WO2012011471A1

WO2012011471A1 - Organic electroluminescence display device manufacturing method and organic electroluminescence display device

Info

Publication number: WO2012011471A1
Application number: PCT/JP2011/066369
Authority: WO
Inventors: 小野　善伸
Original assignee: 住友化学株式会社
Priority date: 2010-07-21
Filing date: 2011-07-19
Publication date: 2012-01-26
Also published as: JP2012044160A; TW201213500A

Abstract

Disclosed is method of manufacturing an organic electroluminescence display device formed so as to have multiple pixels comprising organic electroluminescence elements which include: an electrode pair consisting of a positive electrode and a negative electrode; a light-emitting layer positioned between said electrodes; and an electron injection layer positioned between the aforementioned negative electrode and light-emitting layer. The disclosed organic electroluminescence display device manufacturing method involves a step of forming a light-emitting layer by coating with a solution containing a light-emitting material the substrate on which the aforementioned positive electrode is formed, a step of forming an electron injection layer by coating the aforementioned light-emitting layer with a solution containing an ionic polymer, and a step of forming the negative electrode on the aforementioned electron injection layer.

Description

Organic electroluminescence display device manufacturing method and organic electroluminescence display device

The present invention relates to a method for manufacturing an organic electroluminescence display device, and an organic electroluminescence display device obtained by the manufacturing method.

An organic electroluminescence display device (hereinafter also referred to as an organic EL display device) includes a plurality of pixels composed of organic electroluminescence elements (hereinafter also referred to as organic EL elements), and is individually provided according to an image signal. An image is displayed by creating a pixel circuit for driving each organic EL element for each pixel.

The organic EL element constituting the organic EL display device has a basic structure in which a light emitting layer made of an organic light emitting material is formed between an anode and a cathode as a thin film. In the organic EL element having such a basic configuration, when a voltage is applied between the electrodes, holes are injected from the anode and electrons are injected from the cathode. Light emission is generated by combining holes and electrons in the light emitting layer.

Ordinarily, it is difficult for an organic EL element to obtain desired characteristics only with the above basic configuration. Therefore, a predetermined organic layer is provided in addition to the light emitting layer. For example, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and the like are provided as the predetermined organic layer.

The organic layer between the anode and the cathode of the organic EL element is formed by a vacuum deposition method or a coating method. Since the coating method does not require a vacuum process, it is characterized by easy area enlargement and low manufacturing costs.

Conventionally, it has been difficult to produce an organic EL display device including electrodes up to a coating method without going through a vacuum process, and usually an electron injection layer and a cathode were formed by a vacuum process. This has been an obstacle to the increase in area and cost of the organic EL display device.

The reason why the above-described vacuum process is necessary is that Ba and NaF, which are generally used as electron injection layer materials, are unstable in the atmosphere. For example, when the cathode is formed by a coating method, the electron injection layer easily reacts with moisture and oxygen at that time and chemically changes.

In order to solve the above-described problems, conventionally, “an organic EL device including at least a light emitting layer between an opposing anode and a main cathode, in which an electron is disposed between the light emitting layer and the main cathode. An organic EL device comprising an electron injection layer made of an injectable metal complex and in which the main cathode is formed by applying a first liquid containing a conductive material has been proposed. (For example, refer to Patent Document 1).

JP 2005-79064 A

However, there are a limited number of electron injection materials that are relatively stable in atmospheric air at atmospheric pressure and that facilitate electron injection from the cathode. Development of electron injection materials is underway.
Accordingly, an object of the present invention is to provide a method for manufacturing an organic electroluminescence display device formed by using a novel electron injection material that is relatively stable in an atmosphere of about atmospheric pressure.

The present inventors have found that an ionic polymer has electron injectability, is stable in an atmosphere at normal pressure, and further stable in the air, and is dissolved in a solvent to form a solution, and the solution is formed into a film. It has been found that a stable electron injection layer can be obtained in an atmosphere at a pressure level or even in the air. The present invention has been made based on such knowledge. The present invention provides an organic light emitting display device manufacturing method and an organic EL display device that employ the following configuration.

In the present invention, the term “in the atmosphere” means all atmospheres that allow the inclusion of oxygen and moisture in a broad sense for the purpose of the present invention. More specifically, it includes an unadjusted atmospheric atmosphere at ordinary temperature and normal pressure, and an atmosphere in which temperature, pressure, and components are adjusted with oxygen and moisture contained in the atmospheric atmosphere. included. As the adjustment atmosphere, a process for adjusting composition components such as nitrogen, hydrogen, oxygen, carbon dioxide, etc. with respect to the air atmosphere under the condition that the production method of the present invention including “coating” can be carried out, and a composition ratio thereof. The degree of cleanliness of suspended particulates and suspended microorganisms may be adjusted, and environmental conditions such as temperature, humidity, and pressure are adjusted on condition that the production method of the present invention can be carried out. An atmosphere that may be used is included, and the pressure is normally a normal pressure of 1013 hPa ± 100 hPa.

In the following description, one side in the thickness direction of the substrate may be referred to as upper (or upper), and the other in the thickness direction of the substrate may be referred to as lower (or lower). This notation of the vertical relationship is set for convenience of explanation, and is not necessarily applied to a process in which an organic EL element is actually manufactured and a situation in which it is used.

[1] A plurality of pixels each including an organic electroluminescence element including a pair of electrodes including an anode and a cathode, a light emitting layer positioned between the electrodes, and an electron injection layer positioned between the cathode and the light emitting layer. An organic electroluminescence display device manufacturing method comprising:
Applying a solution containing a light emitting material on the substrate on which the anode is formed, and forming a light emitting layer by forming a film;
Applying a solution containing an ionic polymer on the light emitting layer and forming a film to form an electron injection layer;
Forming a cathode on the electron injection layer;
A method for producing an organic electroluminescence display device, comprising:
[2] In the step of forming the electron injection layer, a solution containing an ionic polymer is commonly applied to all pixels on the substrate on which the light emitting layer is formed, and an electron injection layer continuous over all pixels is formed. The method for producing an organic electroluminescence display device according to [1] above, which is characterized by the following.
[3] In the step of forming the cathode, the cathode is formed by applying a liquid material containing a conductive material and forming a film. Manufacturing method of luminescence display device.
[4] The plurality of pixels are composed of a blue organic electroluminescence element that emits blue light and an organic electroluminescence element of another color that emits light having a spectrum different from that of the blue light,
In the step of forming the light emitting layer, a solution containing a light emitting material to be a light emitting layer of the organic electroluminescent element of the other color is applied to a region where the organic electroluminescent element of the other color is provided and formed into a film. Furthermore, a solution containing a light emitting material to be a light emitting layer of the blue organic electroluminescent element is applied to a region where the blue organic electroluminescent element and the organic electroluminescent element of the other color are provided to form a film. The method for producing an organic electroluminescence display device according to any one of [1] to [3] above, which is characterized in that
[5] An organic electroluminescence display device manufactured by the manufacturing method according to any one of [1] to [4] above.

FIG. 1 is a schematic sectional view showing a first embodiment of an organic EL display device according to the present invention. FIG. 2 is a schematic sectional view showing a second embodiment of the organic EL display device according to the present invention.

1 Substrate 2 Pixel electrode (anode)
3 pixel 31 R pixel 32 G pixel 33 B pixel 4 first bank layer 5 second bank layer 6 hole injection layer 7 hole transport layer 81 R light emission layer 82 G light emission layer 83 B light emission layer 9 electron injection layer 10 cathode

As described above, the organic electroluminescence display device manufacturing method of the present invention includes a pair of electrodes including an anode and a cathode, a light emitting layer positioned between the electrodes, and a position between the cathode and the light emitting layer. An organic electroluminescence display device manufacturing method comprising a plurality of pixels comprising an organic electroluminescence element including an electron injection layer, wherein a solution containing a light emitting material is applied on the substrate on which the anode is formed, Forming a light emitting layer by forming a film; applying a solution containing an ionic polymer on the light emitting layer; forming an electron injecting layer by forming a film; and forming a cathode on the electron injecting layer. Forming.

Each element of the present invention having the above configuration will be described in detail below. First, an ionic polymer that is another option for an electron-injecting material that can form a stable electron-injecting layer in an atmosphere at atmospheric pressure by forming a solution dissolved in a solvent. Will be described. Next, the configuration of the organic EL element will be described, and subsequently, the manufacturing method of the organic EL display device and the organic EL display device obtained by the manufacturing method will be described in detail.

[Ionic polymer]
Examples of the ionic polymer that can be used in the present invention include structural units containing one or more groups selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2). The polymer which has is mentioned. As one form of the ionic polymer, a structural unit containing one or more groups selected from the group consisting of the group represented by the formula (1) and the group represented by the formula (2) Examples thereof include a polymer having 15 to 100 mol%.

