2, a2, b2 and n3 are the same as defined above. Meaning, m3 and m4 are independent, and represent an integer of 1 or more. Q ² , Q ³ , Y ² , m ² , Z ² , Y ³ , n2, a2, b2, and n3 are each plural, and may be the same or different.

In the formula (17), R ⁵ is a monovalent group having a group represented by the formula (18), R ⁶ is a monovalent group having a group represented by the formula (19), and Ar ³ is a group other than R ⁵ and R ⁶ The (2+n6+n7)valent aromatic group with or without a substituent. N6 and n7 are integers each independently representing 1 or more. R ⁵ and R ^{6 are} each a plurality of cases, and may be the same or different.

-R ⁷ -{(Q ¹ ) _n1 -Y ¹ (m ¹ ) _a1 (Z ¹ ) _b1 } _m5 (18)

In the formula (18), R ⁷ is a direct bond or an organic group representing a (1+m5) valence, and Q ¹ , Y ¹ , m ¹ , Z ¹ , n1, a1 and b1 are the same meanings as described above. M5 represents an integer of 1 or more. Each of Q ¹ , Y ¹ , m ¹ , Z ¹ , n1 , a1 and b1 is plural, and may be the same or different.

-R ⁸ -{(Q ³ ) _n3 -Y ³ } _m6 (19)

In the formula (19), R ⁸ represents a single bond or an organic group of (1+m6) valence, Y ³ and n3 represent the same meaning as described above, and m6 represents an integer of 1 or more. However, when R ⁸ is a single bond, m6 represents 1. Each of Q ³ , Y ³ and n3 is plural, and may be the same or different.

In the formula (20), R ⁹ is a monovalent group having a group represented by the formula (21), R ¹⁰ is a monovalent group having a group represented by the formula (22), and Ar ⁴ is a group other than R ⁹ and R ¹⁰ The (2+n8+n9) valent aromatic group with or without a substituent. N8 and n9 are integers each independently representing 1 or more. R ⁹ and R ^{10 are} each a plurality of cases, and may be the same or different.

-R ¹¹ -{(Q ² ) _n2 -Y ² (m ² ) _a2 (Z ² ) _b2 } _m7 (21)

In the formula (21), R ¹¹ is an organic group representing a single bond or a (1+m7) valence, and Q ² , Y ² , m ² , Z ² , n2, a2 and b2 are the same meanings as described above, m7 Is an integer representing 1 or more. However, when R ¹¹ is a single bond, m7 represents 1. Q ² , Y ² , m ² , Z ² , n2, a2, and b2 are each a plural number, and may be the same or different.

-R ¹² -{(Q ³ ) _n3 -Y ³ } _m8 (22)

In the formula (22), R ¹² is an organic group representing a single bond or a (1+m8) valence, Y ³ and n3 are the same meanings as described above, and m8 is an integer of 1 or more. However, when R ¹² is a single bond, m8 represents 1. Each of Q ³ , Y ³ and n3 is plural, and may be the same or different.

The structural unit in the ionic polymer may contain two or more kinds of the group represented by the formula (1), and the group represented by the formula (2) may contain two or more types, and the group represented by the formula (3) may contain two types. the above.

(base shown in equation (1))

In the formula (1), the divalent organic group represented by Q ¹ may, for example, be a methylene group, an exoethyl group, a 1,2-extended propyl group, a 1,3-propanyl group or a 1,2-extended group. Base, 1,3-butylene, 1,4-tert-butyl, 1,5-exopentyl, 1,6-extension, 1,9-extension, 1,12-extension a valence-saturated hydrocarbon group having 1 to 50 carbon atoms with or without a substituent of at least one hydrogen atom in the group substituted with a substituent; a vinyl group, a propenyl group, a 3-butene group a group, a 2-butenyl group, a 2-endopentenyl group, a 2-extended hexenyl group, a 2-extended alkenyl group, a 2-extended dodecenyl group, at least one hydrogen atom of the group a 2- to 50-membered alkenyl group having a substituent or the like, having or without a substituent, and a divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms with or without a ethynyl group; Cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclodecyl, cyclododecyl, ferrocene, an adamantyl, such a group a divalent cyclic saturated hydrocarbon group having 3 to 50 carbon atoms with or without a substituent in which at least one hydrogen atom is substituted by a substituent; 1,4-phenylene, 1,4-naphthyl, 1,5-anthranyl, 2,6-anthranyl, biphenyl-4,4'-diyl, at least a aryl group having 6 to 50 carbon atoms with or without a substituent substituted by a substituent; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a group in which at least one hydrogen atom of the group is substituted with a substituent, etc., with or without a substituent, an alkyloxy group having 1 to 50 carbon atoms; having a carbon atom An imido group of a substituent; a mercapto group having a substituent containing a carbon atom. From the viewpoint of easiness of synthesis of a monomer which is a raw material of an ionic polymer (hereinafter also referred to as "raw material monomer"), it is preferably a divalent saturated hydrocarbon group, an extended aryl group or an alkylene group. .

As the substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyloxy group, an aralkylthio group, an aralkenyl group, or an aromatic group can be mentioned. Alkynyl group, amine group, substituted amine group, fluorenyl group, substituted fluorenyl group, halogen atom, fluorenyl group, decyloxy group, imine residue, decylamino group, oxyquinone group, monovalent heterocyclic group, hydroxy group , carboxyl group, substituted carboxyl group, cyano group and nitro group. The above substituents are in the plural case, and these may be the same or different. Among these, a substituent other than an amine group, a mercapto group, a halogen atom, a hydroxyl group, and a nitro group contains a carbon atom.

Hereinafter, the description of the substituents will be given. Further, the term "C _m to C _n " (m, n is a positive integer of m < n) indicates that the number of organic carbon atoms described simultaneously with this term is m to n. For example, if C _m to C _n alkyl, it means that the number of carbon atoms of the alkyl group is from m to n, and if C _m to C _n alkaryl, the number of carbon atoms of the alkyl group is from m to n, if The aryl-C _m to C _n alkyl group means that the alkyl group has from m to n carbon atoms.

The alkyl group may be linear or branched, or may be a cycloalkyl group. The alkyl group usually has 1 to 20 carbon atoms and is preferably 1 to 10. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group or a octyl group. Base, sulfhydryl, sulfhydryl, lauryl, and the like. The hydrogen atom in the aforementioned alkyl group may also 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. Further, 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 second butyl group, a tert-butyl group, and a pentyl group. Isoamyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl.

The alkoxy group may be linear or branched, and may be a cycloalkoxy group or a substituent. The alkoxy group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, and a pentyloxy group. , hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, decyloxy, decyloxy, lauryloxy and the like.

The hydrogen atom in the aforementioned 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. Further, the alkoxy group also includes a methoxymethyloxy group and a 2-methoxyethyloxy group. Further, examples of the C ₁ to C ₁₂ alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and an s-butoxy group. T-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, 3,7-dimethyl Octyloxy, lauryloxy.

The alkylthio group may be linear or branched, and may be a cycloalkylthio group or a substituent. The alkylthio group usually has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. As the alkylthio group, there may be mentioned: methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, second butylthio group, tert-butylthio group, pentane Sulfur, hexylthio, cyclohexylthio, heptylthio, octylthio, sulfonylthio, sulfonylthio, laurel, and the like. The hydrogen atom in the aforementioned alkylthio group may also be substituted with a fluorine atom. As the fluorocarbon The substituted alkylthio group may, for example, be a trifluoromethylthio group or the like.

The aryl group is an atomic group remaining in an aromatic hydrocarbon which is a hydrogen atom bonded to one aromatic ring, and has a benzene ring group, and has a condensed ring group. The independent benzene ring or two or more condensed rings are via A single bond or a divalent organic group such as a vinyl group-extended alkenyl group. The aryl group usually has 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. As the aryl group, a phenyl group, a C ₁ to C ₁₂ alkoxyphenyl group, a C ₁ to C ₁₂ alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, and a 2-anthracene group are exemplified. Base, 9-mercapto and the like. The hydrogen atom in the aforementioned aryl group may also be substituted by a fluorine atom. Examples of the fluorine atom-substituted aryl group include a pentafluorophenyl group and the like. Among the aryl groups, a C ₁ to C ₁₂ alkoxyphenyl group and a C ₁ to C ₁₂ alkylphenyl group are preferred.

Among the above aryl groups, examples of the C ₁ to C ₁₂ alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, an isopropoxyphenyl group, and a butoxybenzene group. , isobutoxyphenyl, s-butoxyphenyl, t-butoxyphenyl, pentoxyphenyl, hexyloxyphenyl, cyclohexyloxyphenyl, heptyloxyphenyl, Octyloxyphenyl, 2-ethylhexyloxyphenyl, nonyloxyphenyl, nonyloxyphenyl, 3,7-dimethyloctyloxyphenyl, lauryloxyphenyl, and the like.

Among the above aryl groups, as the C ₁ to C _{1 2} alkylphenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a propylphenyl group, a trimethylphenyl group, a methyl group B may be mentioned. Phenylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl, isopentylphenyl, hexylphenyl, heptylphenyl, octyl Phenyl, nonylphenyl, nonylphenyl, dodecylphenyl, and the like.

The aryloxy group usually has 6 to 60 carbon atoms, 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 pentafluoro group. Phenoxy group and the like. Among the aryloxy groups, a C ₁ to C ₁₂ alkoxyphenoxy group and a C ₁ to C ₁₂ alkylphenoxy group are preferred.

Among the above aryloxy groups, examples of the C ₁ to C ₁₂ alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propoxyphenoxy group, and an isopropoxyphenoxy group. , butoxyphenoxy, isobutoxyphenoxy, s-butoxyphenoxy, t-butoxyphenoxy, pentyloxyphenoxy, hexyloxyphenoxy, ring Hexyloxyphenoxy, heptyloxyphenoxy, octyloxyphenoxy, 2-ethylhexyloxyphenoxy, nonyloxyphenoxy, decyloxyphenoxy, 3,7- Dimethyloctyloxyphenoxy, lauryloxyphenoxy, and the like.

Among the above aryloxy groups, examples of the C ₁ to C ₁₂ alkylphenoxy group include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, and 1,3. ,5-trimethylphenoxy, methylethylphenoxy, isopropylphenoxy, butylphenoxy, isobutylphenoxy, t-butylphenoxy, tert-butyl Phenoxy, pentylphenoxy, isopentylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, nonylphenoxy, dodecane Phenoxy group and the like.

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 aforementioned aryl group. The arylthio group usually has 6 to 60 carbon atoms, preferably 6 to 30. 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 pentafluoro group. Phenylthio and the like.

The aralkyl group is, for example, a group in which the aforementioned alkyl group is bonded to the aforementioned aryl group. The aralkyl group may also have a substituent. The aralkyl group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. As the aralkyl group, there may be mentioned phenyl-C ₁ to C ₁₂ alkyl group, C ₁ to C ₁₂ alkoxyphenyl group - C ₁ to C ₁₂ alkyl group, and C ₁ to C ₁₂ alkylphenyl group C. ₁ to C ₁₂ alkyl, 1-naphthyl-C ₁ to C ₁₂ alkyl, 2-naphthyl-C ₁ to C ₁₂ alkyl, and the like.

The arylalkoxy group is, for example, a group in which the aforementioned alkoxy group is bonded to the aforementioned aryl group. The aralkyloxy group may have a substituent. The arylalkoxy group has usually from 7 to 60 carbon atoms, preferably from 7 to 30 carbon atoms. As the aryl alkoxy group, a phenyl-C ₁ to C ₁₂ alkoxy group, a C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkoxy group, a C ₁ to C ₁₂ alkyl group may be mentioned. Phenyl-C ₁ to C ₁₂ alkoxy, 1-naphthyl-C ₁ to C ₁₂ alkoxy, 2-naphthyl-C ₁ to C ₁₂ alkoxy 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 also have a substituent. The arylalkylthio group has usually from 7 to 60 carbon atoms, preferably from 7 to 30 carbon atoms. As the arylalkylthio group, a phenyl-C ₁ to C ₁₂ alkylthio group, a C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylthio group, a C ₁ to C ₁₂ alkyl group may be mentioned. Phenyl-C ₁ to C ₁₂ alkylthio, 1-naphthyl-C ₁ to C ₁₂ alkylthio, 2-naphthyl-C ₁ to C ₁₂ alkylthio, and the like.

The arylalkenyl group is, for example, a group having an alkenyl group bonded to the aforementioned aryl group. The arylalkenyl group usually has 8 to 60 carbon atoms, preferably 8 to 30 carbon atoms. As the aralkenyl group, a phenyl-C ₂ to C ₁₂ alkenyl group, a C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkenyl group, and a C ₁ to C ₁₂ alkylphenyl-C may be mentioned. ₂ to C ₁₂ alkenyl, 1-naphthyl-C ₂ to C ₁₂ alkenyl, 2-naphthyl-C ₂ to C ₁₂ alkenyl, etc., as C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkenyl group, C ₂ to C ₁₂ alkylphenyl group -C ₂ to C ₁₂ alkenyl group is preferred. Further, examples of the C ₂ to C ₁₂ alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2- Pentenyl, 1-hexenyl, 2-hexenyl, 1-octenyl.

The arylalkynyl group is, for example, a group having an alkynyl group bonded to the aforementioned aryl group. The number of carbon atoms of the aralkynyl group is usually from 8 to 60, preferably from 8 to 30. As the aralkynyl group, a phenyl-C ₂ to C ₁₂ alkynyl group, a C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl group, and a C ₁ to C ₁₂ alkylphenyl-C may be mentioned. ₂ to C ₁₂ alkynyl, 1-naphthyl-C ₂ to C ₁₂ alkynyl, 2-naphthyl-C ₂ to C ₁₂ alkynyl, etc., as C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl group, C ₁ to C ₁₂ alkylphenyl group -C ₂ to C ₁₂ alkynyl group are preferred. Further, examples of the C ₂ to C ₁₂ alkynyl group include acetylene, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, and 2 a pentynyl group, a 1-hexynyl group, a 2-hexynyl group, a 1-octynyl group.

The substituted amine group is one or two groups of at least one hydrogen atom in the amine group selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Substituted amine groups are preferred. The alkyl group, the aryl group, the arylalkyl group or the monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amine group, the number of carbon atoms of the alkyl group, the aryl group, the aralkyl group or the monovalent heterocyclic group which may have a substituent, usually from 1 to 60, preferably from 2 to 48 . As the substituted amine group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, an isopropylamine group, a diisopropylamino group, a butylamine group, an isobutylamine can be exemplified. Base, s-butylamino, t-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, decylamino, decylamino , 3,7-dimethyloctylamino, laurylamine, cyclopentylamino, dicyclopentylamino, cyclohexylamino, dicyclohexylamino, bis(trifluoromethyl)amino, benzene Amino group, diphenylamino group, (C ₁ to C ₁₂ alkoxyphenyl)amino group, di(C ₁ to C ₁₂ alkoxyphenyl)amino group, di(C ₁ to C ₁₂ alkyl group) Phenyl)amino, 1-naphthylamino, 2-naphthylamino, pentafluoroanilino, vinylamino, pyridazinylamino, pyrimidinylamino, piperidinylamino, triazinyl Amino, (phenyl-C ₁ to C ₁₂ alkyl) amine, (C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl) amine, (C ₁ to C ₁₂ alkyl benzene) -C ₁ to C ₁₂ alkyl)amino group, di(C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl)amino group, di(C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl)amino, 1-naphthyl-C ₁ to C _{1 2} alkylamino group, 2-naphthyl-C ₁ to C ₁₂ alkylamino group and the like.

As the substituted fluorenyl group, at least one hydrogen atom among the fluorenyl groups may be exemplified by 1 to 3 groups selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and a monovalent heterocyclic group. The thiol group substituted by the base. The alkyl group may have an aryl group, an aralkyl group or a monovalent heterocyclic group as a substituent. The number of carbon atoms of the substituted indenyl group is not limited to the number of carbon atoms which may have a substituent of the alkyl group, the aryl group, the aralkyl group or the monovalent heterocyclic group, and is usually from 1 to 60, preferably from 3 to 48. Further, examples of the substituted fluorenyl group include a trimethyl fluorenyl group, a triethyl decyl group, a tripropyl decyl group, a triisopropyl decyl group, an isopropyl dimethyl fluorenyl group, and an isopropyl di Base, tributyl dimethyl fluorenyl, pentyl dimethyl fluorenyl, hexyl dimethyl fluorenyl, heptyl dimethyl fluorenyl, octyl dimethyl fluorenyl, 2-ethylhexyl Dimethyl decyl, decyl dimethyl fluorenyl, decyl dimethyl fluorenyl, 3,7-dimethyloctyl dimethyl fluorenyl, lauryl dimethyl fluorenyl, (phenyl-C ₁ to C ₁₂ alkyl)fluorenyl, (C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl)fluorenyl, (C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkane () fluorenyl, (1-naphthyl-C ₁ to C ₁₂ alkyl) fluorenyl, (2-naphthyl-C ₁ to C ₁₂ alkyl) fluorenyl, (phenyl-C ₁ to C ₁₂ alkyl) a dimethyl fluorenyl group, a triphenyl fluorenyl group, a tris(p-xylyl) fluorenyl group, a tribenzyl fluorenyl group, a diphenylmethyl fluorenyl group, a tert-butyldiphenyl fluorenyl group, a dimethyl group Phenylphenyl fluorenyl and the like.

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

The fluorenyl group usually has 2 to 20 carbon atoms, preferably 2 to 18. Examples of the fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a trimethyl ethane group, a benzindenyl group, a trifluoroethyl fluorenyl group, and a pentafluorobenzyl group.

The number of carbon atoms of the methoxy group is usually from 2 to 20, preferably from 2 to 18. Examples of the decyloxy group include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, an isobutyloxy group, a trimethylacetoxy group, a benzhydryloxy group, and a trifluoroacetoxy group. Pentafluorobenzyloxy and the like.

The imine residue is an imine compound having a structure represented by at least one of the formula: HN=C< and the formula: -N=CH-, and the residue after removing one hydrogen atom in the structure means. As such an imine compound, for example, an aldimine, a ketimine, and a hydrogen atom bonded to a nitrogen atom in an aldimine may be an alkyl group, an aryl group, an arylalkyl group, an aralkenyl group or an aral alkyne. a compound substituted by a group or the like. The number of carbon atoms of the imine residue is usually from 2 to 20, preferably from 2 to 18. As the imine residue, for example, a general formula: -CR ^β =NR ^γ or a general formula: -N=C(R ^γ ) ₂ (wherein R ^β represents a hydrogen atom, an alkyl group, or the like, An aryl group, an aralkyl group, an aralkenyl group, or an aralkynyl group, R ^γ independently represents an alkyl group, an aryl group, an arylalkyl group, an aralkenyl group, or an arylalkynyl group, but two of R ^γ In this case, two R ^γ are a divalent group which are integrated with each other, and for example, an ethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group may be formed as a carbon atom number 2 The base shown by the alkenyl ring to 18). Examples of the imine residue include the following groups.

In the formula, Me represents a methyl group, and the following is the same.

The mercapto group has usually from 1 to 20 carbon atoms, preferably from 2 to 18. Examples of the guanamine group include a mercaptoamine group, an etidamine group, a propylamine group, a butylammonium group, a benzoguanamine group, a trifluoroacetamido group, a pentafluorophenylamine group, and a dimethyl group. An amidino group, a diethylamine group, a dipropylammonium group, a dibutylammonium group, a diphenylguanamine group, a bis(trifluoroacetamidine)amine group, a bis(pentafluorophenylhydrazine)amine group, or the like.