-(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 (1)
[In Formula (1), Q ¹ represents a divalent organic group, Y ¹ represents —CO ₂ ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , —PO ₃ ²⁻ or —B (R ^a ) ₃ ^- represents, M ¹ is an ammonium cation which does not have or have a metal cation or a substituent, Z ¹ is ^{^{^{F -, Cl -, Br -}}} , I -, OH -, R a SO 3 -, R a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ^-, BF ₄ ^- or PF ₆ ^- represents, n1 represents an integer of 0 or more, a1 represents an integer of 1 or more, b1 represents an integer of 0 or more, provided that, a1 and b1 of the formula (1 ) charge of the group represented by is chosen to be 0, do is a or have a R ^a is 1 to 30 carbon atoms having no or an unsubstituted alkyl group or a substituted group An aryl group having a carbon number of 6 to 50, each of Q ^1, M ¹ and Z ¹ when a plurality, may be the same or different. ]

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

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

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

-S- (R'S) _a4 -R '' (6)
-C (= O)-(R'-C (= O)) _a4 -R '' (7)
-C (= S)-(R'-C (= S)) _a4 -R '' (8)
-N [(R ′) _a4 R ″] ₂ (9)
—C (═O) O— (R′—C (═O) O) _a4 —R ″ (10)
—C (═O) O— (R′O) _a4 —R ″ (11)
—NHC (═O) — (R′NHC (═O)) _a4 —R ″ (12)
(In the formulas (4) to (12), R ′ represents a divalent hydrocarbon group with or without a substituent, and R ″ represents a hydrogen atom, a monovalent with or without a substituent. A hydrocarbon group, —COOH, —SO ₃ H, —OH, —SH, —NR ^c ₂ , —CN or —C (═O) NR ^c ₂ , wherein R ′ ″ has a substituent, or Represents a trivalent hydrocarbon group not having, a3 represents an integer of 1 or more, a4 represents an integer of 0 or more, and R ^c is an alkyl having 1 to 30 carbon atoms with or without a substituent. An aryl group having 6 to 50 carbon atoms, with or without a group or substituent, may be the same or different when there are a plurality of R ′, R ″ and R ′ ″. ]]

The ionic polymer includes a structural unit represented by the following 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). It is preferable that 15 to 100 mol% of one or more structural units selected from the group consisting of:

[In formula (13), R ¹ is a monovalent group containing a group represented by the following formula (14), and Ar ¹ has a (2 + n4) valence with or without a substituent other than R ^1. N4 represents an integer of 1 or more, and when there are a plurality of R ^{1 s} , they may be the same or different. ]

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

[In the formula (15), R ³ is a monovalent group including a group represented by the following formula (16), and Ar ² has (2 + n5) valence with or without a substituent other than R ^3. N5 represents an integer of 1 or more, and when there are a plurality of R ^{3 s} , they may be the same or different. ]

[In the formula (16), R ⁴ represents a (1 + m3 + m4) valent organic group, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3 have the same meaning as described above. M3 and m4 each independently represents an integer of 1 or more. When there are a plurality of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n 2, a 2, b 2 and n 3, they may be the same or different. ]

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

-R ⁷ -[(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 ] _m5 (18)
[In Formula (18), R ⁷ represents a direct bond or a (1 + m5) -valent organic group, Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1, and b1 represent the same meaning as described above, and m5 represents It represents an integer of 1 or more, and when there are a plurality of Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1, they 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 a (1 + m6) -valent organic group, Y ³ and n3 represent the same meaning as described above, m6 represents an integer of 1 or more, provided that R ⁸ is a single group. When bonded, m6 represents 1, and when there are a plurality of Q ³ , Y ³ and n3, they may be the same or different. ]

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

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

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

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

<Group represented by formula (1)>
In the formula (1), examples of the divalent organic group represented by Q ¹ include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, , 3-butylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, at least one of these groups A divalent saturated hydrocarbon group having 1 to 50 carbon atoms, which may or may not have a substituent, such as a group in which a hydrogen atom is substituted with a substituent; ethenylene, propenylene, 3-butenylene, 2- Having a substituent such as a butenylene group, a 2-pentenylene group, a 2-hexenylene group, a 2-nonenylene group, a 2-dodecenylene group, or a group obtained by substituting at least one hydrogen atom of these groups with a substituent. Or Alkeni with 2 to 50 carbon atoms A divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms, including or not having a substituent, including an ethylene group and an ethynylene group; a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexane Number of carbon atoms with or without a substituent, such as a xylene group, a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. 3 to 50 divalent cyclic saturated hydrocarbon groups; 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, biphenyl- An arylene group having 6 to 50 carbon atoms, which may or may not have a substituent, such as a 4,4′-diyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent; Oxy A substituent such as an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. Or an alkyleneoxy group having 1 to 50 carbon atoms; an imino group having a substituent containing a carbon atom; and a silylene group having a substituent containing a carbon atom. Among these, a divalent saturated hydrocarbon group, an arylene group, and an alkyleneoxy group are preferable from the viewpoint of ease of synthesis of a monomer that is a raw material for the ionic polymer (hereinafter referred to as “raw material monomer”). .

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

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

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

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

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

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

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

Among the aryl groups, examples of the C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a propylphenyl group, a mesityl group, a methylethylphenyl group, an isopropylphenyl group, and a butylphenyl group. , Isobutylphenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

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

Among the aryloxy groups, examples of the C ₁ -C ₁₂ alkoxyphenoxy group include methoxyphenoxy group, ethoxyphenoxy group, propyloxyphenoxy group, isopropyloxyphenoxy group, butoxyphenoxy group, isobutoxyphenoxy group, s-butoxy group. Phenoxy group, t-butoxyphenoxy group, pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group 3,7-dimethyloctyloxyphenoxy group, lauryloxyphenoxy group and the like.

Among the aryloxy groups, examples of the C ₁ -C ₁₂ alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, and a methylethylphenoxy group. , Isopropylphenoxy group, butylphenoxy group, isobutylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decyl A phenoxy group, a dodecylphenoxy group, etc. are mentioned.

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

The arylalkyl group is, for example, a group in which the above alkyl group is bonded to the above aryl group. The arylalkyl group may have a substituent. The arylalkyl group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. Examples of the arylalkyl group include a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group, Examples thereof include a ₁ -naphthyl-C ₁ -C ₁₂ alkyl group and a 2-naphthyl-C ₁ -C ₁₂ alkyl group.

The arylalkoxy group is, for example, a group in which the above alkoxy group is bonded to the above aryl group. The arylalkoxy group may have a substituent. The arylalkoxy group usually has 7 to 60 carbon atoms, and preferably 7 to 30 carbon atoms. Examples of the arylalkoxy group include a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, Examples include ₁ -naphthyl-C ₁ -C ₁₂ alkoxy group and 2-naphthyl-C ₁ -C ₁₂ alkoxy group.

The arylalkylthio group is, for example, a group in which the aforementioned alkylthio group is bonded to the aforementioned aryl group. The arylalkylthio group may have a substituent. The arylalkylthio group usually has 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms. Examples of the arylalkylthio group include 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 alkylphenyl-C ₁ to C ₁₂ alkylthio group, Examples thereof include a ₁ -naphthyl-C ₁ -C ₁₂ alkylthio group and a 2-naphthyl-C ₁ -C ₁₂ alkylthio group.

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

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

As the substituted amino group, at least one hydrogen atom in the amino group is substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The amino group formed is preferred. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amino group is usually 1 to 60, not including the number of carbon atoms of the substituent that the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have. 2 to 48 are preferred. Examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, s- Butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group , lauryl group, a cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, (C ₁ ~ C ₁₂ alkoxyphenyl) Amino group, di (C ₁ ~ C ₁₂ alkoxyphenyl) amino group, di (C ₁ ~ C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, (phenyl-C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group , (C ₁ ~ C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkyl) amino group, di (C ₁ ~ C ₁₂ alkoxyphenyl -C ₁ ~ C ₁₂ alkyl) amino group, di (C ₁ ~ C ₁₂ alkylphenyl - C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In formula (2), Y ² represents a carbocation, an ammonium cation, a phosphonyl cation, a sulfonyl cation, or an iodonium cation.
As the carbocation, for example,
-C ⁺ R ₂
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
Examples of ammonium cations include:
-N ⁺ R ₃
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
Examples of phosphonyl cations include:
-P ⁺ R ₃
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
Examples of the sulfonyl cation include:
-S ⁺ R ₂
(Wherein, R is the same or different and represents an alkyl group or an aryl group).
As an iodonium cation, for example,
-I ⁺ R ₂
(Wherein, R is the same or different and represents an alkyl group or an aryl group).