The quinone imine group is a residue obtained by removing a hydrogen atom bonded to a nitrogen atom thereof by a quinone imine, and the number of carbon atoms is usually 4 to 20, preferably 4 to 18. As the quinone imine group, the following groups can be mentioned.

The monovalent heterocyclic group is an atomic group remaining by removing one hydrogen atom from the heterocyclic compound. Here, the heterocyclic compound means that, in the organic compound having a cyclic structure, as an element constituting the ring, not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a ruthenium atom, or a selenium An organic compound of a hetero atom such as an atom, a ruthenium atom or an arsenic atom. The monovalent heterocyclic group may have a substituent. The monovalent heterocyclic group has usually 3 to 60 carbon atoms, preferably 3 to 20. Further, the number of carbon atoms of the monovalent heterocyclic group is the number of carbon atoms which does not contain a substituent. Examples of such a monovalent heterocyclic group include a thienyl group, a C ₁ to C ₁₂ alkylthiophenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ to C ₁₂ alkyl pyridyl group, and a pyridazinyl group. , pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolyl, isoquinolyl, wherein, thienyl, C ₁ to C ₁₂ alkylthiophenyl, pyridyl and C ₁ to A C ₁₂ alkyl pyridyl group is preferred. Further, as the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferred.

The substituted carboxyl group means 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* (wherein, R * is a group represented by an alkyl group, an aryl group, an aralkyl group or a monovalent heterocyclic group). The number of carbon atoms of the substituted carboxyl group is usually from 2 to 60, preferably from 2 to 48. The alkyl group, the aryl group, the aralkyl group or the monovalent heterocyclic group may have a substituent. Further, the number of carbon atoms is not limited to the number of carbon atoms of the alkyl group, the aryl group, the aralkyl group or the monovalent heterocyclic group which may have a substituent. Examples of the substituted carboxyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, an s-butoxycarbonyl group, and a t-butyl group. Oxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, 3 , 7-dimethyloctyloxycarbonyl, dodecyloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyl An oxycarbonyl group, a phenoxycarbonyl group, a naphthyloxycarbonyl group, a pyridyloxycarbonyl group or the like.

In the formula (1), Y ¹ represents ^a monovalent group such as -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^- . As Y ¹ are, from the viewpoint of acidity of the ionic polymer, it is _{^{-CO 2 -, -SO 2 -,}} -PO 3 - ideal to -CO ₂ ^- is preferred, from an ionic polymerization From the viewpoint of the stability of the object, it is preferably -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- or -PO ₃ ^- .

In the formula (1), M ¹ represents a metal cation or an ammonium cation with or without a substituent. The metal cation is preferably a monovalent, divalent or trivalent ion, and examples thereof include Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, and Cu. Ions of Fe, Ga, Mn, Pb, Sn, Ti, V, W, Y, Yb, Zn, Zr, and the like. Among them, Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Ag ⁺ , Mg ²⁺ , and Ca ²⁺ are preferred. Further, examples of the substituent which the ammonium ion may have include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, and a third butyl group having 1 to 10 carbon atoms. alkyl.

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 ^- .

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

In the 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 represented by the formula (1) becomes zero. For example, Y ¹ is -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- , or -B(R ^a ) ₃ ^- , M ¹ is a monovalent metal cation or with or without a substituent Ammonium cation, Z ¹ is F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^a SO ₃ ^- , R ^a COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- The case of CN ^- , NO ₃ ^- , HSO ₄ ^- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- is selected in such a manner as 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 ^- In the case of H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , it is selected in such a manner 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 ^- , HSO ₄ ^- In the case of 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 is a monovalent metal cation or ammonium with or without a substituent In the case where the cation, Z ¹ is SO ₄ ^2- or HPO ₄ ^2- , it is selected so as to satisfy a1=2×b1+1. In any of the above mathematical expressions indicating the relationship between a1 and b1, a1 is ideally an integer of 1 to 5, and more preferably 1 or 2.

R ^a is an aryl group having 6 to 30 carbon atoms or a substituent having 6 to 50 carbon atoms, with or without a substituent. The substituent may be the same as the substituent exemplified in the description of Q ¹ described above. Substituents are in the plural, and these may be the same or different. As R ^a , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and a octyl group are exemplified. Carbon having 1 to 20 carbon atoms such as phenyl, fluorenyl, fluorenyl and lauryl, phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl and the like An aryl group having an atomic number of 6 to 30 or the like.

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

-COO ^- M ⁺ -CH ₂ -COO ^- M ⁺ -(CH ₂ ) ₂ -COO ^- M ⁺ -(CH ₂ ) ₃ -COO ^- M ⁺ -(CH ₂ ) ₄ -COO ^- M ⁺

-(CH ₂ ) ₅ -COO ^- M ⁺ -(CH ₂ ) ₆ -COO ^- M ⁺ -(CH ₂ ) ₇ -COO ^- M ⁺ -(CH ₂ ) ₈ -COO ^- M ⁺

-O-CH ₂ -COO ^- M ⁺ -O-(CH ₂ ) ₂ -COO ^- M ⁺ -O-(CH ₂ ) ₃ -COO ^- M ⁺ -O-(CH ₂ ) ₄ -COO ^- M ⁺

-O-(CH ₂ ) ₅ -COO ^- M ⁺ -O-(CH ₂ ) ₆ -COO ^- M ⁺ -O-(CH ₂ ) ₇ -COO ^- M ⁺ -O-(CH ₂ ) ₈ -COO ^- M ⁺

-SO ₃ ^- M ⁺ -CH ₂ -SO ₃ ^- M ⁺ -(CH ₂ ) ₂ -SO ₃ ^- M ⁺ -(CH ₂ ) ₃ -SO ₃ ^- M ⁺ -(CH ₂ ) ₄ -SO ₃ ^- M ⁺

-(CH ₂ ) ₅ -SO ₃ ^- M ⁺ -(CH ₂ ) ₆ -SO ₃ ^- M ⁺ -(CH ₂ ) ₇ -SO ₃ ^- M ⁺ -(CH ₂ ) ₈ -SO ₃ ^- M ⁺

-O-CH ₂ -SO ₃ ^- M ⁺ -O-(CH ₂ ) ₂ -SO ₃ ^- M ⁺ -O-(CH ₂ ) ₃ -SO ₃ ^- M ⁺ -O-(CH ₂ ) ₄ -SO ₃ ^- M ⁺

-O-(CH ₂ ) ₅ -SO ₃ ^- M ⁺ -O-(CH ₂ ) ₆ -SO ₃ ^- M ⁺ -O-(CH ₂ ) ₇ -SO ₃ ^- M ⁺ -O-(CH ₂ ) ₈ -SO ₃ ^- M ⁺

(base shown in equation (2))

In the formula (2), the divalent organic group represented by Q ² may be the same as the divalent organic group represented by the above-mentioned Q ¹ , and the ease of synthesis of the raw material monomer is considered. In general, a divalent saturated hydrocarbon group, an extended aryl group or an alkyleneoxy group is preferred.

The group exemplified as the above-mentioned divalent organic group represented by Q ² may have a substituent, and examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. . In the case where the substituents are plural, these may be the same or different.

In the formula (2), Y ² represents a carbocation, an ammonium cation, a phosphonium cation, a phosphonium cation, or a phosphonium cation.

As the carbocation, for example, a group represented by -C ⁺ R ₂ (wherein R is the same or different and represents an alkyl group or an aryl group) can be mentioned.

Examples of the ammonium cation include a group represented by -N ⁺ R ₃ (wherein R is the same or different and represents a hydrogen atom, an alkyl group or an aryl group).

Examples of the phosphonium cation include a group represented by -P ⁺ R ₃ (wherein R is the same or different and represents a hydrogen atom, an alkyl group or an aryl group).

Examples of the phosphonium cation include a group represented by -S ⁺ R ₂ (wherein R is the same or different and represents a hydrogen atom, an alkyl group or an aryl group).

Examples of the phosphonium cation include a group represented by -I ⁺ R ₂ (wherein R is the same or different and represents a hydrogen atom, an alkyl group or an aryl group).

In the formula (2), Y ^{2 is a} carbocation, an ammonium cation, or the like, from the viewpoint of easiness of synthesis of a raw material monomer and stability of air, moisture or heat of a raw material monomer and an ionic polymer. The phosphonium cation and the phosphonium cation are preferred, and the ammonium cation is more preferred.

In the formula (2), Z ² represents a metal cation or an ammonium cation with or without a substituent. The metal cation is preferably a monovalent, divalent or trivalent ion, and examples thereof include Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, and Fe. Ions such as Ga, Mn, Pb, Sn, Ti, V, W, Y, Yb, Zn, Zr, and the like. Further, examples of the substituent which may be an ammonium cation include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group having 1 to 10 carbon atoms. alkyl.

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 ^- , PF ₆ ^- or BPh ₄ ^- .

In the formula (2), n2 represents an integer of 0 or more, and preferably 0 to 6 The integer is more ideally an integer from 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) becomes 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 ^{- In the case} of NO ₃ ^- , HSO ₄ ^- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , Z ² is a monovalent metal ion or an ammonium ion with or without a substituent, to satisfy a2 Selecting from the mode of =b2+1, if Z ² is a divalent metal ion, it is selected so as to satisfy a2=2×b2+1, and if Z ² is a trivalent metal ion, it is to satisfy a2=3. Select from the mode of ×b2+1. When M ² is SO ₄ ^2- or HPO ₄ ^2- , and Z ² is a monovalent metal ion or an ammonium ion with or without a substituent, it is selected so as to satisfy b2=2×a2-1, Z ^{When 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 mathematical expressions indicating the relationship between a2 and b2, a2 is desirably an integer of 1 to 3, more preferably 1 or 2.

R ^b is 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 examples of the substituent which may be present as such a group include : the same substituent as the substituent exemplified in the description relating to Q ¹ described above. In the case where the substituents are plural, these may be the same or different. As R ^b , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and a octyl group are exemplified. Alkyl, fluorenyl, fluorenyl, lauryl, and the like having 1 to 20 carbon atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl, etc. An aryl group having an atomic number of 6 to 30 or the like.

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

-NMe ₂ Et ⁺ X ^- -CH ₂ -NMe ₂ Et ⁺ X ^- -(CH ₂ ) ₂ -NMe ₂ Et ⁺ X ^- -(CH ₂ ) ₃ -NMe ₂ Et ⁺ X ^- -(CH ₂ ) ₄ - NMe ₂ Et ⁺ X ^-

-(CH ₂ ) ₅ -NMe ₂ Et ⁺ X ^- -(CH ₂ ) ₆ -NMe ₂ Et ⁺ X ^- -(CH ₂ ) ₇ -NMe ₂ Et ⁺ X ^- -(CH ₂ ) ₈ -NMe ₂ Et ⁺ X ^-

-O-CH ₂ -NMe ₂ Et ⁺ X ^- -O-(CH ₂ ) ₂ -NMe ₂ Et ⁺ X ^- -O-(CH ₂ ) ₃ -NMe ₂ Et ⁺ X ^- -O-(CH ₂ ) ₄ -NMe ₂ Et ⁺ X ^-

-O-(CH ₂ ) ₅ -NMe ₂ Et ⁺ X ^- -O-(CH ₂ ) ₆ -NMe ₂ Et ⁺ X ^- -O-(CH ₂ ) ₇ -NMe ₂ Et ⁺ X ^- -O-(CH ₂ ) ₈ -NMe ₂ Et ⁺ X ^-

-NHMe ₂ ⁺ X ^- -CH ₂ -NHMe ₂ ⁺ X ^- -(CH ₂ ) ₂ -NHMe ₂ ⁺ X ^- -(CH ₂ ) ₃ -NHMe ₂ ⁺ X ^- -(CH ₂ ) ₄ -NHMe ₂ ⁺ X ^-

-(CH ₂ ) ₅ -NHMe ₂ ⁺ X ^- -(CH ₂ ) ₆ -NHMe ₂ ⁺ X ^- -(CH ₂ ) ₇ -NHMe ₂ ⁺ X ^- -(CH ₂ ) ₈ -NHMe ₂ ⁺ X ^-

-O-CH ₂ -NHMe ₂ ⁺ X ^- -O-(CH ₂ ) ₂ -NHMe ₂ ⁺ X ^- -O-(CH ₂ ) ₃ -NHMe ₂ ⁺ X ^- -O-(CH ₂ ) ₄ -NHMe ₂ ⁺ X ^-

-O-(CH ₂ ) ₅ -NMe ₃ ⁺ X ^- -O-(CH ₂ ) ₆ -NMe ₃ ⁺ X ^- -O-(CH ₂ ) ₇ -NHMe ₂ ⁺ X ^- -O-(CH ₂ ) ₈ -NHMe ₂ ⁺ X ^-

-NEt ₃ ⁺ X ^- -CH ₂ -NEt ₃ ⁺ X ^- -(CH ₂ ) ₂ -NEt ₃ ⁺ X ^- -(CH ₂ ) ₃ -NEt ₃ ⁺ X ^- -(CH ₂ ) ₄ -NEt ₃ ⁺ X ^-

-(CH ₂ ) ₅ -NEt ₃ ⁺ X ^- -(CH ₂ ) ₆ -NEt ₃ ⁺ X ^- -(CH ₂ ) ₇ -NEt ₃ ⁺ X ^- -(CH ₂ ) ₈ -NEt ₃ ⁺ X ^-

-O-CH ₂ -NEt ₃ ⁺ X ^- -O-(CH ₂ ) ₂ -NEt ₃ ⁺ X ^- -O-(CH ₂ ) ₃ -NEt ₃ ⁺ X ^- -O-(CH ₂ ) ₄ -NEt ₃ ⁺ X ^-

-O-(CH ₂ ) ₅ -NEt ₃ ⁺ X ^- -O-(CH ₂ ) ₆ -NEt ₃ ⁺ X ^- -O-(CH ₂ ) ₇ -NEt ₃ ⁺ X ^- -O-(CH ₂ ) ₈ -NEt ₃ ⁺ X ^-

-NHEt ₂ ⁺ X ^- -CH ₂ -NHEt ₂ ⁺ X ^- -(CH ₂ ) ₂ -NHEt ₂ ⁺ X ^- -(CH ₂ ) ₃ -NHEt ₂ ⁺ X ^- -(CH ₂ ) ₄ -NHEt ₂ ⁺ X ^-

-(CH ₂ ) ₅ -NHEt ₂ ⁺ X ^- -(CH ₂ ) ₈ -NHEt ₂ ⁺ X ^- -(CH ₂ ) ₇ -NHEt ₂ ⁺ X ^- -(CH ₂ ) ₈ -NHEt ₂ ⁺ X ^-

-O-CH ₂ -NHEt ₂ ⁺ X ^- -O-(CH ₂ ) ₂ -NHEt ₂ ⁺ X ^- -O-(CH ₂ ) ₃ -NHEt ₂ ⁺ X ^- -O-(CH ₂ ) ₄ -NHEt ₂ ⁺ X ^-

-O-(CH ₂ ) ₅ -NHEt ₂ ⁺ X ^- -O-(CH ₂ ) ₆ -NHEt ₂ ⁺ X ^- -O-(CH ₂ ) ₇ -NHEt ₂ ⁺ X ^- -O-(CH ₂ ) ₈ -NHEt ₂ ⁺ X ^-

-NEtPh ₂ ⁺ X ^- -CH ₂ -NEtPh ₂ ⁺ X ^- -(CH ₂ ) ₂ -NEtPh ₂ ⁺ X ^- -(CH ₂ ) ₃ -NEtPh ₂ ⁺ X ^- -(CH ₂ ) ₄ -NEtPh ₂ ⁺ X ^-

-(CH ₂ ) ₅ -NEtPh ₂ ⁺ X ^- -(CH ₂ ) ₆ -NEtPh ₂ ⁺ X ^- -(CH ₂ ) ₇ -NEtPh ₂ ⁺ X ^- -(CH ₂ ) ₈ -NEtPh ₂ ⁺ X ^-

-O-CH ₂ -NEtPh ₂ ⁺ X ^- -O-(CH ₂ ) ₂ -NEtPh ₂ ⁺ X ^- -O-(CH ₂ ) ₃ -NEtPh ₂ ⁺ X ^- -O-(CH ₂ ) ₄ -NEtPh ₂ ⁺ X ^-

-O-(CH ₂ ) ₅ -NEtPh ₂ ⁺ X ^- -O-(CH ₂ ) ₆ -NEtPh ₂ ⁺ X ^- -O-(CH ₂ ) ₇ -NEtPh ₂ ⁺ X ^- -O-(CH ₂ ) ₈ -NEtPh ₂ ⁺ X ^-

-NHPh ₂ ⁺ X ^- -CH ₂ -NHPh ₂ ⁺ X ^- -(CH ₂ ) ₂ -NHPh ₂ ⁺ X ^- -(CH ₂ ) ₃ -NHPh ₂ ⁺ X ^- -(CH ₂ ) ₄ -NHPh ₂ ⁺ X ^-

-(CH ₂ ) ₅ -NHPh ₂ ⁺ X ^- -(CH ₂ ) ₆ -NHPh ₂ ⁺ X ^- -(CH ₂ ) ₇ -NHPh ₂ ⁺ X ^- -(CH ₂ ) ₈ -NHPh ₂ ⁺ X ^-

-O-CH ₂ -NHPh ₂ ⁺ X ^- -O-(CH ₂ ) ₂ -NHPh ₂ ⁺ X ^- -O-(CH ₂ ) ₃ -NHPh ₂ ⁺ X ^- -O-(CH ₂ ) ₄ -NHPh ₂ ⁺ X ^-

-O-(CH ₂ ) ₅ -NHPh ₂ ⁺ X ^- -O-(CH ₂ ) ₆ -NHPh ₂ ⁺ X ^- -O-(CH ₂ ) ₇ -NHPh ₂ ⁺ X ^- -O-(CH ₂ ) ₈ -NHPh ₂ ⁺ X ^-

(base shown in formula (3))

In the formula (3), the divalent organic group represented by Q ³ may be the same as those of the divalent organic group represented by Q ¹ described above, and the ease of synthesis from the raw material monomers. From the viewpoint, a divalent saturated hydrocarbon group, an extended aryl group or an alkyleneoxy group is preferred.

The exemplified group of the divalent organic group represented by the above Q ³ may have a substituent, and examples of the substituent include the same substituents as those exemplified in the description of Q ¹ above. Substituents are in the plural, and these are the same or different.

The divalent organic group represented by the above Q ^{3 is} preferably a group represented by -(CH ₂ )-.

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

In the formula (3), Y ³ represents -CN or a group represented by any one of the formulae (4) to (12).

In the formulae (4) to (12), examples of the divalent hydrocarbon group represented by R' include a methylene group, an exoethyl group, a 1,2-extended propyl group, a 1,3-propanyl group, and 1, 2-tert-butyl, 1,3-butylene, 1,4-tert-butyl, 1,5-amyl, 1,6-extension, 1,9-extension, 1,12-extension a dodecyl group, a divalent saturated hydrocarbon group having 1 to 50 carbon atoms with or without a substituent, wherein at least one of the hydrogen atoms is substituted with a substituent; a vinyl group, a propenyl group, a 3-butenyl group, a 2-butenbutenyl group, a 2-endopentenyl group, a 2-extended hexenyl group, a 2-extended alkenyl group, a 2-extended dodecenyl group, and at least An alkenyl group having 2 to 50 carbon atoms with or without a substituent, wherein the hydrogen atom is substituted with a substituent; and a carbon atom having 2 to 50 carbon atoms having or without a substituent of an exetylene group; a divalent unsaturated hydrocarbon group; a cyclopropyl group, a cyclobutene butyl group, a cyclopentylene group, a cyclohexylene group, a fluorenyl group, a fluorene group, a ferronic group, an exoskeleton group, and the like a divalent cyclic saturated hydrocarbon group having 3 to 50 carbon atoms with or without a substituent, wherein at least one hydrogen atom is substituted with a substituent; , 1,4-phenylene, 1,4-naphthyl, 1,5-naphthyl extension, extending 2,6- a naphthyl group, a biphenyl-4,4'-diyl group, an alkyl group having 6 to 50 carbon atoms with or without a substituent, wherein at least one of the hydrogen atoms is substituted with a substituent a methyloxy group, an ethoxylated group, a propenyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, etc. The alkyleneoxy group having 1 to 50 carbon atoms or the like having or having a substituent.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ above. Substituents are in the plural, and these are the same or different.

In the formulae (4) to (12), examples of the monovalent hydrocarbon group represented by R" include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a Tributyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, with or without substitution of at least one hydrogen atom in the group substituted with a substituent An alkyl group having 1 to 20 carbon atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, and at least one hydrogen group An aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group substituted with a substituent, etc. From the viewpoint of solubility of the ionic polymer, a methyl group, an ethyl group, a phenyl group, A 1-naphthyl group or a 2-naphthyl group is preferred. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ above. In the case where a plurality of substituents are present, such a case It is the same or it can be different.

In the formula (5), examples of the trivalent hydrocarbon group represented by R''' include a methane triyl group, an ethane triyl group, a 1,2,3-propane triyl group, and a 1,2,4-butane three group. 1,1,5-pentanetriyl, 1,3,5-pentanetriyl, 1,2,6-hexanetriyl, 1,3,6-hexanetriyl, such radicals An alkanetriyl group having 1 to 20 carbon atoms with or without a substituent substituted with at least one hydrogen atom in the substituent; 1,2,3-benzenetriyl, 1,2,4-benzene A 1,3,5-benzenetriyl group, an aryl group having 6 to 30 carbon atoms, or the like having at least one hydrogen atom substituted by a substituent, or the like. From the viewpoint of solubility of the ionic polymer, a methane triyl group, an ethane triyl group, a 1,2,4-benzenetriyl group or a 1,3,5-benzenetriyl group is preferred. As the substituent, the same substituents as those exemplified in the description of Q ¹ above can be mentioned. Where the substituents are plural, such may be the same or different.

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

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

As Y ³ , from the viewpoint of easiness of synthesis of a raw material monomer, a group represented by -CN, formula (4), a group represented by formula (6), a group represented by formula (10), and formula (11) The group shown is preferably a group represented by the formula (4), a group represented by the formula (6), and a group represented by the formula (11), and the following groups are particularly preferred.

-O-(CH ₂ CH ₂ O) ₂ Me -O-(CH ₂ CH ₂ O) ₃ Me -O-(CH ₂ CH ₂ O) ₄ Me

-O-(CH ₂ CH ₂ O) ₅ Me -O-(CH ₂ CH ₂ O) ₆ Me -O-(CH ₂ CH ₂ O) ₇ Me

-O-(CH ₂ CH ₂ O) ₂ H -O-(CH ₂ CH ₂ O) ₃ H -O-(CH ₂ CH ₂ O) ₄ H

-O-(CH ₂ CH ₂ O) ₅ H -O-(CH ₂ CH ₂ O) ₆ H -O-(CH ₂ CH ₂ O) ₇ H

(structural unit in ionic polymer)

The ionic polymer used in the present invention is a structural unit represented by the above formula (13), a structural unit represented by the above formula (15), a structural unit represented by the above formula (17), and the above formula (20). It is desirable that the structural unit is preferably an ionic polymer having 15 to 100 mol% in the entire structural unit.

(structural unit shown in formula (13))

In the formula (13), R ¹ is a monovalent group containing a group represented by the formula (14), and Ar ¹ is a (2+n4)-valent aromatic group having a substituent other than R ¹ , and n 4 is a An integer of 1 or more.

Formula (14) shown in the group may be directly bonded to Ar ^1, can also be bonded via the following groups ¹ and Ar: methylene, stretching ethyl, propyl stretched, stretch-butyl, pentyl extension, Extending a hexyl group, stretching a thiol group, stretching a 12-carbon group, stretching a propyl group, stretching a butyl group, stretching a cyclopentyl group, stretching a cyclohexyl group, stretching a fluorenyl group, stretching a 12-carbon group, stretching a norbornene group, An exosmandine group, an alkyl group having 1 to 50 carbon atoms with or without a substituent, wherein at least one hydrogen atom in the group is substituted with a substituent; an oxymethylene group, an oxygen-extended ethylene group, Oxypropyl propyl, oxybutylene, oxopentyl, oxyhexyl, oxo, oxydecafluoro, cyclopropoxy, cyclobutoxy, cyclopentyloxy, exo a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a ferroceneoxy group, an exo-adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like An oxygen-free alkyl group having 1 to 50 carbon atoms without a substituent; an imine group having or without a substituent; a mercapto group having or without a substituent; a vinyl group having or without a substituent; Ethylene group; with or without Substituent -methanetriyltris; hetero atom an oxygen atom, a nitrogen atom, a sulfur atom and the like.

The above Ar ¹ may have a substituent other than R ¹ . The substituent similar to the substituent exemplified in the description of Q ¹ above may be mentioned as the substituent. The above substituents are plural cases, and these may be the same or different.

The substituent other than R ¹ in the above 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 easiness of synthesis of the raw material monomer.

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

In the formula (13), examples of the (2+n4)-valent aromatic group represented by Ar ¹ include a (2+n4)-valent aromatic hydrocarbon group and a (2+n4)-valent aromatic heterocyclic group. It is preferable that only a carbon atom or a carbon atom is a (2+n4)-valent aromatic group formed by one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom. Examples of the (2+n4)-valent aromatic group include a benzene ring, a pyridine ring, a 1,2-dioxazine ring, a 1,3-dioxazine ring, and a 1,4-dioxazine ring. a monocyclic aromatic ring such as a 1,3,5-triazine ring, a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring or an indazole ring, which removes (2+n4) hydrogen atoms (2) +n4) valence group; (2+n4) valence group for removing (2+n4) hydrogen atoms by condensed condensed polycyclic aromatic ring selected from two or more ring groups of the monocyclic aromatic ring Selecting two or more aromatic rings from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring, and removing the aromatic ring by a single bond, a vinyl group or an ethynyl group ( 2+n4) (2+n4) valence of a hydrogen atom; the condensed polycyclic aromatic ring or two adjacent aromatic rings of the aromatic ring are methylene, ethyl, carbonyl, etc. The (2+n4) valence group in which (2+n4) hydrogen atoms are removed from the bridged polycyclic aromatic ring having a crosslink.

As the monocyclic aromatic ring, for example, the ring represented by the following structures 1 to 12 can be cited.

Examples of the condensed polycyclic aromatic ring include the rings shown in the following structures 13 to 27.

As the aromatic ring collector, for example, the rings shown in the following structures 28 to 36 can be cited.

As the bridged polycyclic aromatic ring, for example, the ring shown by the following structures 37 to 44 can be cited.

As the aromatic radical of the above (2+n4) valence, it is removed by a ring represented by the structures 1 to 14, 26 to 29, 37 to 39 or 41 from the viewpoint of easiness of synthesis of the raw material monomers (2) Preferably, the group of +n4) hydrogen atoms is ideal, and the group of (2+n4) hydrogen atoms is preferably removed from the ring represented by the structure 1 to 6, 8, 13, 26, 27, 37 or 41. It is more preferable that the ring represented by 37 or 41 removes a group of (2+n4) hydrogen atoms.

In the formula (14), examples of the organic group having a valence of (1+m1+m2) represented by R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. a group of (m1+m2) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-fluorenyl a 9-fluorenyl group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed by (m1+m2) hydrogen atoms. Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like The alkoxy group having 1 to 50 carbon atoms with or without a substituent removes (m1+m2) hydrogen atoms a group which removes (m1+m2) hydrogen atoms from an amine group having a substituent having a carbon atom; a group in which (m1+m2) hydrogen atoms are removed from a thiol group having a substituent having a carbon atom, from a raw material From the viewpoint of easiness of monomer synthesis, a group in which (m1+m2) hydrogen atoms are removed by an alkyl group, a group in which (m1+m2) hydrogen atoms are removed from an aryl group, and alkoxy group is removed (m1) The base of +m2) hydrogen atoms is preferred.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. The above substituents are in the plural case, and these may be the same or different.

(structural unit shown in equation (15))

In the formula (15), R ³ is a monovalent group containing a group represented by the formula (16), and Ar ² is an (2+n5)-valent aromatic group having or without a substituent other than R ³ , and n5 represents 1 The above integer.

Formula (16) shown in the group may be directly bonded to Ar ^2: may be bonded to Ar ² through the following groups: methylene, stretching ethyl, propyl stretched, stretch-butyl, pentyl extension, extending Hexyl, thiol, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluorenyl, fluorene, tetradecyl, borneol a group of alkyl groups having 1 to 50 carbon atoms with or without a substituent substituted by a substituent such as at least one hydrogen atom in the group; an oxygen-extension methyl group, an oxygen-extended ethyl group, and an oxygen-extended group Base, oxybutylene, oxopentyl, oxyhexanyl, oxo, oxydecaxenylene, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a fluorenyl group, a fluorenyloxy group, a decyloxy group, a ferroceneoxy group, an exo-adamantyloxy group, a group having at least one hydrogen atom substituted with a substituent, etc., with or without a substituent Oxyalkylene group having 1 to 50 carbon atoms; imino group with or without a substituent; exudyl group with or without a substituent; vinyl group with or without a substituent; ethynyl group; with or without Substituted methane triyl; Atom hetero atom, a nitrogen atom, a sulfur atom and the like.

The Ar ² may be a substituent other than R ³ . As the substituent, the same substituents as those exemplified in the description of Q ¹ above can be mentioned. In the case where the aforementioned substituents are plural, these may be the same or different.

In the case where the Ar ² is a substituent other than R ³ , an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group is preferred from the viewpoint of easiness 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. It is preferred that only a carbon atom or an aromatic group having a (2+n5) valence of one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom is preferred. As the (2+n5)-valent aromatic group, a benzene ring, a pyridine ring, a 1,2-dioxazine ring, a 1,3-dioxazine ring, a 1,4-dioxazine ring, 1, a monocyclic aromatic ring such as a 3,5-triazine ring, a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring or an oxadiazole ring, removes (2+n5) hydrogen atoms (2+n5) a valence group; a (2+n5) valence group of (2+n5) hydrogen atoms removed by a condensed polycyclic aromatic ring in which two or more rings are condensed by a group of the monocyclic aromatic rings; Two or more aromatic rings are selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring, and are removed by a single bond, a vinyl group or an ethynyl group. +n5) a (2+n5) valent group of a hydrogen atom; a divalent group derived from the condensed polycyclic aromatic ring or two adjacent aromatic rings of the aromatic ring, such as a methylene group, an ethyl group, a carbonyl group or the like The bridged polycyclic aromatic ring having a cross-linking removes (2+n5) valence groups of (2+n5) hydrogen atoms and the like.

As the monocyclic aromatic ring, for example, a ring represented by the structures 1 to 12 exemplified in the description of the structural unit represented by the formula (13) can be cited.

The condensed polycyclic aromatic ring may, for example, be a ring represented by the structures 13 to 27 exemplified in the description of the structural unit represented by the formula (13).

As the aromatic ring collector, for example, a ring represented by the structures 28 to 36 exemplified in the description of the structural unit shown by the formula (13) can be cited.

As the bridged polycyclic aromatic ring, for example, a ring represented by the structures 37 to 44 exemplified in the description of the structural unit represented by the formula (13) can be cited.

The (2+n5)-valent aromatic group is removed by a ring represented by the structures 1 to 14, 26 to 29, 37 to 39 or 41 from the viewpoint of easiness of synthesis of the raw material monomers ( Preferably, a group of 2+n5) hydrogen atoms is preferred, and a group of (2+n5) hydrogen atoms is preferably removed by a ring represented by the structure 1 to 6, 8, 13, 26, 27, 37 or 41. It is more preferable to remove (2+n5) hydrogen atoms from the ring represented by the structure 1, 37 or 41.

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

In the formula (16), examples of the organic group having a valence of (1+m3+m4) represented by R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. a group of (m3+m4) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl a 9-fluorenyl group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed by (m3+m4) hydrogen atoms. Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like Removal of (m3+m4) hydrogen atoms with an alkoxy group having 1 to 50 carbon atoms with or without a substituent Group; a substituted group having the carbon-atom of the amine was removed (m3 + m4) hydrogen atoms of the group; the silicon based substituent group removed (m3 + m4) hydrogen atoms by a group having a carbon-atoms. From the viewpoint of easiness of synthesis of a raw material monomer, a group of (m3+m4) hydrogen atoms is removed from an alkyl group, and a group of (m3+m4) hydrogen atoms is removed from the aryl group, and is removed by an alkoxy group. The base of (m3+m4) hydrogen atoms is preferred.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ above. In the case where the above substituents are plural, these may be the same or different.

(Structural unit shown in equation (17))

In the formula (17), R ⁵ is a monovalent group containing a group represented by the formula (18), R ⁶ is a monovalent group containing a group represented by the formula (19), and Ar ³ is a group other than R ⁵ and R ⁶ Or an unsubstituted (2+n6+n7)-valent aromatic group, and n6 and n7 are each independently and represent an integer of 1 or more.

(18) and a group of formula (19) represents a group of formula, ³ can be directly bonded to Ar, may also be combined with Ar ³ through the group: a methylene group, an ethyl stretching, stretching propyl, butyl extension , pentyl group, hexanyl group, hydrazine group, 12 carbon group, propyl group, butyl ring, pentylene group, cyclohexyl group, fluorene ring, fluorene ring, 12 carbon base a norbornyl group, an exo-adamantyl group, an alkyl group having 1 to 50 carbon atoms with or without a substituent substituted with at least one hydrogen atom in the group; Ethyl, oxypropyl propyl, oxobutyl, oxopentyl, oxetyl, oxo, oxydecafluoro, cyclopropoxy, cyclobutoxy, cyclopentyl a hexyloxy group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclodecadecenyloxy group, a ferroceneoxy group, an exo-adamantyloxy group, and a group in which at least one hydrogen atom is substituted with a substituent Or an alkyl group having 1 to 50 carbon atoms with or without a substituent; an imine group with or without a substituent; a mercapto group with or without a substituent; a vinyl group with or without a substituent; Ethylene group; with or without substituent Three alkyl groups; hetero atom an oxygen atom, a nitrogen atom, sulfur atom and the like.

Ar ³ may be a substituent other than R ⁵ and R ⁶ . As the substituent, the same substituents as those exemplified in the description of Q ¹ above can be mentioned. In the case where the above substituents are plural, these may be the same or different.

As a substituent other than R ⁵ and R ⁶ in the above Ar ³ , an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group is used from the viewpoint of easiness of synthesis of a raw material monomer. It is better.

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

In the formula (17), n7 represents an integer of 1 or more, and is 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 (2+n6+n7)-valent aromatic hydrocarbon groups and (2+n6+n7) valences. An aromatic heterocyclic group is a (2+n6+n7) aromatic having only a carbon atom or a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom. The base is good. Examples of the (2+n6+n7)-valent aromatic group include a benzene ring, a pyridine ring, a 1,2-dioxazine ring, a 1,3-dioxazine ring, and 1,4-dioxene. (2+n6+n7) valence group of (2+n6+n7) hydrogen atoms removed by a monocyclic aromatic ring such as a azine ring, a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring or an oxazole ring; Selecting two or more ring-condensed condensed polycyclic aromatic rings in a group of cyclic aromatic rings to remove (2+n6+n7) valence groups of (2+n6+n7) hydrogen atoms; Two or more aromatic rings are selected from the group consisting of an aromatic ring and the condensed polycyclic aromatic ring, and are removed by a single bond, a vinyl group or an ethynyl group, and are removed from the aromatic ring set (2+n6+) N7) a (2+n6+n7) valence group of a hydrogen atom; the condensed polycyclic aromatic ring or the two adjacent aromatic rings of the aromatic ring group having a methylene group, an ethyl group, a carbonyl group, etc. The bridged polycyclic aromatic ring having a cross-linking has a (2+n6+n7) valence group of (2+n6+n7) hydrogen atoms.

As a monocyclic aromatic ring, for example, it can be mentioned in the formula (13) The structures shown in the related description of the structural unit are shown in the structures 1 to 5 and the structures shown in the structures 7 to 10.

The condensed polycyclic aromatic ring may, for example, be a ring represented by the structures 13 to 27 exemplified in the description of the structural unit represented by the formula (13).

As the aromatic ring collector, for example, a ring represented by the structures 28 to 36 exemplified in the description of the structural unit represented by the formula (13) can be cited.

As the bridged polycyclic aromatic ring, for example, a ring represented by the structures 37 to 44 exemplified in the description of the structural unit represented by the formula (13) can be cited.

As the above-mentioned (2+n6+n7)-valent aromatic group, from the viewpoint of easiness of synthesis of the raw material monomers, from the structures 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to The group represented by 39, 41 or 42 removes (2+n6+n7) hydrogen atoms, and is preferably removed by the ring represented by structure 1, 37, 38, 41 or 42 (2+n6+n7) The group of a hydrogen atom is preferred, and a group of (2+n6+n7) hydrogen atoms is preferably removed by a ring represented by the structure 1, 38 or 42.

In the formula (18), R ⁷ is an organic group having a single bond or a (1+m5) valence, and preferably an organic group having a (1+m5) valence.

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, and a second group. a group, a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a group in which at least one hydrogen atom is substituted by a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove a group of m5 hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl a group in which at least one hydrogen atom is substituted with a substituent, and the aryl group having 6 to 30 carbon atoms with or without a substituent is substituted for a group of m5 hydrogen atoms; methoxy group, ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclo a decyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a carbon atom having or without a substituent, wherein at least one of the hydrogen atoms is substituted with a substituent or the like Alkoxy groups of 1 to 50 to remove m5 hydrogen atoms; The amine group having a substituent containing a carbon atom removes a group of m5 hydrogen atoms; the group of m5 hydrogen atoms is removed from a mercapto group having a substituent having a carbon atom, from the viewpoint of easiness of synthesis of a raw material monomer In other words, a group in which m5 hydrogen atoms are removed from an alkyl group, a group in which m5 hydrogen atoms are removed from the aryl group, and a group in which m5 hydrogen atoms are removed from the alkoxy group is preferred.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ above. In the case where the aforementioned substituents are plural, these may be the same or different.

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

In the formula (19), R ⁸ represents a single bond or a (1+m6)-valent organic group, and an organic group having a (1+m6) valence is preferred.

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, and a second group. a group, a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a group in which at least one hydrogen atom is substituted by a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove a group of m6 hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl, a group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent removes a group of m6 hydrogen atoms; a methoxy group, an ethoxy group, Propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclooxyl a ring, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group having at least one hydrogen atom substituted by a substituent, etc., having or having no substituent a group of m6 hydrogen atoms removed by an alkoxy group of 50; The amino group-substituted carbon atom of the group m6 removal of one hydrogen atom; atoms of a carbon-containing substituent group having one hydrogen atom removed m6 group of silicon based groups. From the viewpoint of easiness of synthesis of the raw material monomers, a group in which m6 hydrogen atoms are removed from the alkyl group, a group in which m6 hydrogen atoms are removed from the aryl group, and a group in which m6 hydrogen atoms are removed from the alkoxy group is preferred.

Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ above. In the case where the aforementioned substituents are plural, these may be the same or different.