In the formula (2), Y ² represents a carbocation, an ammonium cation, a phosphonyl cation, a sulfonyl cation from the viewpoint of ease of synthesis of the raw material monomer and stability of the raw material monomer and the ionic polymer against air, moisture or heat. Are preferred, and ammonium cations are more preferred.

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

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

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

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

a2 and b2 are selected such that the charge of the group represented by the formula (2) is zero. For example, M ² is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ^{_{^{_{-, nO 3 -, HSO 4}}}} -, H 2 PO 4 -, BF 4 - or PF ₆ ^- if it is, if an ammonium ion Z ² has no or have a monovalent metal ion or a substituent , A2 = b2 + 1 is selected and Z ² is a divalent metal ion, a2 = 2 × b2 + 1 is selected and Z ² is a trivalent metal ion, a2 = 3 Xb2 + 1 is selected to satisfy. When M ² is SO ₄ ²⁻ or HPO ₄ ²⁻ , if Z ² is a monovalent metal ion or an ammonium ion with or without a substituent, b2 = 2 × a2-1 is satisfied. If Z ² is a trivalent metal ion, it is selected so as to satisfy the relationship of 2 × a2 = 3 × b2 + 1. In any of the above mathematical expressions representing the relationship between a2 and b2, a2 is preferably an integer of 1 to 3, more preferably 1 or 2.

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

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

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

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

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

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

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

In the formulas (4) to (12), examples of the divalent hydrocarbon group represented by R ′ include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2 -Butylene group, 1,3-butylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, A divalent saturated hydrocarbon group having 1 to 50 carbon atoms, with or without a substituent, such as a group in which at least one hydrogen atom is substituted with a substituent; an ethenylene group, a propenylene group, 3- A butenylene group, a 2-butenylene group, a 2-pentenylene group, a 2-hexenylene group, a 2-nonenylene group, a 2-dodecenylene group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like, 2 carbon atoms with or without substituents A divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms including or not having a substituent, including 50 alkenylene group and ethynylene group; cyclopropylene group, cyclobutylene group, cyclopentylene group, Carbons having or not having a substituent such as a cyclohexylene group, a cyclononylene group, a cyclododecylene group, a norbornylene group, an adamantylene group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A divalent cyclic saturated hydrocarbon group having 3 to 50 atoms; 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, Arylene having 6 to 50 carbon atoms, with or without a substituent, such as a biphenyl-4,4′-diyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent A substitution such as a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, or a group obtained by substituting at least one hydrogen atom of these groups with a substituent. Examples thereof include an alkyleneoxy group having 1 to 50 carbon atoms which may or may not have a group.

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

In the formulas (4) to (12), 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, and an s-butyl group. , T-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, etc. Alkyl groups having 1 to 20 carbon atoms with or without substituents; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, etc. And an aryl group having 6 to 30 carbon atoms, which may or may not have a substituent, such as a group in which at least one hydrogen atom in the group is substituted with a substituent. Among these, from the viewpoint of solubility of the ionic polymer, a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group are preferable. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of substituents are present, they may be the same or different.

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

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

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

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

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

<Structural Unit Represented by Formula (13)>
In formula (13), R ¹ is a monovalent group containing a group represented by formula (14), and Ar ¹ has a (2 + n4) -valent aromatic group with or without a substituent other than R ^1. Represents a group, and n4 represents an integer of 1 or more.

The group represented by the formula (14) may be directly bonded to Ar ¹ , for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, nonylene group, dodecylene group, cyclopropylene. Groups, cyclobutylene groups, cyclopentylene groups, cyclohexylene groups, cyclononylene groups, cyclododecylene groups, norbornylene groups, adamantylene groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. An alkylene group having 1 to 50 carbon atoms with or without a substituent; oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene group, oxynonylene group, oxide Decylene group, cyclopropyleneoxy group, cyclobutyleneoxy group, cyclopentyleneoxy Si group, cyclohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbornyleneoxy group, adamantyleneoxy group, and at least one hydrogen atom in these groups is substituted with a substituent An oxyalkylene group having 1 to 50 carbon atoms, which may or may not have a substituent; an imino group which may or may not have a substituent; a silylene group which may or may not have a substituent; An ethenylene group with or without a group; an ethynylene group; a methanetriyl group with or without a substituent; even if bonded to Ar ¹ through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom Good.

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

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

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

Examples of the (2 + n4) -valent aromatic group represented by Ar ¹ in Formula (13) include (2 + n4) -valent aromatic hydrocarbon groups and (2 + n4) -valent aromatic heterocyclic groups. Among these, a carbon atom alone or a (2 + n4) -valent aromatic group composed of a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom is preferable. Examples of the (2 + n4) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a monocyclic aromatic ring such as a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring or an azadiazole ring; a group consisting of the monocyclic aromatic ring A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a condensed polycyclic aromatic ring in which two or more rings selected from the above are condensed; and consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from an aromatic ring assembly formed by linking two or more aromatic rings selected from the group by a single bond, ethenylene group or ethynylene group; Next to an aromatic ring or set of aromatic rings A (2 + n4) -valent group obtained by removing (2 + n4) hydrogen atoms from a bridged polycyclic aromatic ring having a bridge in which two matching aromatic rings are bridged by a divalent group such as a methylene group, an ethylene group, or a carbonyl group Etc.

Examples of the monocyclic aromatic ring include the following rings.

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

Examples of the aromatic ring assembly include the following rings.

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

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

In the formula (14), examples of the (1 + m1 + m2) -valent organic group represented by R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m1 + m2) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl An aryl group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent (M1 + m2) groups excluding hydrogen atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyl Substitution, such as an oxy group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m1 + m2) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a group; removing (m1 + m2) hydrogen atoms from an amino group having a substituent containing a carbon atom A group obtained by removing (m1 + m2) hydrogen atoms from a silyl group having a substituent containing a carbon atom. It is. Among these, from the viewpoint of ease of synthesis of the raw material monomer, a group obtained by removing (m1 + m2) hydrogen atoms from an alkyl group, a group obtained by removing (m1 + m2) hydrogen atoms from an aryl group, and an alkoxy group ( A group in which m1 + m2) hydrogen atoms have been removed is preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

In the formula (16), examples of the (1 + m3 + m4) -valent organic group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group in which (m3 + m4) hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl An aryl group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent (M3 + m4) groups excluding hydrogen atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyl Substitution, such as an oxy group, a cyclohexyloxy group, a cyclononyloxy group, a cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m3 + m4) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a group; removing (m3 + m4) hydrogen atoms from an amino group having a substituent containing a carbon atom A group obtained by removing (m3 + m4) hydrogen atoms from a silyl group having a substituent containing a carbon atom. It is. Among these, from the viewpoint of ease of synthesis of the raw material monomer, a group obtained by removing (m3 + m4) hydrogen atoms from an alkyl group, a group obtained by removing (m3 + m4) hydrogen atoms from an aryl group, and an alkoxy group ( A group in which m3 + m4) hydrogen atoms have been removed is preferred.

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

The group represented by the formula (18) and the group represented by the formula (19) may be directly bonded to Ar ³ , for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene. Group, nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group, adamantylene group, at least one hydrogen in these groups An alkylene group having 1 to 50 carbon atoms, which may or may not have a substituent, such as a group in which an atom is substituted with a substituent; an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group Oxyhexylene group, oxynonylene group, oxide decylene group, cyclopropyleneoxy group, cyclobutyleneoxy Group, cyclopentyleneoxy group, cyclohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbonyleneoxy group, adamantyleneoxy group, at least one hydrogen atom in these groups An oxyalkylene group having 1 to 50 carbon atoms, with or without a substituent, such as a group substituted with a substituent; an imino group with or without a substituent; with or with a substituent No silylene group; an ethenylene group with or without a substituent; an ethynylene group; a methanetriyl group with or without a substituent; through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, to Ar ³ It may be bonded.

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

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

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

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

Examples of the (2 + n6 + n7) -valent aromatic group represented by Ar ³ in Formula (17) include a (2 + n6 + n7) -valent aromatic hydrocarbon group and a (2 + n6 + n7) -valent aromatic heterocyclic group. Among these, a carbon atom alone or a (2 + n6 + n7) -valent aromatic group composed of a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom is preferable. Examples of the (2 + n6 + n7) -valent aromatic group include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan ring, a pyrrole ring, a pyrazole ring, A (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from a monocyclic aromatic ring such as an imidazole ring or an oxazole ring; a condensation in which two or more rings selected from the group consisting of the monocyclic aromatic rings are condensed A (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from the polycyclic aromatic ring; two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring; (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from an aromatic ring assembly connected by a single bond, ethenylene group or ethynylene group; adjacent to the condensed polycyclic aromatic ring or the aromatic ring assembly (2 + n6 + n7) -valent group obtained by removing (2 + n6 + n7) hydrogen atoms from a bridged polycyclic aromatic ring having a bridge in which two aromatic rings are bridged by a divalent group such as a methylene group, an ethylene group, or a carbonyl group Etc.