In the formula (19), m6 represents an integer of 1 or more, but when R ⁸ is a single bond, m6 represents 1.

(Structural unit shown in equation (20))

In the formula (20), R ⁹ is a monovalent group containing a group represented by the formula (21), R ¹⁰ is a valent group having a group 1 represented by the formula (22), and Ar ⁴ represents a group other than R ⁹ and R ¹⁰ or The (2+n8+n9)-valent aromatic group having no substituent, and n8 and n9 each independently represent an integer of 1 or more.

Of formula (21) and a group shown in the formula (22) group is bonded directly to Ar ⁴ may be bonded via the following groups and Ar ^4: methylene, stretching ethyl, propyl stretched, stretch-butyl , pentyl group, hexanyl group, hydrazine group, 12 carbon group, propyl group, butyl ring, pentylene group, cyclohexyl group, fluorene ring, fluorene ring, 12 carbon base a norbornyl group, an exo-adamantyl group, an alkyl group having 1 to 50 carbon atoms with or without a substituent substituted with at least one hydrogen atom in the group; Ethyl, oxypropyl propyl, oxobutyl, oxopentyl, oxetyl, oxo, oxydecafluoro, cyclopropoxy, cyclobutoxy, cyclopentyl a hexyloxy group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a ferroceneoxy group, an exo-adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, etc. An oxygen-extended alkyl group having 1 to 50 carbon atoms with or without a substituent; an imine group with or without a substituent; a mercapto group with or without a substituent; a vinyl group with or without a substituent; Acetylene; with or without a substituent Three; hetero atom an oxygen atom, a nitrogen atom, sulfur atom and the like.

The above Ar ⁴ may have a substituent other than R ⁹ and R ¹⁰ . The substituent similar to the substituent exemplified in the above description of Q ¹ may be mentioned as the substituent. In the case where the aforementioned substituents are plural, these may be the same or different.

As a substituent other than R ⁹ and R ¹⁰ in the above Ar ⁴ , an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group is used from the viewpoint of easiness of synthesis of a raw material monomer. It is better.

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

In the formula (20), n9 represents an integer of 1 or more, and is preferably an integer of 1 to 4, 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 (2+n8+n9)-valent aromatic hydrocarbon groups and (2+n8+n9) valences. An aromatic heterocyclic group is a (2+n8+n9) aromatic having only one carbon atom or a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom. The base is good. Examples of the (2+n8+n9)-valent aromatic group include a benzene ring, a pyridine ring, a 1,2-dioxazine ring, a 1-dioxazine ring, and a 1-diindole. a monocyclic aromatic ring such as a azine ring, a furan ring, a pyrrole ring, a pyrazole ring, or an imidazole ring, which removes (2+n8+n9) valence groups of (2+n8+n9) hydrogen atoms; Selecting two or more ring-condensed condensed polycyclic aromatic rings to remove (2+n8+n9) valence groups of (2+n8+n9) hydrogen atoms in a group of rings; from the monocyclic aromatic ring And the condensed polycyclic aromatic ring is selected from the group consisting of two or more aromatic rings, and a single bond, a vinyl group or an ethynyl group is bonded to form an aromatic ring to remove (2+n8+n9) hydrogen atoms. (2+n8+n9) valence group; the condensed polycyclic aromatic ring or two adjacent aromatic rings of the aromatic ring are bridged by a divalent group such as a methylene group, an ethyl group or a carbonyl group. The linked polycyclic aromatic ring removes (2+n8+n9) valence groups of (2+n8+n9) hydrogen atoms.

Examples of the monocyclic aromatic ring include, for example, the structures 1 to 5 and the structures 7 to 10 exemplified in the description of the structural unit represented by the formula (13).

The condensed polycyclic aromatic ring may, for example, be a ring represented by the structures 13 to 27 exemplified in the description of the structural unit represented by the formula (13).

As the aromatic ring collector, for example, a ring represented by the structures 28 to 36 exemplified in the description of the structural unit represented by the formula (13) can be cited.

As the bridged polycyclic aromatic ring, for example, a ring represented by the structures 37 to 44 exemplified in the description of the structural unit represented by the formula (13) can be cited.

As the above-mentioned (2+n8+n9)-valent aromatic group, from the viewpoint of the ease of synthesis of the raw material monomers, by the structures 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to 39 The ring represented by 41 or 42 removes the radical of (2+n8+n9) hydrogen atoms, and is preferably represented by a structure of 1 to 5, 8, 14, 27, 28, 37, 38, 41 or 42. A hydrogen atom (2+n8+n9) removing group is preferred, and a group of (2+n8+n9) hydrogen atoms is preferably removed from the ring represented by the structure 1, 37 or 41.

In the formula (21), R ¹¹ is an organic group having a single bond or a (1+m7) valence, and preferably an organic group having a (1+m7) valence.

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, and a second group. a group, a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a group in which at least one hydrogen atom is substituted by a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove a group of m7 hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl, a group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent removes a group of m7 hydrogen atoms; a methoxy group, an ethoxy group, Propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclopropane An oxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a number of carbon atoms having or without a substituent, etc., wherein at least one of the hydrogen atoms is substituted with a substituent Alkoxy group 1 to 50 excluding a group of 7 hydrogen atoms; A group having an amino group having a substituent of a carbon atom to remove m7 hydrogen atoms; a group having m7 hydrogen atoms removed from a mercapto group having a substituent having a carbon atom. From the viewpoint of easiness of synthesis of the raw material monomers, a group in which m7 hydrogen atoms are removed from the alkyl group, a group in which m7 hydrogen atoms are removed from the aryl group, and a group in which m7 hydrogen atoms are removed from the alkoxy group is preferred.

Examples of the substituent include the same substituents as those exemplified in the above description of Q ¹ . The above substituents are in the plural case, and these may be the same or different.

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

In the formula (22), R ¹² represents a single bond or an organic group of (1+m8) valence, and an organic group having a (1+m8) valence is preferred.

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, and a second group. a group, a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a group in which at least one hydrogen atom is substituted by a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove a group of m8 hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl, a group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent removes a group of m8 hydrogen atoms; a methoxy group, an ethoxy group, Propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclopropane An oxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a number of carbon atoms having or without a substituent, etc., wherein at least one of the hydrogen atoms is substituted with a substituent Alkoxy group of 1 to 50 to remove a group of m8 hydrogen atoms; The substituted amino group containing carbon atoms of the group m8 removal of one hydrogen atom; atoms having the carbon-containing silicon based substituent group m8 removal of one hydrogen atom. From the viewpoint of easiness of synthesis of the raw material monomers, a group in which m8 hydrogen atoms are removed from the alkane group, a group in which m8 hydrogen atoms are removed from the aryl group, and a group in which m8 hydrogen atoms are removed from the alkoxy group is preferred.

Examples of the substituent include the same substituents as those exemplified in the above description of Q ¹ . In the case where the aforementioned substituents are plural, these may be the same or different.

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

(Example of a structural unit represented by the formula (13))

As a structural unit represented by the formula (13), from the viewpoint of obtaining electron transport properties of the ionic polymer, the structural unit represented by the formula (23) and the structural unit represented by the formula (24) are preferable, and the formula (24) is preferable. The structural unit shown is preferred.

In the formula (23), R ¹³ represents an organic group having a valence of (1+m9+m10), R ¹⁴ represents a monovalent organic group, and Q ¹ , Q ³ , Y ¹ , m1, Z ¹ , Y ³ , n1, a1 B1 and n3 are the same meanings as described above, and m9 and m10 each independently represent an integer of 1 or more. Each of Q ¹ , Q ³ , Y ¹ , m1, Z ¹ , Y ³ , n1, a1, b1, and n3 is plural, and may be the same or different.

In the formula (23), examples of the organic group having a valence of (1+m9+m10) represented by R ¹³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. a group of (m9+m10) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl a 9-fluorenyl group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed by (m9+m10) hydrogen atoms. Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like Removal of (m9+m10) hydrogenogens with alkoxy groups having 1 to 50 carbon atoms with or without a substituent a group of (m9+m10) hydrogen atoms removed from an amine group having a substituent having a carbon atom; a group having (m9+m10) hydrogen atoms removed from a mercapto group having a substituent having a carbon atom. From the viewpoint of easiness of synthesis of the raw material monomers, a group of (m9+m10) hydrogen atoms is removed from the aryl group by a group in which (m9+m10) hydrogen atoms are removed by an alkyl group, and is removed by an alkoxy group ( The base of m9+m10) hydrogen atoms is 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 second butyl group, and a third group. a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent in which at least one hydrogen atom of the group is substituted with a substituent or the like An alkyl group having 1 to 20 carbon atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, and at least one hydrogen atom among these groups is substituted An aryl group having 6 to 30 carbon atoms with or without a substituent; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a decyloxy group, or the like. Dodecanoyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclododecyloxy, norbornyloxy, adamantyloxy An alkoxy group having 1 to 50 carbon atoms with or without a substituent substituted by a substituent such as at least one hydrogen atom in the group; and 1 by an amine group having a substituent having a carbon atom; a group of a hydrogen atom; having a substituent having a carbon atom Silicon based. From the viewpoint of easiness of synthesis of the raw material monomers, an alkyl group, an aryl group or an alkoxy group is preferred.

The structural unit represented by the formula (23) includes the following structural units.

In the formula (24), R ¹³ represents an organic group having a (1+m11+m12) valence, and Q ¹ , Q ³ , Y ¹ , m1, Z ¹ , Y ³ , n1, a1, b1 and n3 are the same as defined above. In the meantime, m11 and m12 each independently represent an integer of 1 or more. Each of R ¹³ , m11 , m12 , Q ¹ , Q ³ , Y ¹ , m1 , Z ¹ , Y ³ , n1 , a1 , b1 and n3 is plural, and may be the same or different.

In the formula (24), examples of the organic group having a valence of (1+m11+m12) represented by ^R13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. a group of (m11+m12) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-fluorenyl a 9-fluorenyl group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed by (m11+m12) hydrogen atoms. Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like Removal of alkoxy groups having 1 to 50 carbon atoms with or without a substituent (m11+m12) Atoms group; a substituted amino group of (removed m11 + m12) hydrogen atoms by a group having a carbon-atoms; group of removed silicon based (m11 + m12) group hydrogen atoms replaced by atoms having the carbon-containing. From the viewpoint of easiness of synthesis of a raw material monomer, a group of (m11+m12) hydrogen atoms is removed from an aryl group by a group of (m11+m12) hydrogen atoms removed from the alkyl group, and is removed by an alkoxy group (m11) The base of +m12) hydrogen atoms is preferred.

The structural unit represented by the formula (24) includes the following structural units.

The structural unit represented by the formula (13) is preferably a structural unit represented by the formula (25) from the viewpoint of obtaining durability of the ionic polymer.

In the formula (25), R ¹⁵ represents an organic group having a valence of (1+m13+m14), and Q ¹ , Q ³ , Y ¹ , m1, Z ¹ , Y ³ , n1, a1, b1 and n3 represent the same as described above. It is meant that m13, m14 and m15 each independently represent an integer of 1 or more. Each of R ¹⁵ , m13 , m14 , Q ¹ , Q ³ , Y ¹ , m1 , Z ¹ , Y ³ , n1 , a1 , b1 and n3 is plural, and may be the same or different.

In the formula (25), examples of the organic group having a valence of (1+m13+m14) represented by R ¹⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. a group of (m13+m14) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl a 9-fluorenyl group, wherein at least one of the hydrogen atoms is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed (m13+m14) of hydrogen atoms. Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like Removal of alkoxy groups having 1 to 50 carbon atoms with or without a substituent (m13+m14) Atoms group; a substituted amino group having the carbon-atoms removed (m13 + m14) hydrogen atoms of the group; the silicon based substituent group removed (m13 + m14) hydrogen atoms by a group having a carbon-atoms. From the viewpoint of easiness of synthesis of a raw material monomer, a group of (m13+m14) hydrogen atoms is removed from the aryl group by a group in which (m13+m14) hydrogen atoms are removed by an alkyl group, and is removed by an alkoxy group ( The base of m13+m14) hydrogen atoms is preferred.

The structural unit represented by the formula (25) includes the following structural units.

(Example of a structural unit represented by the formula (15))

The structural unit represented by the formula (15) is preferably a structural unit represented by the formula (26) or a structural unit represented by the formula (27) from the viewpoint of obtaining electron transport properties of the ionic polymer. 27) The structural unit shown is more preferred.

In the formula (26), R ¹⁶ is an organic group having a (1+m16+m17) valence, and R ¹⁷ is a monovalent organic group, and Q ² , Q ³ , Y ² , m2, Z ² , Y ³ , and n2 A, b2, and n3 are the same meanings as described above, and m16 and m17 each independently represent an integer of 1 or more. Each of Q ² , Q ³ , Y ² , m2, Z ² , Y ³ , n2, a2, b2, and n3 is plural, and may be the same or different.

In the formula (26), as R (1 + m16 + m17) valent organic group shown by ^16, for example, include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, first Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. a group of (m16+m17) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl a 9-fluorenyl group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed (m16+m17) of hydrogen atoms. Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like Removal of alkoxy groups having 1 to 50 carbon atoms with or without a substituent (m16+m17) Atoms group; a substituted amino group having the carbon-atoms removed (m16 + m17) hydrogen atoms of the group; the group of silicon-based removing (m16 + m17) group hydrogen atoms replaced by atoms having the carbon-containing. From the viewpoint of easiness of synthesis of the raw material monomers, a group of (m16+m17) hydrogen atoms is removed from the aryl group by a group in which (m16+m17) hydrogen atoms are removed by an alkyl group, and is removed by an alkoxy group ( The base of m16+m17) hydrogen atoms 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 second butyl group, and a third group. a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent in which at least one hydrogen atom of the group is substituted with a substituent or the like An alkyl group having 1 to 20 carbon atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, and at least one hydrogen atom among these groups is substituted An aryl group having 6 to 30 carbon atoms with or without a substituent; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a decyloxy group, or the like. Dodecanoyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclododecyloxy, norbornyloxy, adamantyloxy An alkoxy group having 1 to 50 carbon atoms with or without a substituent substituted with a substituent such as at least one hydrogen atom in the group; an amine group having a substituent containing a carbon atom; having a carbon group The thiol group of the substituent of an atom. From the viewpoint of easiness of synthesis of the raw material monomers, an alkyl group, an aryl group or an alkoxy group is preferred.

The structural unit represented by the formula (26) includes the following structural units.

In the formula (27), R ¹⁶ represents an organic group having a (1+m18+m19) valence, and Q ² , Q ³ , Y ² , m2, Z ² , Y ³ , n2, a2, b2 and n3 are the same as defined above. In the meantime, m18 and m19 each independently represent an integer of 1 or more. Each of R ¹⁶ , m18 , m19 , Q ² , Q ³ , Y ² , m2 , Z ² , Y ³ , n2, a2, b2, and n3 is plural, and may be the same or different.

In the formula (27), as R (1 + m18 + m19) valent organic group shown by ^16, for example, include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, first Dibutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, a group in which at least one hydrogen atom is substituted with a substituent, etc. A group of (m18+m19) hydrogen atoms removed by an alkyl group having 1 to 20 carbon atoms with or without a substituent; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl a 9-fluorenyl group in which at least one hydrogen atom in the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent is removed (m18+m19). Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy a group, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom is substituted with a substituent, or the like Removal of alkoxy groups having 1 to 50 carbon atoms with or without a substituent (m18+m19) a group of atoms; a group having (m18+m19) hydrogen atoms removed from an amine group having a substituent having a carbon atom; a group having (m18+m19) hydrogen atoms removed from a thiol group having a substituent having a carbon atom, From the viewpoint of easiness of synthesis of a raw material monomer, a group in which a hydrogen atom is removed from an alkyl group (m18+m19), and a group of (m18+m19) hydrogen atoms is removed from the aryl group, and is removed by an alkoxy group (m18) The base of +m19) hydrogen atoms is preferred.

The structural unit represented by the formula (27) includes the following structural units.

In terms of the durability of the ionic polymer which can be obtained, the structural unit represented by the formula (15) is preferably a structural unit represented by the formula (28).

In the formula (28), R ¹⁸ is an organic group representing a valence of (1+m20+m21), and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2 and n3 are represented by Similarly, m20, m21, and m22 are integers each representing 1 or more independently. When each of R ¹⁸ , m20 , m21 , Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2 and n3 is plural, it may be the same or different.

In the formula (28), the organic group of the (1+m20+m21) valence represented by R ¹⁸ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted with a substituent, or the like Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove (m20+m21) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9 - mercapto group, at least one hydrogen atom among these groups, a group substituted with a substituent, etc., with or without a substituent, an aryl group having 6 to 30 carbon atoms, which removes (m20 + m21) hydrogen atoms Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, a cyclohexyloxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom among the groups, or the like The alkoxy group having 1 to 50 carbon atoms of the substituent removes (m20+m21) hydrogen atoms Removing a group of (m20+m21) hydrogen atoms from an amine group having a substituent containing a carbon atom; removing a group of (m20+m21) hydrogen atoms from a mercapto group having a substituent containing a carbon atom, but synthesizing In terms of easiness of the raw material monomer, it is preferably a group of (m20+m21) hydrogen atoms removed from the alkyl group, a (m20+m21) hydrogen atom group removed from the aryl group, and removed from the alkoxy group (m20+ M21) a group of hydrogen atoms.

The structural unit represented by the formula (28) includes the following structural units.

(Example of structural unit represented by the formula (17))

As far as the electron transportability of the ionic polymer is available, The structural unit indicated by (17) is preferably a structural unit represented by the formula (29).

In the formula (29), R ¹⁹ is an organic group representing a single bond or a (1+m23) valence, and R ²⁰ is an organic group representing a single bond or a (1+m24) valence, Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are the same as described above, and m23 and m24 are each independently an integer representing 1 or more. However, when R ¹⁹ is a single bond, m23 represents 1 and R ²⁰ represents a single bond, and m24 represents 1. When a plurality of Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are plural, they may be the same or different.

In the formula (29), the organic group of the (1+m23) valence represented by R ¹⁹ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a group such as a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in the group is substituted with a substituent or the like The unsubstituted alkyl group having 1 to 20 carbon atoms removes (m23) hydrogen atom groups; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl The aryl group having 6 to 30 carbon atoms with or without a substituent of at least one hydrogen atom in the group, which is substituted with a substituent, or the like, removes (m23) a hydrogen atom; , ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Alkoxy group having 1 to 50 carbon atoms to remove (m23) hydrogen atom groups; The amine group having a substituent containing a carbon atom removes a group of (m23) hydrogen atoms; the group of (m23) hydrogen atoms is removed from a mercapto group having a substituent having a carbon atom, but the ease of synthesizing a raw material monomer In general, it is preferably a group which removes (m23) hydrogen atoms from the alkyl group, a group which removes (m23) hydrogen atoms from the aryl group, and a group which removes (m23) hydrogen atoms from the alkoxy group.

In the formula (29), the organic group of the (1+m24) valence represented by R ²⁰ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted by a substituent, or the like An unsubstituted alkyl group having 1 to 20 carbon atoms to remove (m24) hydrogen atom groups; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl a aryl group having 6 to 30 carbon atoms with or without a substituent substituted by a substituent, such as a group substituted with a substituent, or the like, wherein (m24) a hydrogen atom; , ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Alkoxy group having 1 to 50 carbon atoms to remove (m24) hydrogen atom groups; The amine group having a substituent containing a carbon atom removes a group of (m24) hydrogen atoms; the base of a (m24) hydrogen atom is removed from a mercapto group having a substituent having a carbon atom, but the ease of synthesizing a raw material monomer In general, it is preferably a group in which (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 structural unit represented by the formula (29) includes the following structural units.