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

The (2 + n6 + n7) -valent aromatic group is a ring represented by the formula 1 to 5, 7 to 10, 13, 14, 26 to 29, 37 to 39 or 41 from the viewpoint of ease of synthesis of the raw material monomer. A group obtained by removing (2 + n6 + n7) hydrogen atoms from the ring is preferred, and a group obtained by removing (2 + n6 + n7) hydrogen atoms from the ring represented by formula 1, 37 or 41 is more preferred, represented by formula 1, 38 or 42 A group obtained by removing (2 + n6 + n7) hydrogen atoms from the ring is more preferable.

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

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

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

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

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

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

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

The group represented by the formula (21) and the group represented by the formula (22) may be directly bonded to Ar ⁴ , for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene. Group, nonylene group, dodecylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclononylene group, cyclododecylene group, norbornylene group, adamantylene group, at least one hydrogen in these groups An alkylene group having 1 to 50 carbon atoms, which may or may not have a substituent, such as a group in which an atom is substituted with a substituent; an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group Oxyhexylene group, oxynonylene group, oxide decylene group, cyclopropyleneoxy group, cyclobutyleneoxy Group, cyclopentyleneoxy group, cyclohexyleneoxy group, cyclononyleneoxy group, cyclododecyleneoxy group, norbonyleneoxy group, adamantyleneoxy group, at least one hydrogen atom in these groups An oxyalkylene group having 1 to 50 carbon atoms, with or without a substituent, such as a group substituted with a substituent; an imino group with or without a substituent; with or with a substituent No silylene group; an ethenylene group with or without a substituent; an ethynylene group; a methanetriyl group with or without a substituent; through a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, to Ar ⁴ It may be bonded.

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

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

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

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

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

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

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

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

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

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

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

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

<Example of Structural Unit Represented by Formula (13)>
As the structural unit represented by the formula (13), from the viewpoint of the electron transport property of the obtained ionic polymer, the structural unit represented by the following formula (23) and the structural unit represented by the formula (24) Is preferable, and the structural unit represented by Formula (24) is more preferable.

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

In the formula (23), examples of the (1 + m9 + m10) -valent organic group represented by R ¹³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, and t-butyl. A substituent such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent. A group obtained by removing (m9 + m10) hydrogen atoms from an alkyl group having 1 to 20 carbon atoms with or without: phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl An aryl group having 6 to 30 carbon atoms, with or without a substituent, such as a group, a 9-anthracenyl group, or a group in which at least one hydrogen atom in these groups is substituted with a substituent A group in which (m9 + m10) hydrogen atoms have been removed from the group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy Groups, cyclopentyloxy groups, cyclohexyloxy groups, cyclononyloxy groups, cyclododecyloxy groups, norbornyloxy groups, adamantyloxy groups, groups in which at least one hydrogen atom in these groups is substituted with a substituent, etc. A group obtained by removing (m9 + m10) hydrogen atoms from an alkoxy group having 1 to 50 carbon atoms with or without a substituent; (m9 + m10) hydrogens from an amino group having a substituent containing a carbon atom A group excluding atoms; (m9 + m10) hydrogen atoms from a silyl group having a substituent containing a carbon atom; Like stomach group. Among these, from the viewpoint of ease of synthesis of the raw material monomer, a group obtained by removing (m9 + m10) hydrogen atoms from an alkyl group, a group obtained by removing (m9 + m10) hydrogen atoms from an aryl group, and an alkoxy group ( A group in which m9 + m10) hydrogen atoms have been removed 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 s-butyl group, a t-butyl group, It has a substituent such as a pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, or a group obtained by substituting at least one hydrogen atom of these groups with a substituent. Or a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, which is not present; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9- One hydrogen atom from an aryl group having 6 to 30 carbon atoms, which may or may not have a substituent, such as an anthracenyl group or a group in which at least one hydrogen atom in these groups is substituted with a substituent. Excluded group Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, dodecyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group , A cyclododecyloxy group, a norbornyloxy group, an adamantyloxy group, a group in which at least one hydrogen atom in these groups is substituted with a substituent, and the like, having 1 or less carbon atoms A group obtained by removing one hydrogen atom from 50 alkoxy groups; a group obtained by removing one hydrogen atom from an amino group having a substituent containing a carbon atom; one from a silyl group having a substituent containing a carbon atom And a group in which a hydrogen atom is removed. Among these, from the viewpoint of easy synthesis of the raw material monomer, a group in which one hydrogen atom is removed from an alkyl group, a group in which one hydrogen atom is removed from an aryl group, and one hydrogen atom from an alkoxy group Groups other than are preferred.

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

[In the formula (24), R ¹³ represents a (1 + m11 + m12) -valent organic group, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 have the same meaning as described above. M11 and m12 each independently represents an integer of 1 or more, and R ¹³ , m 11, m 12, Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 When there are a plurality of each, they may be the same or different. ]

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

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

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

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

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

<Example of structural unit represented by 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 electron transport properties of the obtained ionic polymer. The structural unit represented by formula (27) is more preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As the structural unit represented by the formula (17), the structural unit represented by the formula (30) is preferable from the viewpoint of durability of the obtained ionic polymer.

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

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

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

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

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

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

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

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

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

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

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

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

[In formula (33), Ar ⁵ represents a divalent aromatic group with or without a substituent or a divalent aromatic amine residue with or without a substituent, and X ′ represents a substituted group. Represents an imino group with or without a group, a silylene group with or without a substituent, an ethenylene group with or without a substituent, or an ethynylene group, and m33 and m34 are each independently 0 or 1 And at least one of m33 and m34 is 1. ]

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

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

Examples of the monocyclic aromatic ring include the following rings.

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

Examples of the aromatic ring assembly include the following rings.

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

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

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

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

[In the formula (34), Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ are each independently an arylene group having or not having a substituent, or a divalent heterocyclic ring having or without a substituent. Each of Ar ¹⁰ , Ar ¹¹ and Ar ¹² independently represents an aryl group with or without a substituent or a monovalent heterocyclic group with or without a substituent, and n10 and m35 represents 0 or 1 each independently. ]

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

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

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

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

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

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

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

The aromatic amines represented by Formulas 101 to 110 may have a substituent as long as a divalent aromatic amine residue can be generated. Examples of the substituent include the same substituents as those exemplified in the description of Q ¹ described above. When a plurality of the substituents are present, they may be the same or different.

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

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

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

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

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

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

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

<Terminal unit>
Examples of the terminal structural unit (terminal group) of the ionic polymer used in the present invention include a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl, pentyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, lauryl methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy , S-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy Group, lauryloxy group, methylthio group, ethylthio group, Pyrthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, laurylthio group, methoxy Phenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, s-butoxyphenyl group, t-butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxy Phenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctylo Siphenyl group, lauryloxyphenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t-butylphenyl group, Pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group , Dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclo Hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, Dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂₎ Alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, (phenyl-C ₁ ~ C ₁₂ Al ) Amino group, (C ₁ ~ C ₁₂ alkoxyphenyl -C ₁ ~ C ₁₂ alkyl) amino group, (C ₁ ~ C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkyl) amino group, di (C ₁ ~ C ₁₂ Alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl- C ₁ -C ₁₂ alkylamino group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethyl Silyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, Le dimethylsilyl group, decyldimethylsilyl group, a 3,7-dimethyl silyl group, lauryl dimethyl silyl group, (phenyl -C ₁ ~ C ₁₂ alkyl) silyl group, (C ₁ ~ C ₁₂ alkoxyphenyl -C ₁ ~ C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) silyl group, (1-naphthyl-C ₁ -C ₁₂ alkyl) silyl group, (2-naphthyl-C ₁ -C ₁₂ alkyl) silyl group, (phenyl-C ₁ -C ₁₂ alkyl) dimethylsilyl group, triphenylsilyl group, tri (p-xylyl) silyl group, tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group Dimethylphenylsilyl group, thienyl group, C ₁ -C ₁₂ alkylthienyl group, pyrrolyl group, furyl group, pyridyl group, C ₁ -C ₁₂ alkyl Examples include rupyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, isoquinolyl group, hydroxy group, mercapto group, fluorine atom, chlorine atom, bromine atom and iodine atom. When a plurality of the terminal structural units are present, they may be the same or different.