In terms of the durability of the ionic polymer which can be obtained, the structural unit represented by the formula (17) is preferably a structural unit represented by the formula (30).

In the formula (30), R ²¹ is an organic group representing a single bond or a (1+m25) valence, and R ²² is an organic group representing a single bond or a (1+m26) valence, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are the same as described above. M25 and m26 are integers each representing 1 or more independently. However, when R ²¹ is a single bond, m25 represents 1 and R ²² represents a single bond, and m26 represents 1. M27 and m28 are integers each representing 1 or more independently. When m25, m26, R ²¹ , R ²² , Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are each plural, they may be the same, Can be different.

In the formula (30), the (1+m25)-valent organic group represented by R ²¹ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a third butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted with a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove (m25) hydrogen atom groups; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorene a group in which at least one hydrogen atom from the group is substituted with a substituent or the like, and an aryl group having 6 to 30 carbon atoms with or without a substituent removes (m25) a hydrogen atom; Base, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Alkoxy group having 1 to 50 carbon atoms to remove (m25) hydrogen atom groups Removing (m25) hydrogen atom groups from an amine group having a substituent containing a carbon atom; removing (m25) hydrogen atom groups from a mercapto group having a carbon atom-containing substituent, but synthesizing a raw material monomer In terms of easiness, it is preferably a group which removes (m25) hydrogen atoms from the alkyl group, a group which removes (m25) hydrogen atoms from the aryl group, and a group which removes (m25) hydrogen atoms from the alkoxy group.

In the formula (30), the organic group of the (1+m26) valence represented by R ²² may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted by a substituent, or the like (m26) groups of hydrogen atoms in an unsubstituted alkyl group having 1 to 20 carbon atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-anthracene a group having at least one hydrogen atom from the group substituted with a substituent, such as a group substituted with a substituent or the like, having an aryl group having 6 to 30 carbon atoms, having a substituent of (m26) a hydrogen atom; Base, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Removal of (m26) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms Removing (m26) hydrogen atom groups from an amine group having a substituent containing a carbon atom; removing (m26) hydrogen atom groups from a mercapto group having a carbon atom-containing substituent, but synthesizing a raw material monomer In terms of easiness, it is preferably a group in which (m26) hydrogen atoms are removed from the alkyl group, (m26) hydrogen atoms are removed from the aryl group, and (m26) hydrogen atoms are removed from the alkoxy group.

The structural unit represented by the formula (30) includes the following structural units.

(Example of structural unit represented by the formula (20))

The electron transporting property of the ionic polymer which can be obtained is preferably a structural unit represented by the formula (31).

In the formula (31), R ²³ is an organic group representing a single bond or a (1+m29) valence, and R ²⁴ is an organic group representing a single bond or a (1+m30) valence, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 are the same as described above. M29 and m30 are integers each independently representing 1 or more. However, when R ²³ is a single bond, m29 represents 1 and R ²⁴ represents a single bond, and m30 represents 1. When each of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 is plural, it may be the same or different.

In the formula (31), the organic group of the (1+m29) valence represented by R ²³ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a third butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted with a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove (m29) hydrogen atom groups; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorene A group of (m29) hydrogen atoms is removed from an aryl group having 6 to 30 carbon atoms with or without a substituent, such as a group substituted with a substituent, such as a group substituted with a substituent; Oxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyl An oxy group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom among the groups, or the like, substituted or not Removal of (m29) hydrogen atoms from alkoxy groups having 1 to 50 carbon atoms a group of (m29) hydrogen atoms removed from an amine group having a substituent containing a carbon atom; a base of (m29) hydrogen atoms is removed from a mercapto group having a substituent having a carbon atom, but a synthetic raw material is used. In terms of the easiness of the body, it is preferably a group which removes (m29) hydrogen atoms from the alkyl group, a group which removes (m29) hydrogen atoms from the aryl group, and a group which removes (m29) hydrogen atoms from the alkoxy group.

In the formula (31), the (1+m30)-valent organic group represented by R ²⁴ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a third butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted with a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove (m30) hydrogen atom groups; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorene a group having at least one hydrogen atom from the group substituted with a substituent, such as a group substituted with a substituent or the like, having an aryl group having 6 to 30 carbon atoms, having a substituent of (m30) a hydrogen atom; Base, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Alkoxy group having 1 to 50 carbon atoms to remove (m30) hydrogen atom groups Removing (m30) hydrogen atom groups from an amine group having a substituent containing a carbon atom; removing (m30) hydrogen atom groups from a mercapto group having a carbon atom-containing substituent, but synthesizing a raw material monomer In terms of easiness, it is preferably a group in which (m30) hydrogen atoms are removed from the alkyl group, (m30) hydrogen atoms are removed from the aryl group, and (m30) hydrogen atoms are removed from the alkoxy group.

The structural unit represented by the formula (31) includes the following structural units.

In terms of the durability of the ionic polymer which can be obtained, the structural unit represented by the formula (20) is preferably a structural unit represented by the formula (32).

In the formula (32), R ²⁵ is an organic group representing a single bond or a (1+m31) valence, and R ²⁶ is an organic group representing a single bond or a (1+m32) valence, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 are the same as described above. M31 and m32 are integers each representing 1 or more independently. However, when R ²⁵ is a single bond, m31 represents 1 and R ²⁶ represents a single bond, and m32 represents 1. M33 and m34 are integers each independently representing 1 or more. When m31, m32, R ²⁵ , R ²⁶ , Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 are each plural, they may be the same, Can be different.

In the formula (32), the organic group of the (1+m31) valence represented by R ²⁵ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a second butyl group. a tributyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted by a substituent, or the like An unsubstituted alkyl group having 1 to 20 carbon atoms which removes (m31) a hydrogen atom; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorene a group having at least one hydrogen atom from the group substituted with a substituent, such as a group substituted with a substituent or the like, having an aryl group having 6 to 30 carbon atoms, having a substituent of (m31) a hydrogen atom; Base, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Alkoxy groups having 1 to 50 carbon atoms to remove (m31) hydrogen atom groups; Removal of (m31) hydrogen atom groups from an amine group having a substituent containing a carbon atom; removal of (m31) hydrogen atom groups from a mercapto group having a substituent having a carbon atom, but it is easy to synthesize a raw material monomer To the extent, it is preferred to remove (m31) hydrogen atom groups from the alkyl group, (m31) hydrogen atom groups from the aryl group, and (m31) hydrogen atom groups from the alkoxy group.

Formula (32), as (1 + m32) the divalent organic group represented by R ^26, although may be for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, a third butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a group in which at least one hydrogen atom among the groups is substituted with a substituent, etc. Or an unsubstituted alkyl group having 1 to 20 carbon atoms to remove (m32) hydrogen atom groups; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-anthracene a group having at least one hydrogen atom from the group substituted with a substituent, such as a group substituted with a substituent or the like, having an aryl group having 6 to 30 carbon atoms, having a substituent of (m32) a hydrogen atom; Base, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, dodecyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group, a cyclodecyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group substituted with at least one hydrogen atom from the group, or the like, with or without a substituent Alkoxy group having 1 to 50 carbon atoms to remove (m32) hydrogen atom groups Removing (m32) hydrogen atom groups from an amine group having a substituent containing a carbon atom; removing (m32) hydrogen atom groups from a mercapto group having a carbon atom-containing substituent, but synthesizing a raw material monomer In terms of easiness, it is preferably a group in which (m32) hydrogen atoms are removed from the alkyl group, (m32) hydrogen atoms are removed from the aryl group, and (m32) hydrogen atoms are removed from the alkoxy group.

The structural unit represented by the formula (32) includes the following structural units.

(other structural units)

The ionic polymer used in the present invention may have one or more structural units represented by the formula (33).

In the formula (33), Ar ⁵ is a divalent aromatic amine group having or without a substituent, or a divalent aromatic amine residue having or without a substituent, and X' is an imido group having or without a substituent. An extended or unsubstituted alkyl group or an ethynyl group with or without a substituent. M35 and m36 are independent of 0 or 1, and at least one of m35 and m36 is 1.

The divalent aromatic group represented by Ar ⁵ in the formula (33) includes a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. Examples of the divalent aromatic hydrocarbon group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, and 1,3,5-three. a monovalent aromatic ring such as a azine ring, a furan ring, a pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, an oxadiazole ring or a thiadiazole ring, and a divalent group obtained by removing two hydrogen atoms; a divalent group obtained by removing two hydrogen atoms from two or more condensed condensed polycyclic aromatic rings selected from the group consisting of the monocyclic aromatic rings; selected from the monocyclic aromatic ring and the condensation Two or more aromatic rings in a group formed by a polycyclic aromatic ring, a divalent group obtained by removing a single hydrogen atom by a single ring, a vinyl group or an ethynyl group; a polycyclic aromatic ring or two adjacent aromatic rings of the aromatic ring, which are bridged by a bimodal group having a crosslinked bridged polycyclic aromatic ring, such as a methylene group, an ethyl group, a carbonyl group or an imido group. A divalent group after two hydrogen atoms.

The number of the condensed monocyclic aromatic rings in the condensed polycyclic aromatic ring is preferably from 2 to 4, more preferably from 2 to 3, and more preferably 2, in terms of solubility of the ionic polymer. The number of the aromatic rings to be bonded to the above aromatic ring group is preferably from 2 to 4 in terms of solubility, and preferably from 2 to 3. And 2 is better. The number of the aromatic rings bridged in the above-mentioned bridged polycyclic aromatic ring is preferably 2 to 4 in terms of solubility of the ionic polymer, more preferably 2 to 3, and more preferably 2.

The monocyclic aromatic ring may, for example, be a ring represented by the following structures 45 to 60.

The condensed polycyclic aromatic ring may, for example, be a ring represented by the following structures 61 to 80.

Examples of the aromatic ring set include the rings represented by the following structures 81 to 91.

The bridged polycyclic aromatic ring may, for example, be a ring represented by the following structures 92 to 100.

With respect to either or both of the electron acceptability and the hole acceptability of the ionic polymer, the divalent aromatic group represented by Ar ⁵ is preferably from the structures 45 to 60, 61 to 71, 77 to 80, 91, The ring represented by 92, 93 or 96 removes the divalent group after 2 hydrogen atoms, and removes 2 hydrogen atoms from the ring represented by the structure 45 to 50, 59, 60, 77, 80, 91, 92 or 96 The divalent group is preferred.

The above divalent aromatic group may have a substituent. The substituent which is the same as the substituent exemplified in the description of the above Q ¹ (the group represented by the formula (1)) is exemplified.

The divalent aromatic amine residue represented by Ar ⁵ in the formula (33) is a group represented by the formula (34).

In the formula (34), Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ are each a divalent heterocyclic group which independently represents an extended aryl group with or without a substituent or a substituent. Ar ¹⁰ , Ar ¹¹ and Ar ¹² are each a monovalent heterocyclic group which independently or independently represents an aryl group or a substituent. N10 and m37 are independent representations of 0 or 1.

Examples of the substituent which the aryl group, the aryl group, the divalent heterocyclic group, and the monovalent heterocyclic group may have include a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and an aryloxy group. Arylthio, aralkyl, aralkoxy, aralkylthio, alkenyl, alkynyl, aralkenyl, aralkynyl, decyl, decyloxy, decylamino, quinone imine, imine Residue, substituted amino group, substituted fluorenyl group, substituted decyloxy group, substituted thiol group, substituted guanylamino group, cyano group, nitro group, monovalent heterocyclic group, hetero An aryloxy group, a heteroarylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, a heteroaryloxycarbonyl group, a carboxyl group or the like. The substituent may also have a vinyl group, an ethynyl group, a butynyl group, an acrylic group, an acrylate group, an acrylamide group, a methacryl group, a methacrylate group, a methacrylamide group, a vinyl ether group. a group of a vinylamine group, a stanol group, a small member ring (cyclopropyl group, cyclobutyl group, epoxy group, epoxypropyl group, diketene group, cyclothio group, etc.), containing a lactone group, a linoleum A crosslinking group such as a base of a structure of an amine group or a siloxane derivative.

When n1 is 0, the carbon atom in Ar ⁶ may be directly bonded to the carbon atom in Ar ⁸ or may be bonded via a divalent group such as -O- or -S-.

The aryl group or the monovalent heterocyclic group represented by Ar ¹⁰ , Ar ¹¹ or Ar ¹² is the same as the aryl group or the monovalent heterocyclic group exemplified above as the substituent.

Examples of the aryl group represented by Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ include an atomic group obtained by removing two hydrogen atoms bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and a group having a benzene ring. The group having a condensed ring, an independent benzene ring or two or more fused rings is a single bond or a divalent organic group, for example, a group bonded via an alkenyl group such as a vinyl group. The number of carbon atoms of the aryl group is usually from 6 to 60, and preferably from 7 to 48. Specific examples of the aryl group include a phenyl group, a biphenyl group, a C ₁ to C ₁₇ alkoxyphenyl group, a C ₁ to C ₁₇ alkylphenyl group, a 1-naphthyl group, and a 2-stretching group. Naphthyl, 1-extended fluorenyl, 2-extended fluorenyl, 9-extended fluorenyl. The hydrogen atom in the aforementioned aryl group may also be substituted with a fluorine atom. Examples of the fluorine atom-substituted aryl group include a tetrafluorophenylene group and the like. Among the aryl groups, it is preferably a phenyl group, a biphenyl group, a C ₁ to C ₁₂ alkoxyphenyl group, and a C ₁ to C ₁₂ alkyl group.

Examples of the divalent heterocyclic group represented by Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ include an atomic group remaining after removing two hydrogen atoms from the heterocyclic compound. The heterocyclic compound herein refers to an organic compound having a cyclic structure, and the element as a constituent ring is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a germanium atom, An organic compound of a hetero atom such as a selenium atom, a ruthenium atom or an arsenic atom. The divalent heterocyclic group may also have a substituent. The number of carbon atoms of the divalent heterocyclic group is usually from 4 to 60, and preferably from 4 to 20. Further, 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 thiophenediyl group, a C ₁ to C ₁₂ alkylthiophenediyl group, a pyrrole diyl group, a furyl diyl group, a pyridyldiyl group, and a C ₁ to C ₁₂ alkylpyridinediyl group. , pyridazine diyl, pyrimidine diyl, pyrazinediyl, triazinediyl, pyrrolidinyl, piperidinyl, quinolinediyl, isoquinolinediyl, wherein thiophenediyl, C ₁ to C ₁₂ alkyl thiophenediyl, pyridinediyl group and a C ₁ to C ₁₂ alkyl pyridinediyl are preferred.

The ionic polymer containing a divalent aromatic amine residue as a structural unit may have other structural units. Examples of other structural units include an extended aryl group such as a phenylene group and a fluorene group. Further, among these ionic polymers, a compound containing a crosslinking group is preferred.

Meanwhile, as the divalent aromatic amine residue represented by the formula (34), a group in which two hydrogen atoms are removed by an aromatic amine represented by the following structures 101 to 110 can be exemplified.

The aromatic amine represented by the structures 101 to 110 may have a substituent in the range in which a divalent aromatic amine residue can be formed, and examples of the substituent include the same substituents exemplified in the description of the above Q ¹ . Substituents, such as when a plurality of substituents are present, these groups may be the same or different.

In the formula (33), X' is an imido group having or not having a substituent, an extended group having or not having a substituent, and a vinyl group or an ethynyl group having or without a substituent. Examples of the substituent which the imino group, the fluorenyl group or the vinyl group may have include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a t-butyl group. Alkyl group having 1 to 20 carbon atoms such as pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, 3,7-dimethyloctyl, lauryl; benzene a aryl group having 6 to 30 carbon atoms, such as a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, etc., if a plurality of substituents are present, such a group may be used. It is the same or different.

In view of the stability of the aforementioned ionic polymer to air, moisture or heat, X' is preferably an imine group, a vinyl group or an ethynyl group.

In terms of electron acceptability and hole acceptability of the ionic polymer, m35 is preferably 1 and m36 is 0.

The structural unit represented by the formula (33) is preferably a structural unit represented by the formula (35) in terms of electron acceptability of the ionic polymer.

In the formula (35), Ar ¹³ is a pyridyldiyl group having or without a substituent, a pyrazinediyl group with or without a substituent, a pyrimidinediyl group with or without a substituent, and a pyridazine II with or without a substituent. A triazinediyl group with or without a substituent.

Examples of the substituent which the pyridinediyl group may have are the same substituents as those exemplified in the description of the above Q ¹ . Where a plurality of substituents are present, such groups may be the same or different.

Examples of the substituent which the pyrazinediyl group may have include the substituents which are the same as the substituents exemplified in the above description of Q ¹ . Where a plurality of substituents are present, such groups may be the same or different.

Examples of the substituent which the pyrimidinediyl group may have include the same substituents as those exemplified in the above description of Q ¹ . Where a plurality of substituents are present, such groups may be the same or different.

Examples of the substituent which the pyridazine diyl group may have are the same substituents as those exemplified in the above description of Q ¹ . Where a plurality of substituents are present, such groups may be the same or different.

Examples of the substituent which the triazinediyl group may have are the same substituents as those exemplified in the above description of Q ¹ . Where a plurality of substituents are present, such groups may be the same or different.

(proportion of structural units)

The luminous efficiency of the organic EL element, the structural unit represented by the formula (13), the structural unit represented by the formula (15), and the structural unit represented by the formula (17) in the ionic polymer used in the present embodiment. The total ratio of the structural units represented by the formula (20) is preferably from 30 to 100 mol% in the total structural unit contained in the ionic polymer, excluding the structural unit of the terminal.

(structural unit at the end)

Further, examples of the structural unit (terminal group) of the terminal of the ionic polymer used in the present invention include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a second. Butyl, tert-butyl, pentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, methoxy, ethoxy, propoxy, isopropoxy , butoxy, isobutoxy, second butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy Base, decyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio , second butylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, sulfonylthio, sulfonylthio, laurel, methoxyphenyl , ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, butoxyphenyl, isobutoxyphenyl, second butoxyphenyl, tert-butoxyphenyl, pentoxyphenyl, hexyloxybenzene Base, cyclohexyloxyphenyl, heptyloxyphenyl, octyloxyphenyl, 2-ethylhexyloxy Phenyl, anthracenyloxy, decyloxyphenyl, 3,7-dimethyloctoxyphenyl, lauric oxyphenyl, methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl , trimethylphenyl, methylethylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl, isopentylphenyl, hexyl Phenyl, heptylphenyl, octylphenyl, nonylphenyl, nonylphenyl, dodecylphenyl, methylamino, dimethylamino, ethylamino, diethylamine Base, propylamino, dipropylamino, isopropylamino, diisopropylamino, butylamino, isobutylamino, second butylamino, tert-butylamino , pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, decylamino, decylamino, 3,7-dimethyl octyl Amino, laurylamine, cyclopentylamino, dicyclopentylamino, cyclohexylamino, dicyclohexylamino, bis(trifluoromethyl)amino, phenylamino, diphenyl amino group, (C ₁ to C ₁₂ alkoxyphenyl) amino, di (C ₁ to C ₁₂ alkoxyphenyl) amino, di (C ₁ to C ₁₂ alkyl Phenyl)amino, 1-naphthylamino, 2-naphthylamino, pentafluorophenylamino, pyridylamino, pyridazinylamino, pyrimidinylamino, pyrazinylamino, tri Azinylamino, (phenyl-C ₁ to C ₁₂ alkyl)amino, (C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl) amine, (C ₁ to C ₁₂ alkyl) Phenyl-C ₁ to C ₁₂ alkyl)amino group, di(C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl)amino group, di(C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl)amino, 1-naphthyl-C ₁ to C ₁₂ alkylamino, 2-naphthyl-C ₁ to C ₁₂ alkylamino, trimethyldecyl, triethylhydrazine , tripropyl decyl, triisopropyl decyl, isopropyl dimethyl fluorenyl, isopropyl diethyl decyl, tert-butyl dimethyl decyl, pentyl dimethyl fluorenyl , hexyl dimethyl fluorenyl, heptyl dimethyl fluorenyl, octyl dimethyl fluorenyl, 2-ethylhexyl dimethyl fluorenyl, decyl dimethyl fluorenyl, decyl dimethyl fluorenyl , 3,7-dimethyloctyldimethylhydrazine, lauryl dimethyl fluorenyl, (phenyl-C ₁ to C ₁₂ alkyl) fluorenyl, (C ₁ to C ₁₂ alkoxyphenyl- a C ₁ to C ₁₂ alkyl) silicon based, (C ₁ to C ₁₂ alkylphenyl group -C ₁ to C ₁₂ alkyl) silicon , (1-naphthyl -C ₁ to C ₁₂ alkyl) of silicon-based, (2-naphthyl -C ₁ to C ₁₂ alkyl) silicon based, (phenyl -C ₁ to C ₁₂ alkyl) dimethyl Mercapto, triphenylsulfonyl, tris(p-xylphenyl)indenyl, tritylmethylindenyl, diphenylmethylindenyl, tert-butyldiphenylindenyl, dimethylphenyl Mercapto, thienyl, C ₁ to C ₁₂ alkylthiophenyl, pyrrolyl, furyl, pyridyl, C ₁ to C ₁₂ alkyl pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, Pyrrolinyl group, piperidinyl group, quinolyl group, isoquinolyl group, hydroxyl group, thiol group, fluorine atom, chlorine atom, bromine atom, iodine atom, and the like. Where there are a plurality of structural units of the foregoing ends, such structural units may be the same or different.