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

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

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

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

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

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

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

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

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

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

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

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

<Method for producing ionic polymer>
Next, a method for producing the ionic polymer used in the present invention will be described. As a suitable method for producing the ionic polymer used in the present invention, for example, a compound represented by the following general formula (36) is selected and used as one of the raw materials. ) in -A _a - compound is a structural unit represented by the formula (13), said -A _a - compound is a structural unit represented by the formula (15), said -A _a - is the formula ( 17) A compound which is a structural unit represented by 17) and a compound wherein -A _a -is a structural unit represented by formula (20) are contained as essential raw materials, and this is subjected to condensation polymerization. A method can be mentioned.
Y ⁴ -A _a -Y ⁵ (36)
[In Formula (36), A _a is represented by Formula (3) and one or more groups selected from the group consisting of the group represented by Formula (1) and the group represented by Formula (2). A repeating unit containing a group of at least species is represented, and Y ⁴ and Y ⁵ each independently represent a group involved in condensation polymerization. ]

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

Examples of the compound having two condensation-polymerizable substituents used to contain such other structural units include compounds represented by the formula (37). Thus, in addition to the compound represented by Y ⁴ -A _a -Y ⁵ , the structural unit represented by -A _b- is obtained by condensation polymerization of the compound represented by Formula (37). Furthermore, the ionic polymer used in the present invention can be produced.
Y ⁶ -A _b -Y ⁷ (37)
[In the formula (37), _Ab is a structural unit represented by the general formula (33) or a structural unit represented by the general formula (35), and Y ⁶ and Y ⁷ are each independently a condensation polymerization. The group which participates in is shown. ]

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

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

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

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

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

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

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

In addition, as a phosphonate methyl group that can be selected as a group involved in the condensation polymerization,
Following formula:
-CH ₂ PO (OR ^d ) ₂
(Wherein, R ^d represents an alkyl group, an aryl group, or an arylalkyl group).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As a solvent used for film formation from such a solution, for example, alcohols other than water, ethers, esters, nitrile compounds, nitro compounds, alkyl halides, aryl halides, thiols, Of the solvents such as sulfides, sulfoxides, thioketones, amides, and carboxylic acids, those having a solubility parameter of 9.3 or more are preferable. Examples of the solvent (values in parentheses represent solubility parameter values of each solvent) include methanol (12.9), ethanol (11.2), 2-propanol (11.5), 1- Butanol (9.9), t-butyl alcohol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7), N, N-dimethylformamide (11.5), dimethyl sulfoxide (12.8), acetic acid (12.4), nitrobenzene (11.1), nitromethane (11.0), 1,2-dichloroethane (9.7), dichloromethane (9.6), chlorobenzene (9.6) ), Bromobenzene (9.9), dioxane (9.8), propylene carbonate (13.3), pyridine (10.4), carbon disulfide (10.0), and a mixed solvent thereof. Be . Here, a mixed solvent obtained by mixing two kinds of solvents (solvent 1 and solvent 2) will be described. The solubility parameter (δ _m ) of the mixed solvent is δ _m = δ ₁ × φ ₁ + δ _2. Xφ ₂ (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 layer containing the ionic polymer varies depending on the ionic polymer used, so the driving voltage and luminous efficiency should be selected to be appropriate, and a thickness that does not cause pinholes is required. It is. From the viewpoint of lowering the driving voltage of the element, the film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and even more preferably 2 nm to 200 nm. From the viewpoint of protecting the light emitting layer, the film thickness is preferably 5 nm to 1 μm.

Among the above-described ionic polymers used in the present invention, some preferred examples are shown as experimental examples of synthetic examples and organic EL devices produced using the synthesized ionic polymers. . The following experimental examples explain the present invention more specifically, but the present invention is not limited to the following experimental examples.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were determined by using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation: HLC-8220 GPC), polystyrene equivalent weight average molecular weight and number average molecular weight. As sought. The sample to be measured was dissolved in tetrahydrofuran so as to have a concentration of about 0.5% by weight, and 50 μL was injected into GPC. Furthermore, tetrahydrofuran was used as the mobile phase of GPC and allowed to flow at a flow rate of 0.5 mL / min. The structural analysis of the polymer was performed by ¹ H-NMR analysis using a 300 MHz NMR spectrometer manufactured by Varian. In addition, the measurement was performed by dissolving the sample in a soluble heavy solvent (a solvent in which a hydrogen atom in a solvent molecule was substituted with a deuterium atom) so as to have a concentration of 20 mg / mL. The orbital energy of the highest occupied molecular orbital (HOMO) of the polymer was determined by measuring the ionization potential of the polymer and using the obtained ionization potential as the orbital energy. On the other hand, the orbital energy of the lowest unoccupied molecular orbital (LUMO) of the polymer was obtained by calculating the energy difference between HOMO and LUMO and using the sum of the value and the ionization potential measured above as the orbital energy. . For the measurement of ionization potential, a photoelectron spectrometer (trade name “AC-2” manufactured by Riken Keiki Co., Ltd.) was used. The energy difference between HOMO and LUMO was determined from the absorption terminal by measuring the absorption spectrum of the polymer using an ultraviolet / visible / near infrared spectrophotometer (trade name “Cary 5E” manufactured by Varian).

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

[Reference Example 2]
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis [3-ethoxycarbonyl-4- [2- [2- ( Synthesis of 2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound B) Compound A (15 g), bis (pinacolato) diboron (8.9 g), [1,1′-bis (diphenylphos) under nitrogen atmosphere Fino) ferrocene] dichloropalladium (II) dichloromethane complex (0.8 g), 1,1′-bis (diphenylphosphino) ferrocene (0.
5 g), potassium acetate (9.4 g), and dioxane (400 mL) were mixed, heated to 110 ° C., and heated to reflux for 10 hours. The reaction liquid was filtered after standing_to_cool and the filtrate was concentrate | evaporated under reduced pressure. The reaction mixture was washed 3 times with methanol. The precipitate was dissolved in toluene, and activated carbon was added to the solution and stirred. Thereafter, filtration is performed, and the filtrate is concentrated under reduced pressure to give 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis. [3-Ethoxycarbonyl-4- [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] phenyl] -fluorene (Compound B) (11.7 g) was obtained.

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

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

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

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

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

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

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

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

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

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

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

N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-butyl-2,6-dimethylphenyl) 1,4-phenylenediamine is disclosed in, for example, JP-A-2008-74917. It can be synthesized by the method described in the publication.

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

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

The number average molecular weight in terms of polystyrene of the polymer D was 2.7 × 10 ⁴ . The polymer D consists of a structural unit represented by the formula (J).

3,7-dibromo-N- (4-n-butylphenyl) phenoxazine is based on the method described in JP-A-2007-70620 or the method described in JP-A-2004-137456. Synthesized with reference.

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

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

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

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

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

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

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

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

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

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

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

The number average molecular weight in terms of polystyrene of the polymer G was 6.0 × 10 ⁴ . The polymer G consists of a structural unit represented by the following formula (P).

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

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

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

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

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

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

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

The number average molecular weight in terms of polystyrene of the polymer I was 2.0 × 10 ³ . The polymer I is represented by the formula (T). In addition, 2- (4,4,5,5-tetramethyl-1,2,3-dioxaboran-2-yl) -9,9-dioctylfluorene is, for example, The Journal of Physical Chemistry B 2000, 104, 9118. It can be synthesized by the method described in -9125.

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

[Reference Example 17]
Synthesis of Compound E Under a nitrogen atmosphere, 2,7-dibromo-9-fluorenone (92.0 g, 272 mmol) and diethyl ether (3.7 L) were mixed, cooled to 0 ° C., and 1 mol / L methylmagnesium iodide. -Diethyl ether solution (0.5 L, 545 mmol) was added dropwise and stirred for 3 hours. An aqueous ammonium chloride solution was added to the reaction mixture to remove the aqueous layer, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain compound E (92.81 g, 262 mmol, yield 96%).

[Reference Example 18]
Synthesis of Compound F Under a nitrogen atmosphere, Compound E (83.0 g, 234 mmol), p-toluenesulfonic acid monohydrate (4.49 g, 23.6 mmol), and chloroform (2.5 L) were refluxed for 1 hour. An aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer was removed. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain Compound F (73.6 g, 219 mmol, 93% yield).

[Reference Example 19]
Synthesis of Compound G Under nitrogen atmosphere, compound F (70.0 g, 208 mmol), ethyl salicylate (104 g, 625 mmol), mercaptoacetic acid (4.20 g, 45.6 mmol), and methanesulfonic acid (1214 g) were added at 70 ° C. for 8 hours. The reaction mixture was added dropwise to ice water and the precipitated solid was collected by filtration and washed with methanol. The crude product was purified by silica gel column chromatography to obtain compound G (52.14 g, 104 mmol, yield 50%).

[Reference Example 20]
Synthesis of Compound H Compound G (41.2 g, 82.0 mmol), 2- [2- (2-methoxyethoxy) ethoxy] -ethyl-p-toluenesulfonate (75.8 g, 238 mmol), dimethylformamide under nitrogen atmosphere (214 g), potassium carbonate (54.4 g, 394 mmol), and 18-crown-6 (4.68 g, 18 mmol) were stirred at 105 ° C. for 2 hours, and the reaction mixture was added to water and extracted with ethyl acetate. The crude product obtained by drying the organic layer with anhydrous sodium sulfate and concentrating under reduced pressure was purified by silica gel column chromatography to obtain compound H (40.2 g, 62.0 mmol, yield 76%).

¹ H NMR (400 MHz, CDCl ₃ , rt)
δ (ppm) 1.37 (3H), 1.84 (3H), 3.36 (3H), 3.53 (2H), 3.58-3.79 (6H), 3.73 (2H), 4.12 (2H), 4.34 (2H), 6.80 (1H), 6.90 (1H), 7.28 (2H), 7.48 (2H), 7.58 (2H), 7 .70 (1H).

[Reference Example 21]
Synthesis of Compound I Compound H (28.4 g, 43.8 mmol), bis (pinacolato) diboron (24.30 g, 95.7 mol), [1,1′-bis (diphenylphosphino) ferrocene] palladium under nitrogen atmosphere (II) Dichloride dichloromethane adduct (0.35 g, 0.4 mmol), 1,1′-bis (diphenylphosphino) ferrocene (0.24 g, 0.4 mmol), potassium acetate (25.60 g, 260 mmol), And 1,4-dioxane (480 mL) were stirred at 120 ° C. for 17 hours and the reaction mixture was filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure, purified by silica gel column chromatography, and then purified by recrystallization to obtain compound I (18.22 g, 24.5 mmol, yield 56%).

¹ H NMR (400 MHz, CDCl ₃ , rt)
δ (ppm) 1.30-1.47 (27H), 1.88 (3H), 3.35 (3H), 3.53 (2H), 3.60-3.69 (4H), 3.73 (2H), 3.84 (2H), 4.10 (2H), 4.34 (2H), 6.74 (1H), 6.87 (1H), 7.58 (2H), 7.72- 7.89 (5H).

[Reference Example 22]
Synthesis of Polymer J Compound H (0.47 g), Compound I (0.48 g), dichlorobis (triphenylphosphine) palladium (0.6 mg), tetrabutylammonium bromide (6 mg), toluene (6 mL) under an argon atmosphere A 2 mol / L aqueous sodium carbonate solution (2 mL) was stirred at 105 ° C. for 6 hours, and then phenylboronic acid (35 mg) was added and stirred at 105 ° C. for 14 hours. Sodium diethyldithiocarbamate trihydrate (0.65 g) and water (13 mL) were added to the reaction mixture, and the mixture was stirred at 80 ° C. for 2 hours. The mixture was added dropwise to methanol, and the precipitate was collected by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel chromatography. The eluate was added dropwise to methanol, and the precipitate was collected by filtration and dried to obtain polymer J (0.57 g).

The number average molecular weight in terms of polystyrene of the polymer J was 2.0 × 10 ⁴ . The polymer J consists of a structural unit represented by the formula (V).

[Experimental Example 13]
Synthesis of Polymer J Cesium Salt Under argon atmosphere, Polymer J (0.20 g), THF (18 mL), methanol (9 mL), cesium hydroxide monohydrate (97 mg), and water (1 mL) were added at 65 ° C. Stir for 2 hours, then add methanol (52 mL) and stir at 65 ° C. for 6 hours. The reaction mixture was concentrated and dried, methanol was added to the solid and filtered, the filtrate was added dropwise to isopropanol, and the solid was collected by filtration and dried to obtain a polymer J cesium salt (0.20 g). The obtained polymer J cesium salt is referred to as a conjugated polymer compound 13. The conjugated polymer compound 13 is composed of a structural unit represented by the formula (W).

The conjugated polymer compound 13 had a HOMO orbital energy of −5.51 eV and a LUMO orbital energy of −2.64 eV.

[Reference Example 23]
Synthesis of Compound J 2,7-Dibromo-9,9-bis (3,4-dihydroxy) -fluorene (138.4 g), 2- [2- (2-methoxyethoxy) ethoxy] -ethyl- under a nitrogen stream p-Toluenesulfonate (408.6 g), potassium carbonate (358.5 g) and acetonitrile (2.5 L) were mixed and heated to reflux for 3 hours. After allowing to cool, the reaction mixture was filtered off, the filtrate was concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound J (109.4).

[Reference Example 24]
Synthesis of Compound K Compound J (101.2 g), bis (pinacolato) diboron (53.1 g), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (3) under nitrogen atmosphere 0.7 g), 1,1′-bis (diphenylphosphino) ferrocene (5.4 g), potassium acetate (90.6 g) and dioxane (900 mL) were mixed, heated to 110 ° C., and heated to reflux for 8 hours. . After allowing to cool, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound K (51.4 g).

[Reference Example 25]
Synthesis of Polymer K Compound K (0.715 g), Compound J (0.426 g), aliquot 336 (6.60 mg), bis (triphenylphosphine) dichloropalladium (0.460 mg), 2 mol / L aqueous sodium carbonate solution (10 mL) ), Toluene (20 mL) was added, and the mixture was stirred at 105 ° C. for 5 hours, and then phenylboronic acid (32 mg) was added and stirred at 105 ° C. for 6 hours. Sodium diethyldithiocarbamate trihydrate (0.72 g) and water (14 mL) were added to the reaction mixture, and the mixture was stirred at 80 ° C. for 2 hours. The mixture was added dropwise to methanol, and the precipitate was collected by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel chromatography, and the eluate was concentrated and dried. The concentrate was dissolved in toluene, added dropwise to methanol, and the precipitate was collected by filtration and dried to obtain polymer K (0.55 g).

The number average molecular weight in terms of polystyrene of the polymer K was 2.3 × 10 ⁴ . The polymer K consists of a structural unit represented by the formula (X).

[Experimental Example 14]
Synthesis of Polymer K Cesium Salt Under argon atmosphere, polymer K (0.15 g), THF (20 mL), methanol (10 mL), cesium hydroxide monohydrate (103 mg), and water (1 mL) were added at 65 ° C. Stir for 2 hours, then add methanol (20 mL) and stir at 65 ° C. for 2 hours. The reaction mixture was concentrated and dried, and methanol was added to the solid and filtered. The obtained filtrate was concentrated and dried, and the obtained solid was washed with water and dried to obtain a cesium salt of polymer K (0.14 g). The obtained cesium salt of polymer K is referred to as conjugated polymer compound 14. The conjugated polymer compound 14 is composed of a structural unit represented by the formula (Y).

The orbital energy of HOMO of the conjugated polymer compound 14 was −5.56 eV, and the orbital energy of LUMO was −2.67 eV.

[Reference Example 26]
Synthesis of Compound L Under a nitrogen atmosphere, 5-bromo-2-hydroxybenzoic acid (92.85 g), ethanol (1140 mL), and concentrated sulfuric acid (45 mL) were refluxed for 48 hours and concentrated under reduced pressure, and then ethyl acetate (1000 mL) was added. In addition, the organic layer was washed with water and a 10 wt% aqueous sodium carbonate solution. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain compound L (95.38 g, yield 91%).

[Reference Example 27]
Synthesis of Compound M Dichloromethane adduct of Compound L (95.0 g), bis (pinacolato) diboron (108.5 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride under nitrogen atmosphere (3.3 g), 1,1′-bis (diphenylphosphino) ferrocene (2.2 g), potassium acetate (117.2 g), and 1,4-dioxane (1.3 L) were stirred at 105 ° C. for 22 hours. The reaction mixture was filtered and washed with dioxane and toluene. The filtrate was concentrated under reduced pressure, ethyl acetate was added, washed with saturated brine, the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain compound M (90.1 g, 308 mmol).

[Reference Example 28]
Synthesis of Compound N Under a nitrogen atmosphere, 1,5-dihydroxynaphthalene (15.0 g), triethylamine (28.5 g), and chloroform (150 mL) were mixed and cooled to 0 ° C., and trifluoromethanesulfonic anhydride (68 0.7 g) was added dropwise and stirred for 1 hour. Water and chloroform were added to the reaction mixture to remove the aqueous layer, and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the resulting solid was purified by recrystallization to obtain Compound N (31.46 g). In the following formula, Tf represents a trifluoromethylsulfonyl group.