(Characteristics of ionic polymers)

The ionic polymer used in the present embodiment is preferably a conjugated compound. The ionic polymer used in the present invention is a conjugated compound, and means that the ionic polymer contains a single bond in the main chain and has a plurality of bonds (for example, a double bond or a hydrazone bond) or a nitrogen atom. The field of non-shared electron pairs such as oxygen atoms. When the ionic polymer is a conjugated compound, in terms of electron transportability of the conjugated compound, it is a non-consensus electron having a plurality of bonds or a nitrogen atom or an oxygen atom in a single bond. The number of atoms in the main chain in the pair) / (the number of all atoms in the main chain)} × 100% calculated ratio is preferably 50% or more, and more preferably 60% or more, more than 70% Preferably, it is preferably 80% or more, and more preferably 90% or more.

Meanwhile, the ionic polymer used in the present embodiment is preferably a polymer compound, and a conjugated polymer compound is preferred. Here, the polymer compound refers to a compound having a number average molecular weight of 1 × 10 ³ or more in terms of polystyrene. Meanwhile, the ionic polymer used in the present invention is a conjugated polymer compound, and the ionic polymer is a conjugated compound and is a polymer compound.

The number average molecular weight of the ionic polymer-converted polystyrene is preferably from 1 × 10 ³ to 1 × 10 ⁸ and is 2 × from the viewpoint of coating the film forming property of the ionic polymer used in the embodiment. 10 ³ to 1 × 10 ^{7 is} preferable, more preferably 3 × 10 ³ to 1 × 10 ⁷ , and more preferably 5 × 10 ³ to 1 × 10 ⁷ . Meanwhile, in terms of the purity of the ionic polymer, the number average molecular weight of the converted polystyrene is preferably from 1 × 10 ³ to 5 × 10 ⁷ , and preferably from 1 × 10 ³ to 1 × 10 ⁷ , and is 1 ×10 ³ to 5×10 ^{6 is more} preferable. Meanwhile, in terms of solubility of the ionic polymer, the number average molecular weight of the converted polystyrene is preferably from 1 × 10 ³ to 5 × 10 ⁵ , and preferably from 1 × 10 ³ to 5 × 10 ⁴ , 1 × 10 ³ to 3 × 10 ^{3 is more} preferable. The number average molecular weight and the weight average molecular weight of the ionic polymer-converted polystyrene used in the present invention can be determined, for example, by a gel permeation chromatography (GPC).

In the purity of the ionic polymer used in the present embodiment, the number of the entire structural units (that is, the degree of polymerization) contained in the ionic polymer is preferably 1 or more and 20 or less, and the terminal structure unit is removed. It is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

In terms of electron acceptability and hole acceptability of the ionic polymer used in the present embodiment, the orbital energy of the lowest non-occupied molecular orbital (LUMO) of the ionic polymer is preferably -5.0 eV or more - 2.0 eV. Hereinafter, it is preferably -4.5 eV or more to 2.0 eV or less. Meanwhile, from the same viewpoint, the orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer is preferably -6.0 eV or more to 3.0 eV or less, and is -5.5 eV or more to 3.0 eV or less. Preferably. However, the orbital energy of HOMO is less than the orbital energy of LUMO. Further, 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 energy as the orbital energy. On the other hand, the orbital energy of the lowest non-occupied molecular orbital (LUMO) of the ionic polymer is the difference between the HOMO and the LUMO, and the sum of the value and the measured ionized potential energy is used as the orbital energy. Got it. When measuring the ionization potential energy, a photoelectron spectroscopic device can be used. At the same time, the difference between the HOMO and the LUMO is determined by measuring the absorption spectrum of the ionic polymer using an ultraviolet light, a visible light, a near-infrared spectrophotometer, and the absorption end.

Further, when the polymer used in the present embodiment is used in an electric field light-emitting device, it is preferably a non-light-emitting property. Here, a certain polymer is substantially non-luminescent, and is as follows. First, an electroluminescent element A having a layer containing a certain polymer is produced. On the other hand, an electroluminescent element 2 having no polymer-containing layer was produced. The electric field light-emitting element A has a polymer-containing layer, and the electric field light-emitting element 2 does not have a polymer-containing layer, and only this point is different from the electric field light-emitting element A and the electric field light-emitting element 2. Next, after the forward voltage of a voltage of 10 V was applied to the electric field light-emitting element A and the electric field light-emitting element 2, the emission spectrum was measured. In the luminescence spectrum obtained by the electric field light-emitting element 2, the wavelength λ at which the maximum peak can be given is obtained. The luminescence intensity of the wavelength λ is set to 1, and the luminescence spectrum obtained by the electric field light-emitting element 2 is normalized, and the normalized luminescence amount S _{0 is} calculated after the wavelength is integrated. On the other hand, the luminous intensity of the wavelength λ is set to 1, and the luminescence spectrum obtained by the electric field light-emitting element A is normalized, and the normalized luminescence amount S is calculated after the wavelength is integrated. When the value calculated by (SS ₀ ) / S ₀ × 100% is 30% or less, that is, the normalized luminescence amount of the electroluminescent element A having the polymer-containing layer and the electric field luminescence without the polymer-containing layer When the increase in the normalized luminescence amount comparison of the element 2 is 30% or less, the polymer used is a compound which is substantially non-luminescent. The value calculated by (SS ₀ ) / S ₀ × 100% is preferably 15% or less, and preferably 10% or less.

The ionic polymer containing the group represented by the above formula (1) and the group represented by the above formula (3) includes an ionic polymer formed only of the structural unit represented by the formula (23), and is selected from the formula (23). The structural unit and the structure represented by the group 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 are one or more groups in which a group of two hydrogen atoms is removed. The formed ionic polymer, the ionic polymer formed only by the structural unit represented by the formula (24), the structural unit represented by the formula (24), and the structures 45 to 50, 59, 60, 77, 80, 91, An ionic polymer formed by one or more groups in a group formed by removing a base of two hydrogen atoms represented by 92, 96, 101 to 110, and an ionic property formed only by a structural unit represented by the formula (25) a polymer, a structural unit selected from the formula (25), and a group formed by the group represented by the formula 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 from which two hydrogen atoms are removed An ionic polymer formed of one or more kinds of groups in the group, an ionic polymer formed only of a structural unit represented by the formula (29), and a structural unit selected from the formula (29) An ionic polymer formed by one or more groups in the group formed by removing a group of two hydrogen atoms represented by structures 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 An ionic polymer formed only by the structural unit represented by the formula (30), selected from the group consisting of (30) The structural unit and the structure represented by the structure 45 to 50, 59, 60, 77, 80, 91, 92, 96, and 101 to 110 are one or more groups in which a group of two hydrogen atoms is removed. An ionic polymer formed on the basis of the base.

The ionic polymer containing the group represented by the above formula (1) and the group represented by the above formula (3) includes the following polymer compounds. Among these polymer compounds, the ratio of the structural unit on the left side is p mol%, and the ratio of the structural unit on the right side is (100) in the polymer compound represented by the formula "" in the two structural units. -p) Mohr%, these structural units are arranged in a random manner. Meanwhile, in the following formula, n is a degree of polymerization.

(where p is a number representing 15 to 100.)

The ionic polymer containing the group represented by the above formula (2) and the group represented by the above formula (3) includes an ionic polymer formed only of the structural unit represented by the formula (26), and is selected from the formula (26). The structural unit and the structure represented by the group 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 are one or more groups in which a group of two hydrogen atoms is removed. The formed ionic polymer is formed only by the structural unit represented by the formula (27) a daughter polymer, a structural unit selected from the group consisting of the formula (27) and a group represented by the structures 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110, which are formed by removing two hydrogen atoms. An ionic polymer formed by one or more kinds of groups in the group, an ionic polymer formed only of a structural unit represented by the formula (28), a structural unit selected from the formula (28), and structures 45 to 50, An ionic polymer formed by one or more groups in a group formed by removing a group of two hydrogen atoms represented by 59, 60, 77, 80, 91, 92, 96, and 101 to 110, only by the formula ( 31) The ionic polymer formed by the structural unit represented, the structural unit selected from the formula (31), and the group removal represented by the structures 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110 An ionic polymer formed by one or more groups in a group formed by two hydrogen atom groups, an ionic polymer formed only of a structural unit represented by the formula (32), or a selected from the group consisting of the formula (32) Structural unit and structure: 45 to 50, 59, 60, 77, 80, 91, 92, 96, 101 to 110, one or more base groups in a group formed by removing two hydrogen atoms The ionic polymer.

The ionic polymer containing the group represented by the above formula (2) and the group represented by the above formula (3) includes the following polymer compounds. Among these polymer compounds, the ratio of the structural unit on the left side is p mol%, and the ratio of the structural unit on the right side is (100) in the polymer compound represented by the formula "" in the two structural units. -p) Mohr%, these structural units are arranged in a random manner. Meanwhile, in the following formula, n is a degree of polymerization.

(where p is a number representing 15 to 100.)

(Method for producing ionic polymer)

Next, a method for producing the ionic polymer used in the present embodiment will be described. As a suitable method for producing the ionic polymer used in the present embodiment, for example, a compound represented by the following formula (36) is selected as one of the raw materials, and -A _a - in the formula (36) is contained (13) A compound indicating a structural unit, -A _a - is a compound represented by the formula (15), _a compound of -A _a - is a compound represented by the formula (17), and -A _a - is a structure represented by the formula (20) A method in which at least one of the compounds of the unit is used as an essential raw material to carry out condensation polymerization.

Y ⁴ -A _a -Y ⁵ (36)

In the formula (36), A _a is one or more groups including a group selected from the group represented by the formula (1) and a group represented by the formula (2), and one represented by the formula (3) The structural unit of the above base (repeating unit). Y ⁴ and Y ⁵ are each independently a group representing a condensation polymerization.

In the ionic polymer used in the present embodiment, when the structural unit represented by -A _a - in the above formula (36) and the structural unit other than the above -A _a - are simultaneously contained, the above-mentioned - A structural unit other than A _a - and a compound having two substituents relating to condensation polymerization may be coexisted with the compound represented by the above formula (36) to be condensed and polymerized.

The compound represented by the formula (37) can be exemplified as the compound which is used in the case of having such a different structural unit and having two condensable polymerizable substituents. Then, by adding _a compound represented by the above Y ⁴ -A _a -Y ^{5 and} condensing and polymerizing the compound represented by the formula (37), the ionicity used in the present invention having a structural unit represented by -A _b - can be produced. polymer.

Y ⁶ -A _b -Y ⁷ (37)

In the formula (37), A _b represents a structural unit represented by the above formula (33) or a structural unit represented by the formula (35), and Y ⁶ and Y ⁷ each independently represent a group relating to condensation polymerization.

Examples of such a group for the condensation polymerization (Y ⁴ , Y ⁵ , Y ⁶ and Y ⁷ ) include a hydrogen atom, a halogen atom, an alkylsulfonate group, an arylsulfonate group, and an aralkylsulfonic acid. Ester group, borate ester residue, thiomethyl group, phosphonium methyl group, methyl phosphate group, monohalogenated methyl group, -B(OH) ₂ , formamyl group, cyano group, vinyl group and the like.

The halogen atom selected as a group for such condensation polymerization may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Meanwhile, as the alkylsulfonate group selected as the base of the above condensation polymerization, for example, a methanesulfonate group, an ethanesulfonate group, a trifluoromethanesulfonate group, and an arylsulfonate group can be exemplified. For example, a benzenesulfonate group or a p-toluenesulfonate group can be exemplified.

The aralkylsulfonate group selected as the group of the above condensation polymerization may, for example, be a benzylsulfonate group.

In the meantime, the boronic acid ester residue selected as the group of the condensation polymerization may be a group represented by the following formula.

In addition, the thioxanthylmethyl group selected as the group of the condensation polymerization may be a group represented by the following formula.

-CH ₂ S ⁺ Me ₂ E ^- or -CH ₂ S ⁺ Ph ₂ E ^-

(In the formula, E is a halogen atom. Ph is a phenyl group, and the same applies hereinafter.)

In the meantime, the phosphonium methyl group selected as the group of the condensation polymerization may be a group represented by the following formula.

-CH ₂ P ⁺ Ph ₃ E ^-

(wherein E is a halogen atom.)

At the same time, as a base for the aforementioned condensation polymerization, a phosphate ester A is selected. The base may be a group represented by the following formula.

-CH ₂ PO(OR ^d ) ₂

(wherein R ^d represents an alkyl group, an aryl group or an aralkyl group.)

Further, as the monohalogenated methyl group which can be selected as the group relating to the above condensation polymerization, a fluorinated methyl group, a methyl chloride group, a methyl bromide group or a methyl iodide group can be exemplified.

In addition, as a suitable group of the base of the condensation polymerization, the type of the polymerization reaction may vary. However, when a zero-valent nickel complex such as a Yamamoto coupling reaction is used, a halogen atom or an alkane may be mentioned. A sulfonate group, an aryl sulfonate group, an aralkyl sulfonate group. Meanwhile, when a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction is used, an alkylsulfonate group, a halogen atom, a boronic acid ester residue, -B(OH) ₂ or the like can be given. When oxidative polymerization or electrochemical oxidative polymerization using an oxidizing agent is used, a hydrogen atom is mentioned.

In the production of the ionic polymer used in the present embodiment, for example, a compound (monomer) represented by the above formula (36) or formula (37) having a plurality of groups related to condensation polymerization may be used, if necessary. A polymerization method which is dissolved in an organic solvent and which is reacted at a temperature equal to or higher than the melting point of the organic solvent or below the boiling point using an alkali or a suitable catalyst. As such a polymerization method, for example, "Organic Reactions", Vol. 14, pp. 270 to 490, John Wiley & Sons, Inc., 1965, "Organic Syntheses", Collective Vol. 6, pages 407 to 411, John Wiley & Sons, Inc., 1988, Chemical Review, Vol. 95, 2, 457 (1995), J. Organomet. Chem., vol. 576, p. 147 (1999), Macromolecular Chemistry Macromolecular Symposium, A well-known method described in Volume 12, page 229 (1987).

Meanwhile, in the production of the ionic polymer used in the present embodiment, a known condensation polymerization reaction may be employed in association with the group of the condensation polymerization. Examples of such a polymerization reaction include a method in which the monomer is subjected to Suzuki coupling reaction polymerization, a method in which Grignard reaction polymerization is applied, a method in which a nickel-valent complex polymerization is applied, a method in which an oxidizing agent such as FeCl ₃ is used, and electrolysis. A method of oxidative polymerization, a method of decomposing and polymerizing a polymer compound having a suitable debonding group, and the like. Among these polymerization reactions, the method of applying Suzuki coupling reaction polymerization, the method of applying Grignard reaction polymerization, and the method of applying zero-valent nickel complex polymerization are preferred, since the structure of the obtained ionic polymer can be easily Regulation.

The aspect of the preferred production method of the ionic polymer used in the present embodiment is formed by using a group selected from the group consisting of a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an aralkyl sulfonate group. The group in the group is a raw material monomer related to the condensation polymerization, and is a method of producing an ionic polymer by condensation polymerization in the presence of a zero-valent nickel complex. The raw material monomer used in such a method may, for example, be a dihalogenated compound, a bis(alkylsulfonate) compound, a bis(arylsulfonate) compound, a bis(aralkylsulfonate) compound, or a halogen. - alkyl sulfonate compound, halo-aryl sulfonate compound, halo-aralkyl sulfonate compound, alkyl sulfonate-aryl sulfonate compound, alkyl sulfonate - aralkyl sulfonate An acid ester compound and an aryl sulfonate-aralkyl sulfonate compound.

Another aspect of the preferred method for producing the ionic polymer is to use a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aralkyl sulfonate group, -B(OH) ₂ and The group in the group formed by the borate residue serves as a base for the condensation polymerization, and the whole raw material monomer has a halogen atom, an alkylsulfonate group, an arylsulfonate group, and an aralkylsulfonate group. The ratio of the total number of moles (J) to the total (K) of the molar number of the -B(OH) ₂ and the borate residue (K) is a substantial one (usually K/J is 0.7 to A method for producing an ionic polymer by condensing and polymerizing a raw material monomer in the range of 1.2 in the presence of a nickel catalyst or a palladium catalyst.

The organic solvent may be used depending on the compound or reaction to be used. However, it is generally preferred to use an organic solvent which is sufficiently deoxidized to suppress the formation of side reactions. In the production of an ionic polymer, it is preferred to carry out the reaction under an inert gas atmosphere using such an organic solvent. However, there is no such limitation in the reaction in the two-phase system with water such as the Suzuki coupling reaction.

Examples of such an organic solvent include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; carbon tetrachloride and chloroform; Halogenated saturated hydrocarbons such as dichloromethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane; chlorobenzene, dichlorobenzene, three Halogenated unsaturated hydrocarbons such as chlorobenzene; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and butanol; carboxylic acids such as formic acid (formic acid), acetic acid, and propionic acid; dimethyl ether, diethyl ether, Ethers such as methyl-tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane; trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine, Amines such as pyridine; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylmorpholine oxide . These organic solvents may be used singly or in combination of two or more. At the same time, in this organic Among the solvents, from the viewpoint of the reaction, ethers are preferred, and tetrahydrofuran and diethyl ether are more preferred. From the viewpoint of the reaction rate, it is preferably toluene or xylene.

As for the production of the aforementioned ionic polymer, it is preferred to add a base or a suitable catalyst to react the raw material monomers. Such a base or a catalyst may be selected in accordance with the polymerization method employed. As such a base or a catalyst, a catalyst which can be sufficiently dissolved in a solvent used in the reaction is preferred. In the meantime, as a method of mixing the above-mentioned alkali or a catalyst, a solution in which a base or a catalyst is slowly added while stirring a reaction liquid in an inert gas atmosphere such as hydrogen or nitrogen may be exemplified, or the reaction liquid may be slowly added to a base or The method in the solution of the catalyst.