[Reference Example 29]
Synthesis of Compound O Under a nitrogen atmosphere, Compound N (16.90 g), Compound M (23.30 g), tetrakis (triphenylphosphine) palladium (0) (4.60 g), potassium phosphate (42.30 g), and 1,2-Dimethoxyethane (340 mL) was stirred at 80 ° C. for 14 hours, the reaction mixture was filtered and washed with chloroform and methanol. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound O (8.85 g).

[Reference Example 30]
Synthesis of Compound P Compound O (8.80 g), 2- [2- (2-methoxyethoxy) ethoxy] -ethyl-p-toluenesulfonate (12.52 g), dimethylformamide (380 mL), potassium carbonate under nitrogen atmosphere (13.32 g) and 18-crown-6 (1.02 g) were stirred at 100 ° C. for 23 hours, and the reaction mixture was added to water and extracted with ethyl acetate. The organic layer was washed with an aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain compound P (7.38 g).

[Reference Example 31]
Synthesis of Compound Q Compound P (5.53 g), bis (pinacolato) diboron (11.25 g), (1,5-cyclooctadiene) (methoxy) iridium (I) dimer (0.15 g) under nitrogen atmosphere , Sigma-Aldrich), 4,4′-di-tert-butyl-2,2′-dipyridyl (0.12 g, Sigma-Aldrich), and 1,4-dioxane (300 mL) at 110 ° C. for 19 hours. Stir and concentrate the reaction mixture in vacuo. The crude product was purified by silica gel column chromatography and then purified by recrystallization to obtain compound Q (5.81 g).

¹ H NMR (400 MHz, CDCl ₃ , rt)
δ (ppm) 1.27-1.41 (30H), 3.39 (6H), 3.57 (4H), 3.66-3.75 (8H), 3.83 (4H), 3.99 (4H), 4.27-4.42 (8H), 7.13 (2H), 7.60 (2H), 7.76 (2H), 7.93 (2H), 8.30 (2H).

[Reference Example 32]
Synthesis of Polymer L In an argon atmosphere, Compound J (0.53 g), Compound Q (0.43 g), dichlorobis (triphenylphosphine) palladium (0.3 mg), Aliquat 336 (5 mg, manufactured by Sigma-Aldrich), toluene ( 12 mL), a 2 mol / L aqueous sodium carbonate solution (1 mL) was stirred at 105 ° C. for 9 hours, and then phenylboronic acid (23 mg) was added and stirred at 105 ° C. for 14 hours. Sodium diethyldithiocarbamate trihydrate (0.40 g) and water (8 mL) were added to the reaction mixture, and the mixture was stirred at 80 ° C. for 2 hours. The mixture was added dropwise to methanol, and the precipitate was collected by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel chromatography. The eluate was added dropwise to methanol, and the precipitate was collected by filtration and dried to obtain polymer L (0.56 g).

The number average molecular weight in terms of polystyrene of the polymer L was 3.4 × 10 ⁴ . The polymer L consists of a structural unit represented by the formula (Z).

[Experimental Example 15]
Synthesis of Polymer L Cesium Salt Under argon atmosphere, polymer L (0.25 g), THF (13 mL), methanol (6 mL), cesium hydroxide monohydrate (69 mg), and water (1 mL) at 65 ° C. After stirring for 6 hours, the reaction mixture was concentrated and added dropwise to isopropanol, and the solid was collected by filtration and dried. Methanol was added to the solid and filtered, the filtrate was added dropwise to isopropanol, and the solid was collected by filtration and dried to obtain a polymer L cesium salt (0.19 g). The obtained polymer L cesium salt is referred to as a conjugated polymer compound 15. The conjugated polymer compound 15 is composed of a structural unit represented by the formula (AA).

The conjugated polymer compound 15 had a HOMO orbital energy of −5.50 eV and a LUMO orbital energy of −2.65 eV.

[Experimental Example 16]
<Production of organic EL element>
A hole injection material solution was applied onto an ITO anode (film thickness: 45 nm) patterned on the surface of a glass substrate, and a hole injection layer was formed to a film thickness of 60 nm by spin coating. The glass substrate on which the hole injection layer is formed is heated in an inert atmosphere (nitrogen atmosphere) at 200 ° C. for 10 minutes to insolubilize the hole injection layer, and the substrate is naturally cooled to room temperature. A substrate on which was formed was obtained.

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

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

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

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

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

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

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

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

[Experimental Example 17]
An organic EL device 2 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 2 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experiment 18]
In Experimental Example 16, methanol and conjugated polymer compound 1 were mixed, and instead of obtaining a composition containing 0.2% by weight of conjugated polymer compound 1, methanol, water and conjugated polymer compound 3 were mixed (methanol). / Water volume ratio = 20/1), and the organic EL device 3 was obtained in the same manner as in Experimental Example 16 except that the composition containing 0.2% by weight of the conjugated polymer compound 3 was used.

[Experimental Example 19]
An organic EL device 4 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 4 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experiment 20]
An organic EL device 5 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 5 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experimental example 21]
An organic EL device 6 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 6 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experimental example 22]
The organic EL device 7 was obtained in the same manner as in the experimental example except that the conjugated polymer compound 7 was used instead of the conjugated polymer compound 1 in Experimental example 16.

[Experimental example 23]
An organic EL device 8 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 8 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experimental Example 24]
An organic EL device 9 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 9 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experiment 25]
In Example 16, the organic EL device 10 was obtained in the same manner as in Example 16 except that the conjugated polymer compound 10 was used instead of the conjugated polymer compound 1.

[Experiment 26]
In Example 16, the organic EL device 11 was obtained in the same manner as in Example 16 except that the conjugated polymer compound 11 was used instead of the conjugated polymer compound 1.

[Experiment 27]
An organic EL device 12 was obtained in the same manner as in Experimental Example 16 except that the conjugated polymer compound 12 was used instead of the conjugated polymer compound 1 in Experimental Example 16.

[Experiment 28]
In Experimental Example 16, instead of mixing methanol and conjugated polymer compound 1 to obtain a composition containing 0.2% by weight of conjugated polymer compound 1, methanol, conjugated polymer compound 1, Al-doped ZnO nanoparticles ( An organic EL device 13 was obtained in the same manner as in Experimental Example 16 except that a composition mixed with Aldrich was used.

[Experimental example 29]
In Experimental Example 16, instead of mixing methanol and conjugated polymer compound 1 to obtain a composition containing 0.2% by weight of conjugated polymer compound 1, methanol, conjugated polymer compound 1, low molecular compound (manufactured by Aldrich) , 3,5-bis (4-tert-butylphenyl) -4-phenyl-4H-1,2,4-triazole), 0.2% by weight of conjugated polymer compound 1 and 0.2% by weight The organic EL device 14 was obtained in the same manner as in Experimental Example 16 except that the composition containing the low molecular compound was obtained.

[Experiment 30]
In Experimental Example 16, an organic EL device 15 was obtained in the same manner as in Experimental Example 16 except that Ag was used instead of Al.

[Experimental example 31]
In the experimental example 16, an electroluminescent element 16 was obtained in the same manner as in the experimental example 16 except that Au was used instead of Al.

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

The above-mentioned ionic polymer used in the organic EL display device of the present invention is excellent in charge injectability and transportability, is stable in an atmosphere of about normal pressure, and further in the air, and can be easily dissolved in a solution by a solvent. The film can be formed by coating in an atmosphere of about normal pressure or in the air. Therefore, when the layer containing the ionic polymer is used for the electron injection layer of the organic EL element, the manufacturing cost can be reduced and the stability in the manufacturing process can be secured. A manufacturing method and an organic EL display device obtained by the manufacturing method can be provided.

[Configuration of organic EL element]
First, the organic EL element used for the pixel of the organic EL display device of the present invention will be described. As the structure of the organic EL element used in the present invention, at least one light-emitting layer and an electron injection layer are provided between a pair of anodes and cathodes, at least one of which is transparent or translucent. . A low molecular and / or high molecular organic light emitting material is used for the light emitting layer, and the above-mentioned ionic polymer is used for the electron injection layer. The electron injection layer is provided between the light emitting layer and the cathode.

In addition to the above-described cathode, anode, light emitting layer, and electron injection layer, the organic EL element may be provided with a predetermined layer.
Examples of the layer provided between the cathode and the light emitting layer include an electron transport layer and a hole blocking layer in addition to the electron injection layer.
For example, when only one layer is provided between the cathode and the light emitting layer, this layer is referred to as an electron injection layer, and when two or more layers are provided between the cathode and the light emitting layer, the layer in contact with the cathode is referred to as an electron injection layer. The other layers are referred to as an electron transport layer.

The electron injection layer is a layer having a function of improving electron injection efficiency from the cathode, and the electron transport layer is a layer having a function of improving electron injection from the electron injection layer or the electron transport layer closer to the cathode.