In the ionic polymer used in the present embodiment, the polymerizable group may remain in the terminal group as it is, and the light-emitting characteristics or lifetime characteristics of the obtained light-emitting element may be lowered. Therefore, the terminal group may be protected by a stable base. When the ionic polymer used in the present invention is a conjugated compound when the terminal group is protected by such a stable group, the terminal group preferably has a conjugated bond which is continuous with the conjugated structure of the main chain of the ionic polymer. The structure of the terminal group may, for example, be a structure in which it is bonded to an aryl group or a heterocyclic group via a carbon-carbon bond. A substituent such as a monovalent aromatic compound group represented by a structural formula of 10 in JP-A-H09-45478 is exemplified.

As another suitable method for producing an ionic polymer having a structural unit containing a group represented by the formula (1), an ionic polymer having no cation is polymerized in the first step, and the second step is carried out in the second step. A method of producing an ionic polymer containing a cation by an ionic polymer. As a method of polymerizing the ionic polymer having no cation in the first step, the former may be mentioned. The condensation polymerization described. The second step includes a hydrolysis reaction using a metal hydroxide, an alkyl ammonium hydroxide or the like.

As another suitable method for producing an ionic polymer having a structural unit containing a group represented by the formula (2), an ionic polymer having no ions is polymerized in the first step, and the second step is carried out in the second step. A method of producing an ion-containing ionic polymer from an ionic polymer. As a method of polymerizing the ionic polymer having no ions in the first step, the above condensation polymerization reaction can be mentioned. The second step includes a quaternary ammonium salt reaction using an amine having a halogenated alkyl group, a halogen removal reaction using SbF ₅ , and the like.

Since the ionic polymer used in the present embodiment is excellent in charge injection property and transport property, an element having high luminance light emission can be obtained.

As a method of forming the layer containing the ionic polymer, for example, a method of forming a film using a solution containing an ionic polymer can be mentioned.

Examples of the solvent used for film formation from such a solution include alcohols, ethers, esters, nitrile compounds, nitro compounds, halogenated alkyls, halogenated aryls, thiols, sulfides, and the like. Among solvents (other than water) such as an anthracene, a thioketone, a guanamine or a carboxylic acid, a solvent having a solubility parameter of 9.3 or more is preferred. Examples of the solvent (values in the respective brackets are values indicating the solubility parameter of each solvent) include methanol (12.9), ethanol (11.2), 2-propanol (11.5), and 1-butanol (9.9). , butanol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7), N,N-dimethylformamide (11.5), dimethyl hydrazine (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), dioxins Alkane (9.8), propyl carbonate (13.3), pyridine (10.4), carbon disulfide (10.0) and a mixed solvent of such solvents. Here, when describing a mixed solvent in which two kinds of solvents (solvent 1 and solvent 2) are mixed, the solubility parameter (δ _m ) of the mixed solvent is δ _m = δ ₁ × φ ₁ + δ ₂ × φ ₂ The value obtained (δ ₁ is the solubility parameter of solvent 1, φ ₁ is the volume fraction of solvent 1, δ ₂ is the solubility parameter of solvent 2, and φ ₂ is the volume fraction of solvent 2.)

The film thickness of the electron injecting layer may be different depending on the ionic polymer to be used. Therefore, it is only necessary to select a driving voltage and a luminous efficiency to be appropriate values, but it is necessary to have a thickness which does not cause pinholes. . The film thickness is preferably from 1 nm to 1 μm in terms of the driving voltage of the element, and is preferably from 2 nm to 500 nm, more preferably from 2 nm to 200 nm. The film thickness is preferably from 5 nm to 1 μm in terms of protecting the light-emitting layer.

<cathode>

As the material of the cathode, a material having high conductivity is preferable. In the organic EL element of the composition which is taken up by the anode side, the material as the cathode is preferably a material having a high visible light reflectance so that light emitted from the light-emitting layer can be reflected from the cathode to the anode side. As the cathode, a monomer of gold, silver, platinum, copper, aluminum, manganese, titanium, cobalt, nickel, tungsten, or tin, or an alloy containing one or more kinds, or a graphite or graphite intercalation compound or the like can be used. At the same time, a conductive metal oxide, a conductive resin, a mixture of a resin and a conductive filler, or the like may be used as the cathode. Specific examples of the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO. Examples of the conductive resin include 3,4-polyethyldioxythiophene/polystyrene sulfonate. Acid, etc.

When a film formed of a resin and a conductive filler is used, a conductive resin can be used for the resin. At the same time, metal particles or conductive wires can be used. As a conductive filler. Au, Ag, Al, or the like can be used as the conductive filler. Further, the cathode may be composed of a laminate of two or more layers.

The film thickness of the cathode is a suitable design after considering the properties sought for, the ease of engineering, and the like, 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 lamination method of hot-press plating a metal thin film. Meanwhile, as a method of producing the cathode, when an ink having a conductive filler and a resin dispersed in a dispersion medium is used, a coating method can be used.

[Examples] <Production of Organic EL Element>

An organic EL element having a laminated structure shown in Fig. 4 was produced on a glass substrate.

A glass substrate on which an ITO film has been formed is prepared. The ITO film corresponds to the first electrode functioning as an anode. The ITO film was formed by sputtering and had a thickness of 50 nm.

Next, a suspension of the polymer compound A was applied onto an ITO thin film by a spin coating method in the air to form a coating film for a hole injection layer having a thickness of 60 nm. The film was dried at 170 ° C for 15 minutes on a heater to form a hole injection layer.

Next, the polymer compound B was dissolved in xylene at a concentration of 0.8% by weight, and the xylene solution was applied onto the hole injection layer by a spin coating method in the air to form a hole transport layer having a film thickness of 15 nm. Coating film. Then, under the pressure of about atmospheric pressure, the oxygen concentration and the water concentration are respectively regulated. In a nitrogen atmosphere having a volume ratio of 10 ppm or less, the coating film was dried at 180 ° C for 60 minutes to obtain a hole transport layer.

Next, the polymer light-emitting material C capable of emitting red light is dissolved in a concentration of 1.6% by weight of xylene, and the xylene solution is applied to the hole transport layer by spin coating in the atmosphere to form a film thickness of 70 nm. The luminescent layer is coated with a film. Then, under a pressure of about atmospheric pressure, the oxygen concentration and the water concentration were respectively adjusted in a nitrogen atmosphere having a volume ratio of 10 ppm or less, and the coating film was dried at 130 ° C for 10 minutes to obtain a light-emitting layer capable of emitting red light.

Next, the conjugated polymer compound 1 obtained in the experimental example 1 described later was dissolved in methanol at a concentration of 0.2% by weight, and the methanol solution was applied onto the light-emitting layer by a spin coating method in the air to form an electron having a film thickness of 10 nm. A coating film is used for the injection layer. Then, the coating film was dried at 130 ° C for 10 minutes in the atmosphere to obtain an electron injecting layer.

Next, in a state where the pressure was reduced to 1.0 × 10 ^-4 Pa, aluminum was vapor-deposited on the electron injecting layer to about 8 nm, and then a take-out electrode formed of an aluminum thin film was formed. Moreover, this aluminum is aluminum which is generally used as a cathode material.

The substrate on which the electrode was taken out was taken out in the air, the conjugated polymer compound 1 was dissolved in methanol having a concentration of 0.2% by weight, and the methanol solution was applied onto the electrode by spin coating in the air to form a film thickness. A coating film for a 10 nm electron injecting layer. Then, the coating film was dried at 130 ° C for 10 minutes in the atmosphere to obtain an electron injecting layer.

Next, the polymer light-emitting material D capable of emitting white light was dissolved in 1.3% by weight of xylene, and the xylene solution was applied onto the electron injecting layer by a spin coating method in the atmosphere to form a film having a film thickness of 70 nm. Coating with luminescent layer membrane. Then, under a pressure of about atmospheric pressure, the oxygen concentration and the water concentration were respectively adjusted in a nitrogen atmosphere having a volume ratio of 10 ppm or less, and the coating film was dried at 130 ° C for 10 minutes to obtain a light-emitting layer capable of emitting white light.

Next, the polymer compound B was dissolved in xylene at a concentration of 0.8% by weight, and the xylene solution was applied onto the light-emitting layer by a spin coating method in the air to form a coating film for a hole transport layer having a film thickness of 15 nm. . Next, the oxygen concentration and the water concentration were respectively adjusted in a nitrogen atmosphere having a volume ratio of 10 ppm or less, and the coating film was dried at 180 ° C for 60 minutes to obtain a hole transport layer.

Next, in a state where the pressure is reduced to 1.0 × 10 ^-4 Pa, a molybdenum oxide is deposited on the hole transporting layer to a thickness of about 30 nm, and then a hole injecting layer formed of molybdenum oxide is obtained.

Next, in a state where the pressure is reduced to 1.0 × 10 ^-4 Pa, gold is vapor-deposited on the hole injection layer for about 60 nm, and then a second electrode made of gold is obtained. This second electrode corresponds to the anode.

After the formation of the second electrode, the glass substrate for sealing is bonded via a bonding material to seal the organic EL element.

[Confirmation of lighting status]

The light emission of the organic EL element produced in the examples was confirmed. After the first electrode, the second electrode, and the extraction electrode are respectively connected to the driving circuit, voltages V1 and V2 are independently applied between the first electrode and the extraction electrode and between the extraction electrode and the second electrode. Further, as the luminance of the light emitted from the organic EL element (the light in which the red light and the white light are superimposed) is 1,000 cd/m ² , V1 and V2 are variously set, and the chromaticity in each applied voltage is measured. .

The measurement results are shown in the CIE chromaticity coordinates of Fig. 6. As shown in Fig. 6, it is confirmed that the illuminating color can be adjusted when the brightness is constant by various adjustments of V1 and V2. That is, it is confirmed that the intensity of light emitted by the light-emitting layer that emits white light and the light-emitting layer that emits red light can be independently regulated.

Next, various ionic polymers produced by the ionic polymer or the like used in the above examples will be described.

[Reference Example 1]

2,7-Dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-indole ( Synthesis of Compound A)

2,7-dibromo-9-indole (52.5 g), ethyl salicylate (154.8 g) and thiol acetic acid (1.4 g) were placed in a 300 mL flask, and the atmosphere in the flask was replaced with nitrogen. (Here, in the flask, the atmosphere gas in the flask was replaced with nitrogen gas, and it was briefly replaced with nitrogen gas.). Therein, methanesulfonic acid (630 mL) was added, and the mixture was stirred at 75 ° C overnight. After the mixture was allowed to cool, it was added to ice water and stirred for 1 hour. The resulting solid was separated by filtration and washed with heated acetonitrile. The solid after washing was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution, followed by filtration. The obtained 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. After the resulting mixture was allowed to cool to room temperature, ice water was added and stirred for 1 hour. Chloroform (300 mL) was added to the reaction mixture for liquid separation extraction. After concentrating the solution, 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2- [2-(2-Methoxyethoxy)ethoxy]ethoxy]phenyl]-indole (Compound A) (51.2 g).

[Reference Example 2]

2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-bis[3-ethoxycarbonyl- Synthesis of 4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-indole (Compound B)

Under the nitrogen atmosphere, (Compound A) (15g), bis(pinacol ester) diboron (8.9g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (II) Mixing dichloromethane complex (0.8g), 1,1'-bis(diphenylphosphino)ferrocene (0.5g), potassium acetate (9.4g), dioxane (400mL), heated to After 110 ° C, it was heated to reflux for 10 hours. After allowing to cool, the reaction liquid was filtered, and the filtrate was concentrated under reduced pressure. The reaction mixture was washed 3 times with methanol. The precipitate was dissolved in toluene, activated carbon was added to the solution, and stirred. Then, filtration and separation are carried out, and the filtrate is concentrated under reduced pressure to obtain 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- -9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-indole (Compound B) ( 11.7g).

[Reference Example 3]

Poly[9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-anthracene] (Polymer A) Synthesis

Compound A (0.55 g), Compound B (0.61 g), triphenylphosphine palladium (0.01 g), and methyltrioctyl ammonium chloride (manufactured by Aldrich, trade name: Aliquat 336 (registered trademark) under an inert gas atmosphere After mixing (0.20 g) and toluene (10 mL), the mixture was heated to 105 °C. 2M sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 8 hours. 4-tert-Butylphenylboronic acid (0.01 g) was added to the reaction mixture, and the mixture was refluxed for 6 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 2 hours. The mixed solution was added dropwise to 300 mL of methanol, and after stirring for 1 hour, the precipitate which precipitated was filtered, dried under reduced pressure for 2 hours, and then dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was 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 gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was added dropwise to methanol (200 mL), and the precipitated solid was filtered and dried. The resulting poly[9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-anthracene] (polymer) The yield of A(BSAFEGP)) is 520mg.

The number average molecular weight of the polymer A-converted polystyrene was 5.2 × 10 ⁴ . The polymer A is formed by a repeating unit represented by the formula (A).

[Experimental Example 1] Synthesis of polymer A sulfonium salt

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. After adding tetrahydrofuran (20 mL) and ethanol (20 mL), the mixture was warmed to 55 °C. Thereto, an aqueous solution in which barium hydroxide (200 mg) was dissolved in water (2 mL) was added, and the mixture was stirred at 55 ° C for 6 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (150 mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer A had completely disappeared. The obtained sulfonium salt of the polymer A is referred to as a conjugated polymer compound 1. The conjugated polymer compound 1 is formed by a repeating unit represented by the formula (B) ("in the entire repeating unit, one containing a group selected from the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 100% by mole.). The orbital energy of HOMO of the conjugated polymer compound 1 was -5.5 eV, and the orbital energy of LUMO was -2.7 eV.

[Experimental Example 2] Synthesis of Polymer A Potassium Salt

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. After adding tetrahydrofuran (20 mL) and methanol (10 mL), an aqueous solution of potassium hydroxide (400 mg) 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 stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (131mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer A completely disappeared. The obtained potassium salt of the polymer A is referred to as a conjugated polymer compound 2. The conjugated polymer compound 2 is formed by a repeating unit represented by the formula (C) ("in the entire repeating unit, the group containing the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 100% by mole.). The orbital energy of HOMO of the conjugated polymer compound 2 was -5.5 eV, and the orbital energy of LUMO was -2.7 eV.

[Experimental Example 3] Synthesis of polymer A sodium salt

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. After mixing tetrahydrofuran (20 mL) and methanol (10 mL), an aqueous solution of sodium hydroxide (260 mg) 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 stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (123 mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer A had completely disappeared. The obtained sodium salt of the polymer A is referred to as a conjugated polymer compound 3. The conjugated polymer compound 3 is formed by a repeating unit represented by the formula (D) ("in the whole repeating unit, one containing a group selected from the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 100% by mole.). The orbital energy of HOMO of the conjugated polymer compound 3 was -5.6 eV, and the orbital energy of LUMO was -2.8 eV.

[Experimental Example 4] Synthesis of Polymer A Ammonium Salt

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. After mixing tetrahydrofuran (20 mL) and methanol (15 mL), an aqueous solution of tetramethylammonium hydroxide (50 mg) 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 of tetramethylammonium hydroxide (50 mg) dissolved in water (1 mL) was added to the reaction solution, and the mixture was stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (150 mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer A had disappeared by 90%. The obtained ammonium salt of the polymer A is referred to as a conjugated polymer compound 4. The conjugated polymer compound 4 is formed by a repeating unit represented by the formula (E) ("in the whole repeating unit, one containing a group selected from the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 90% by mole.). The HOMO orbital energy of the conjugated polymer compound 4 was -5.6 eV, and the orbital energy of LUMO was -2.8 eV.

[Reference Example 4]

2,7-bis[7-(4-methylphenyl)-9,9-dioctylindol-2-yl]-9,9-bis[3-ethoxycarbonyl-4-[2-[2 Synthesis of -(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-indole (Polymer B)

Compound A (0.52g), 2,7-double under inert gas atmosphere (1,3,2-dioxaborolan-2-yl)9,9-dioctylfluorene (1.29 g), triphenylphosphine palladium (0.0087 g), methyltrioctyl chloride Ammonium (manufactured by Aldrich, trade name: Aliquat 336 (registered trademark)) (0.20 g), toluene (10 mL), and 2M sodium carbonate solution (10 mL) were mixed, and then heated to 80 °C. The reaction solution was allowed to react for 3.5 hours. Then, p-bromotoluene (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, and 50 mL of ethyl acetate / 50 mL of distilled water was added, and the aqueous layer was removed. Further, 50 mL of distilled water was added to remove the aqueous layer, and then magnesium sulfate was added as a desiccant, and the insoluble matter was filtered, and then the organic solvent was removed. Then, the residue was redissolved in 10 mL of THF, and 2 mL of a saturated aqueous solution of sodium diethyldithiocarbamate was added thereto, and the mixture was stirred for 30 minutes, and then the organic solvent was removed. It is purified by passing through an alumina column (expanded solvent hexane: ethyl acetate = 1:1, v/v), and the precipitate precipitated is filtered, and after drying under reduced pressure for 12 hours, 2,7-double is obtained. [7-(4-Methylphenyl)-9,9-dioctylindol-2-yl]-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-A) Oxyethoxyethoxy)ethoxy]ethoxy]phenyl]-indole (Polymer B) 524 mg.

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

[Experimental Example 5] Synthesis of polymer B sulfonium salt

Polymer B (262 mg) was placed in a 100 mL flask and replaced with argon. After adding tetrahydrofuran (10 mL) and methanol (15 mL), it will be mixed. The temperature was raised to 55 °C. Thereto, an aqueous solution in which cesium hydroxide (341 mg) was dissolved in water (1 mL) was added, and the mixture was stirred at 55 ° C for 5 hours. After the resulting mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (250 mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer A had completely disappeared. The obtained bismuth salt of the polymer B is referred to as a conjugated polymer compound 5. The conjugated polymer compound 5 is formed by a repeating unit represented by the formula (G) ("in the entire repeating unit, one containing a group selected from the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units, which is rounded off to 23.3 m% after the second decimal place.). The orbital energy of HOMO of the conjugated polymer compound 5 was -5.6 eV, and the orbital energy of LUMO was -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-tert-butyl-2) under an inert atmosphere ,6-Dimethylphenyl)1,4-phenylenediamine (35 mg), triphenylphosphine palladium (8 mg), methyltrioctyl 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. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 8 hr. Phenylboronic acid (0.01 g) was added to the reaction mixture, and the mixture was refluxed for 6 hours. Next, sodium diethyldiaminocarbamate (10 mL, concentration 0.05 g/mL) was added and stirred for 2 hours. The mixed solution was added dropwise to 300 mL of methanol, and after stirring for 1 hour, the precipitate which precipitated was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3% by weight aqueous acetic acid solution, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dissolved in 20 mL of tetrahydrofuran. The solution thus obtained was added dropwise to 200 mL of methanol, and after stirring for 30 minutes, 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 gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was added dropwise to methanol (200 mL), and the solid was filtered and dried. The yield of the obtained polymer C was 526 mg.

The number average molecular weight of the polymer C in terms of polystyrene was 3.6 × 10 ⁴ . Further, the polymer C is formed by a structural unit represented by the formula (H).

Further, N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylene diamine can be, for example The method described in Japanese Laid-Open Patent Publication No. 2008-74017 is synthesized.

[Experimental Example 6] Synthesis of polymer C strontium salt

Polymer C (200 mg) was placed in a 100 mL flask and replaced with nitrogen. gas. 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 stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (150 mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer C had completely disappeared. The obtained sulfonium salt of the polymer C is referred to as a conjugated polymer compound 6. The conjugated polymer compound 6 is formed by a repeating unit represented by the formula (I) ("in the entire repeat unit, the group containing the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 95% by mole.). The orbital energy of HOMO of the conjugated polymer compound 6 was -5.3 eV, and the orbital energy of LUMO was -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-tert-butyl-2) under an inert atmosphere ,6-Dimethylphenyl)1,4-phenylenediamine (0.038g), 3,7-dibromo-N-(4-n-butylphenyl)phenoxazine (0.009g), triphenyl Phosphine palladium (0.01g), A The mixture was mixed with trioctyl ammonium chloride (manufactured by Aldrich, trade name: Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL), and then heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 2 hr. Phenylboronic acid (0.004 g) was added to the reaction mixture, and the mixture was refluxed for 6 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 2 hours. The mixed solution was added dropwise to 300 mL of methanol, and after stirring for 1 hour, the precipitate which precipitated was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 200 mL of methanol and 50 mL of a 3% by weight aqueous acetic acid solution, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dissolved in 20 mL of tetrahydrofuran. The thus obtained solution was added dropwise to 200 mL of methanol, and after stirring for 30 minutes, 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 gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was 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 of the polymer D in terms of polystyrene was 2.7 × 10 ⁴ . Further, the polymer D is formed by a repeating unit represented by the formula (J).

Further, 3,7-dibromo-N-(4-n-butylphenyl)phenoxazine was synthesized by the method described in JP-A-2004-137456.

[Experimental Example 7] Synthesis of polymer D sulfonium salt

Polymer D (200 mg) was placed in a 100 mL flask and replaced with nitrogen. After mixing tetrahydrofuran (15 mL) with methanol (10 mL). 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 stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (210 mg). From the NMR spectrum, it was confirmed that the signal of the ethyl group derived from the ethyl ester moiety in the polymer D had completely disappeared. The obtained sulfonium salt of the polymer D is referred to as a conjugated polymer compound 7. The conjugated polymer compound 7 is formed by a repeating unit represented by the formula (K) ("in the entire repeat unit, one containing a group selected from the group represented by the formula (1) and a group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 95% by mole.). The HOMO orbital energy of the conjugated polymer compound 7 was -5.3 eV, and the orbital energy of LUMO was -2.4 eV.

[Reference Example 7] Synthesis of polymer E

Compound A (0.37 g), Compound B (0.82 g), 1,3-dibromobenzene (0.09 g), triphenylphosphine palladium (0.01 g), methyl group under an inert atmosphere Trioctyl 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. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 7 hr. Phenylboronic acid (0.002 g) was added to the reaction mixture, and the mixture was refluxed for 10 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 1 hour. The mixed solution was added dropwise to 300 mL of methanol, and after stirring for 1 hour, the precipitate which precipitated was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered, and dissolved in 20 mL of tetrahydrofuran. The thus obtained solution was added dropwise to 200 mL of methanol, and after stirring for 30 minutes, 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 gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was 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 of the polymer E-converted polystyrene was 1.8 × 10 ⁴ . The polymer E is formed by a repeating unit represented by the formula (L).

[Experimental Example 8] Synthesis of polymer E sulfonium salt

Polymer E (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (10 mL) and methanol (5 mL) were combined. 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 stirred at 65 ° C for 5 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (170 mg). From the NMR spectrum, it was confirmed that the signal of the ethyl group derived from the ethyl ester moiety in the polymer E had completely disappeared. The obtained sulfonium salt of the polymer E is referred to as a conjugated polymer compound 8. The conjugated polymer compound 8 is formed by a repeating unit represented by the formula (M) ("in the entire repeat unit, one containing a group selected from the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is, at 75 mol%.). The HOMO orbital energy of the conjugated polymer compound 8 was -5.6 eV, and the orbital energy of LUMO was -2.6 eV.

[Reference Example 8] Synthesis of polymer F

Compound B (1.01 g), 1,4-dibromo-2,3,5,6-tetrafluorobenzene (0.30 g), triphenylphosphine palladium (0.02 g), methyl three under an inert atmosphere Xin After mixing ammonium chloride (manufactured by Aldrich, trade name: Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL), the mixture was heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 4 hr. Phenylboronic acid (0.002 g) was added to the reaction mixture, and the mixture was refluxed for 4 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 1 hour. The mixed solution was added dropwise to 300 mL of methanol, and after stirring for 1 hour, the precipitate which precipitated was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3% by weight aqueous acetic acid solution, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dissolved in 20 mL of tetrahydrofuran. The thus obtained solution was added dropwise to 200 mL of methanol, and after stirring for 30 minutes, 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 passed through an alumina column and a gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was 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 number average molecular weight of the polymer F in terms of polystyrene was 6.0 × 10 ⁴ . Further, the polymer F is formed by a repeating unit represented by the formula (N).

[Experimental Example 9] Synthesis of polymer F strontium salt

Polymer F (150 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (10 mL) and methanol (5 mL) were combined. 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, followed by stirring at 65 ° C for 5 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (130 mg). From the NMR spectrum, it was confirmed that the signal of the ethyl group derived from the ethyl ester moiety in the polymer F had completely disappeared. The obtained phosphonium salt of the polymer F is referred to as a conjugated polymer compound 9. The conjugated polymer compound 9 is formed by a repeating unit represented by the formula (0) ("in the entire repeat unit, the group containing the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is, at 75 mol%.). The orbital energy of HOMO of the conjugated polymer compound 9 was -5.9 eV, and the orbital energy of LUMO was -2.8 eV.

[Reference Example 9]

2-[2-(2-methoxyethoxy)ethoxy]-p-toluenesulfonate (11.0g), triethylene glycol (30.0g), calcium hydroxide under inert atmosphere (3.3 g) After mixing, the mixture was stirred under heating at 100 ° C for 18 hours. After allowing to cool, the reaction solution was added to water (100 mL), and the mixture was extracted with chloroform and concentrated. After subjecting the concentrated solution to Kugelrchr distillation (10 mm Torr, 180 ° C), 2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-) Ethoxy)-ethoxy)ethanol (6.1 g).

[Reference Example 10]

2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy) in an inert atmosphere Ethanol (8.0 g), sodium hydroxide (1.4 g), distilled water (2 mL), and tetrahydrofuran (2 mL) were mixed and then water-cooled. To the mixed solution, a solution of p-toluenesulfonyl chloride (5.5 g) in tetrahydrofuran (6.4 mL) was added dropwise over 30 minutes, and the mixture was evaporated 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 6 M sulfuric acid, followed by liquid separation extraction with chloroform. After concentrating the solution, 2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy)) p-Tosylate (11.8 g).

[Reference Example 11]

2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)) Synthesis of -ethoxy)-ethoxy)-ethoxy)ethoxy]phenyl]-indole (Compound C)

2,7-Dibromo-9-indole (127.9 g), ethyl salicylate (375.2 g) and mercaptan acetate (3.5 g) were placed in a 300 mL flask and replaced with nitrogen. After the addition of methanesulfonic acid (1,420 mL), the mixture was stirred at 75 ° C overnight. After the mixture was allowed to cool, it was added to ice water and stirred for 1 hour. The resulting solid was separated by filtration and washed with heated acetonitrile. Dissolving the solid after washing The solid was recrystallized from the obtained acetone solution in acetone, and a solid (167.8 g) was obtained by filtration. The obtained solid (5 g), 2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy) )-p-toluenesulfonate (10.4g), potassium carbonate (5.3g) and 18-crown-6 (0.6g) were dissolved in N,N-dimethylformamide (DMF) (100mL), The solution was transferred to a flask and stirred at 105 ° C for 4 hours. After the resulting mixture was allowed to cool to room temperature, it was added to ice water and stirred for 1 hour. Chloroform (300 mL) was added to the reaction mixture for liquid separation extraction, and the solution was concentrated. The concentrate is dissolved in ethyl acetate, and after passing through the column of alumina, the solution is concentrated to obtain 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-( 2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy)ethoxy]phenyl]-indole ( Compound C) (4.5 g).

[Reference Example 12] Synthesis of polymer G

Compound C (1.0 g), 4-tert-butylphenyl bromide (0.9 mg), 2,2'-bipyridine (0.3 g), dehydrated tetrahydrofuran (50 mL) were placed in a 200 mL flask under an inert atmosphere. mixing. After the mixture was heated 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 cooling the mixture to room temperature, the reaction solution was dropped into methanol. A mixture of (200 mL) and 1 N diluted hydrochloric acid (200 mL). The resulting precipitate was filtered, collected, and redissolved in tetrahydrofuran. A mixed liquid of methanol (200 mL) and 15% aqueous ammonia (100 mL) was added dropwise, and the resulting precipitate was collected by filtration. The precipitate was redissolved in tetrahydrofuran, and a mixture of methanol (200 mL) and water (100 mL) was added dropwise, and the resulting precipitate was collected by filtration. After the collected precipitate was dried under reduced pressure, a polymer G (360 mg) was obtained.

The number average molecular weight of the polymer G in terms of polystyrene was 6.0 × 10 ⁴ . Further, the polymer G is formed by a repeating unit represented by the formula (P).

[Experimental Example 10] Synthesis of polymer G strontium salt

Polymer G (150 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (15 mL) and methanol (5 mL) were combined. 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 evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (95 mg). It was confirmed by NMR spectrum that the signal of the ethyl group derived from the ethyl ester moiety in the polymer G had completely disappeared. The obtained sulfonium salt of the polymer G is referred to as a conjugated polymer compound 10. The conjugated polymer compound 10 is formed by a repeating unit represented by the formula (Q) ("in the entire repeat unit, one containing a group selected from the group represented by the formula (1) and the group represented by the formula (2)) More than one The ratio of the repeating unit of the one or more types of bases represented by the formula (3) and the repeating unit represented by the formula (13), the formula (15), the formula (17), and the formula (20) among the total repeat units The ratio is 100% by mole. ). The orbital energy of HOMO of the conjugated polymer compound 10 was -5.7 eV, and the orbital energy of LUMO was -2.9 eV.

[Reference Example 13]

Synthesis of 1,3-dibromo-5-ethoxycarbonyl-6-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene

3,5-dibromosalic acid (20 g), ethanol (17 mL), concentrated sulfuric acid (1.5 mL), and toluene (7 mL) were mixed under an inert atmosphere, and the mixture was stirred under heating at 130 ° C for 20 hours. After allowing to cool, the reaction solution was added to ice water (100 mL), and the mixture was extracted with chloroform and concentrated. The obtained solid was dissolved in isopropyl alcohol, and the solution was dropped into distilled water. After the obtained precipitate was separated by filtration, a solid (18 g) was obtained. The obtained solid (1 g), 2-[2-(2-methoxyethoxy)ethoxy]-p-toluenesulfonate (1.5 g), potassium carbonate (0.7 g) under an inert atmosphere. After mixing with DMF (15 mL), the mixture was heated and stirred at 100 ° C for 4 hours. After allowing to cool, chloroform was added for liquid separation extraction, and the solution was concentrated. The concentrate was dissolved in chloroform and passed through a gel column for purification. 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-ethylcarbonyl-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. A 2 M aqueous sodium carbonate solution (5 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 5 hr. Phenylboronic acid (6 mg) was added to the reaction mixture, and the mixture was refluxed for 14 hr. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added to the reaction mixture, followed by stirring for 2 hours. After removing the water layer, the organic layer was washed with distilled water, and after concentration, the obtained solid was dissolved in chloroform, and passed through an alumina column and a rubber tube column for purification. The eluate from the column is concentrated and dried. The yield of the obtained polymer H was 0.44 g.

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

[Experimental Example 11] Synthesis of polymer H sulfonium salt

Polymer H (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (14 mL) and methanol (7 mL) were combined. An aqueous solution in which cesium hydroxide (90 mg) was dissolved in water (1 mL) was added to the mixed solution, and stirred at 65 ° C Mix for 1 hour. 5 mL of methanol was added to the reaction solution, and the mixture was stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (190 mg). From the NMR spectrum, it was confirmed that the signal of the ethyl group derived from the ethyl ester moiety in the polymer H had completely disappeared. The obtained phosphonium salt of the polymer H is referred to as a conjugated polymer compound 11. The conjugated polymer compound 11 is formed by a repeating unit represented by the formula (S) ("in the entire repeat unit, the group containing the group represented by the formula (1) and the group represented by the formula (2)) Formula (13), Formula (15), Formula (17), and Formula (20) are represented by "the ratio of the above-mentioned group to the repeating unit of one or more kinds of groups represented by the formula (3)" and "all repeating units" The ratio of repeating units is 100% by mole.). The orbital energy of HOMO of the conjugated polymer compound 11 was -5.6 eV, and the orbital energy of LUMO was -2.8 eV.

[Reference Example 15]

2,7-dibromo-9,9-bis[3,4-bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-5-methoxycarbonylphenyl] - Synthesis of hydrazine (Compound D)

2,7-Dibromo-9-indole (34.1 g), 2,3-dihydroxybenzoic acid methyl ester (101.3 g) and thiol acetic acid (1.4 g) were placed in a 500 mL flask and replaced with nitrogen. After adding methanesulfonic acid (350 mL), the mixture was stirred at 90 ° C for 19 hours. After the mixture was allowed to cool, it was added to ice water and stirred for 1 hour. The resulting solid was separated by filtration and washed with heated acetonitrile. The washed solid was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution, and separated by filtration. The obtained solid (16.3 g), 2-[2-(2-methoxyethoxy)-ethoxy]-p-toluenesulfonate (60.3 g), potassium carbonate (48.6 g) and 18-cr. -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. After the resulting mixture was allowed to cool to room temperature, it was added to ice water and stirred for 1 hour. Ethyl acetate (300 mL) was added to the reaction mixture for liquid separation extraction, and the solution was concentrated, and the concentrate was dissolved in a mixed solvent of chloroform/methanol (50/1 (volume ratio)), and passed through a silica gel column. Concentrate the solution after the liquid column to obtain 2,7-dibromo-9,9-bis[3,4-bis[2-[2-(2-methoxyethoxy)ethoxy] Oxy]-5-ethoxycarbonylphenyl]-indole (Compound D) (20.5 g).

[Reference Example 16]

2,7-bis[7-(4-methylphenyl)-9,9-dioctylfluoren-2-yl]-9,9-bis[5-methoxycarbonyl-3,4-bis[2 Synthesis of [2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]anthracene (Polymer I)

Compound D (0.70 g), 2-(4,4,5,5-tetramethyl-1,2,3-dioxaborolan-2-yl)-9 under an inert atmosphere 9-Dioctylhydrazine (0.62 g), triphenylphosphine palladium (0.019 g), dioxane (40 mL), water (6 mL) and aqueous potassium carbonate solution (1.38 g) were mixed and then heated to 80 °C. The reaction solution was allowed to react for 1 hour. After the reaction, 5 mL of a saturated aqueous solution of sodium diethyldithiocarbamate was added, and the mixture was stirred for 30 minutes, and then the organic solvent was removed. The obtained solid was passed through an alumina column (developing solvent hexane: ethyl acetate = 1:1 (volume ratio)), and the solution was concentrated to obtain 2,7-bis[7-(4-A) base Phenyl)-9,9-dioctylindol-2-yl]-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy) Ethoxy]phenyl]-indole (Polymer I) 660 mg.

The number average molecular weight of the polymer I in terms of polystyrene was 2.0 × 10 ³ . The polymer I is represented by the formula (T). Further, 2-(4,4,5,5-tetramethyl-1,2,3-dioxaborolan-2-yl)-9,9-dioctylfluorene may be, for example, a Japanese special The method described in the publication No. 2008-74017 is synthesized.

[Experimental Example 12] Synthesis of polymer I sulfonium salt

Polymer I (236 mg) was placed in a 100 mL flask and replaced with argon. After adding tetrahydrofuran (20 mL) and methanol (10 mL), the mixture was warmed to 65 °C. Thereto, an aqueous solution in which barium hydroxide (240 mg) was dissolved in water (2 mL) was added, and stirred at 65 ° C for 7 hours. After the resulting mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (190 mg). From the NMR spectrum, it was confirmed that the signal of the ethyl group derived from the ethyl ester site completely disappeared. The obtained polymer I sulfonium salt is referred to as a conjugated polymer compound 12. The conjugated polymer compound 12 is formed by a repeating unit represented by the formula (U) ("all weight In the compound unit, 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) and the repeating unit of one or more groups represented by the formula (3) "Proportion of repeating units expressed by formula (13), formula (15), formula (17), and formula (20)", "33.3 mol% after rounding off the second decimal place" . ). The orbital energy of HOMO of the conjugated polymer compound 12 was -5.6 eV, and the orbital energy of LUMO was -2.8 eV. (p.167)

1, 1a, 1b, 1c, 1d‧‧‧ first electrode

2, 2a, 2b, 2c, 2d‧‧‧ second electrode

3, 3a, 3b, 3c, 3d‧‧‧ take out the electrode

4‧‧‧Lighting units

5a, 5b, 5c, 5d‧‧‧ hole injection layer

6a, 6b, 6c, 6d‧‧‧ hole transport layer

7a, 7b, 7c, 7d‧‧‧ luminescent layer

8a, 8b, 8c, 8d‧‧‧ electron injection layer

9a, 9b, 9c‧‧‧ conductive film of the same material as the cathode

10a, 10b, 109c‧‧‧ Conductive film of the same material as the anode

11‧‧‧Drive circuit

Fig. 1 is a schematic view showing the structure of an organic EL element.

Fig. 2 is a schematic view showing the structure of an organic EL element.

Fig. 3 is a schematic view showing the structure of an organic EL element.

Fig. 4 is a schematic view showing the structure of an organic EL element.

Fig. 5 is a schematic view showing the structure of an organic EL element.

Figure 6 shows a diagram of the illuminating color.

1‧‧‧1st electrode

2‧‧‧2nd electrode

3‧‧‧Removing the electrode

4‧‧‧Lighting units

11‧‧‧Drive circuit

Claims (8)

An organic EL device comprising: a first electrode; a second electrode; and 1 or a plurality of extraction electrodes disposed between the first electrode and the second electrode; and the first electrode and the extraction electrode And in the second electrode, a plurality of light-emitting units having an electron injecting layer and a light-emitting layer disposed between the adjacent electrodes, wherein the electron injecting layer contains an ionic polymer. The organic EL device according to claim 1, wherein the light-emitting layer of the adjacent one of the extraction electrodes is a light-emitting layer having the first electrode as a reference in one of the light-emitting units The order of lamination of the electron injecting layer is different from the order of lamination of the light emitting layer and the electron injecting layer in the other light emitting unit. The organic EL device according to claim 1 or 2, wherein the pair of light-emitting layers provided in the mutually different light-emitting units emit light of mutually different colors. The organic EL device according to claim 1 or 2, wherein the pair of light-emitting layers provided in mutually different light-emitting units emit light of the same color. An illuminating device comprising the organic EL element according to any one of claims 1 to 4. A display device comprising any one of claims 1 to 4 The organic EL element. A method for producing an organic EL device, comprising: a first electrode, a second electrode, or a plurality of extraction electrodes disposed between the first electrode and the second electrode; and the first electrode and the extraction A method for producing an organic EL device having a plurality of light-emitting units having an electron injection layer and a light-emitting layer disposed between adjacent electrodes of the electrode and the second electrode, the method comprising: coating a liquid containing an ionic polymer a step of forming a film and forming the electron injecting layer; and forming a step of forming the light emitting layer before or after forming the electron injecting layer. The method for producing an organic EL device according to claim 7, wherein the coating liquid containing the ionic polymer has a volume ratio of nitrogen of 90% or less and a volume ratio of oxygen of 10% or more. It is coated in an atmosphere of less than %.