When the electron injection layer or the electron transport layer has a function of blocking hole transport, these layers may be referred to as a hole blocking layer.
Having the function of blocking hole transport makes it possible, for example, to produce an element that allows only hole current to flow, and confirm the blocking effect by reducing the current value.

Examples of what is provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer.
When only one layer is provided between the anode and the light emitting layer, this layer is referred to as a hole injection layer. When two or more layers are provided between the anode and the light emitting layer, the layer in contact with the anode is referred to as a hole injection layer. The other layers are referred to as a hole transport layer. The hole injection layer is a layer having a function of improving the hole injection efficiency from the cathode, and the hole transport layer improves the hole injection from the hole injection layer or the hole transport layer closer to the anode. This is a functional layer. In addition, when the hole injection layer or the hole transport layer has a function of blocking electron transport, these layers may be referred to as an electron block layer.
Having the function of blocking electron transport makes it possible, for example, to manufacture an element that allows only electron current to flow and to confirm the blocking effect by reducing the current value.

In addition to the structure in which an electron injection layer is provided between the cathode and the light emitting layer, the organic EL element used for the pixel of the organic EL display device of the present invention further includes electron transport between the cathode and the light emitting layer. Organic EL device provided with a layer, Organic EL device provided with a hole transport layer between the anode and the light emitting layer, Organic provided with a hole transport layer and a hole injection layer between the anode and the light emitting layer EL element etc. are mentioned.
Specifically, the following structures a) to f) are exemplified.
a) Anode / light emitting layer / electron injection layer / cathode b) Anode / hole injection layer / light emitting layer / electron injection layer / cathode c) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / Cathode d) Anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode e) Anode / light emitting layer / electron transport layer / electron injection layer / cathode f) Anode / hole injection layer / hole transport Layer / light emitting layer / electron transport layer / electron injection layer / cathode (wherein / indicates that each layer is laminated adjacently; the same applies hereinafter).

The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

[Configuration of Organic EL Display Device (First Embodiment)]
Next, a first embodiment of the configuration of the organic EL display device according to the present invention will be described with reference to FIG.
FIG. 1 is a schematic sectional view showing a first embodiment of an organic EL display device according to the present invention.

(substrate)
In the case of a so-called top emission type organic EL display device, since emitted light is taken out from the opposite side of the substrate 1, either a transparent substrate or an opaque substrate can be used as the substrate 1. Examples of the opaque substrate include a thin plate made of ceramic such as alumina, a thin metal plate such as stainless steel that has been subjected to an insulation treatment such as surface oxidation, or a thin plate such as a thermosetting resin or a thermoplastic resin.

In the case of a so-called bottom emission type organic EL display device, since the emitted light is taken out from the substrate 1 side, a transparent or translucent substrate 1 is employed. Examples of the substrate 1 include thin plates made of glass, quartz, resin (plastic, plastic film), and the like, and among these, a glass substrate is particularly preferably used.

A circuit unit (not shown) including driving TFTs for driving a plurality of organic EL elements formed on the substrate 1 is provided between the substrate 1 and the pixel electrode 2.

(Anode (pixel electrode))
When the anode (pixel electrode) is composed of a transparent electrode or a semi-transparent electrode, a metal oxide, metal sulfide or metal thin film with high electrical conductivity can be used, and those with high transmittance are preferred. It can be used and is appropriately selected depending on the organic layer to be used. Specifically, for example, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) which is a composite thereof, conductive films such as indium zinc oxide, NESA, gold, platinum, Silver, copper, etc. are used. Among these, ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity. For example, it is 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. is there.

A first bank layer 4 and a second bank layer 5 are formed on the surface of the substrate 1 on which the pixel electrode 2 is formed. The first bank layer 4 is provided mainly in a region excluding each pixel electrode 2, and its end is formed so as to cover the peripheral edge of each pixel electrode 2. The second bank layer 5 is provided on the first bank layer 4 and is composed of a plurality of members extending in a direction orthogonal to the plane of FIG. The plurality of members are arranged at predetermined intervals in the left-right direction in FIG. 1, and are provided between adjacent pixel electrodes 2.

The first bank layer 4 is composed of an organic material or an inorganic material. An acrylic resin, a phenol resin, a polyimide resin, or the like is used as the organic material constituting the first bank layer 4. Further, SiOx, SiNx, or the like is used as the inorganic material constituting the first bank layer 4.

Banks composed of organic materials generally exhibit liquid repellency compared to banks composed of inorganic materials. The second bank layer 5 preferably has liquid repellency in order to retain ink supplied to the area surrounded by the bank layer 5 and prevent overflowing to the outside. On the other hand, the first bank layer 4 is preferably lyophilic because the supplied ink is preferably spread over the bank layer 4. Therefore, it is preferable that the first bank layer 4 is made of an inorganic material and the second bank layer 5 is made of an organic material.

The second bank layer 5 is made of an organic material or an inorganic material. An acrylic resin, a phenol resin, a polyimide resin, or the like is used as the organic material constituting the second bank layer 5. For the inorganic material constituting the second bank layer 5, SiOx, SiNx, or the like is used.

The inside of the opening of the first bank layer 4 constitutes a pixel area. The second bank layer 5 is larger in height than the first bank layer 4, and a plurality of second bank layers 5 are arranged substantially in parallel with each other. A plurality of pixel regions defined by one bank layer 4 are arranged in a line. One of RGB light emitting materials is collectively applied to the plurality of pixel regions arranged in a row. This batch application is enabled by the second bank layer 5.

On the exposed surface (pixel region) of each pixel electrode 2 surrounded by the first bank layer 4, a hole injection layer 6 and a hole transport layer 7 are usually laminated in this order.

(Hole injection layer)
The hole injection layer is provided between the anode and the light emitting layer. Examples of the material for forming the hole injection layer include phenylamine compounds, starburst amine compounds, phthalocyanine compounds, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, Examples include polythiophene derivatives.

The method for forming the hole transport layer is not limited, but for example, a method by film formation from a solution is exemplified.

The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Such solvents include water, chlorine solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, and ethyl acetate. And ester solvents such as butyl acetate and ethyl cellosolve acetate.

Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

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

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

The method for forming the hole transport layer is not limited, but for a low molecular hole transport material, a method of forming a film from a mixed solution with a polymer binder is exemplified. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those that do not strongly absorb visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

(Light emitting layer)
After the hole injection layer 6 and the hole transport layer 7 are formed on the pixel electrode 2 in each pixel region, red, green, and blue (RGB) light is formed on the uppermost hole transport layer 7 in the present embodiment. The light emitting layer 81, the light emitting layer 82, and the light emitting layer 83 are formed. As the light emitting material for forming the light emitting layer, a known light emitting material capable of emitting fluorescence or phosphorescence is used. The illustrated embodiment is a case where full-color display is performed, and the emission wavelength band is formed corresponding to each of the three primary colors of light. That is, three light emitting layers are provided: an R light emitting layer 81 corresponding to red light emission wavelength band, a G light emitting layer 82 corresponding to green color, and a B light emitting layer 83 corresponding to blue color. Three types of organic EL elements each having any one of the R light emitting layer 81, the G light emitting layer 82, and the B light emitting layer 83 emit light at a predetermined light intensity, respectively, so that an organic EL display device for full color display as a whole is obtained. Realized. In this specification, each organic EL element constitutes one pixel. In another embodiment, a blue organic EL element that emits blue light and another organic EL element that emits light having a spectrum different from that of blue are provided, and one type of organic EL element is used as the other organic EL element. Or, three or more types of organic EL elements may be provided.

(Material constituting the light emitting layer)
In the present invention, the light emitting layer is preferably an organic light emitting layer, and is usually formed of an organic substance (low molecular compound and / or high molecular compound) that mainly emits fluorescence or phosphorescence and a dopant that assists this. The Examples of the material for forming the light emitting layer that can be used in the present invention include the following.

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

(Metal complex materials)
Examples of metal complex materials include metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyls. Zinc complex, porphyrin zinc complex, europium complex, etc., which has Al, Zn, Be, Ir, etc. as the central metal or rare earth metal such as Tb, Eu, Dy, etc., and oxadiazole, thiadiazole, phenylpyridine, Examples include metal complexes having phenylbenzimidazole, quinoline structure, and the like.

(Polymer material)
Examples of polymer materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinyl carbazole derivatives, and the above dye bodies and metal complex light emitting materials. And the like.

Among the above light emitting materials, examples of materials that emit blue (B) light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and the like. Can be mentioned. Of these, polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.

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

Further, examples of the material that emits red (R) light include a coumarin derivative, a thiophene ring compound, and a polymer thereof, a polyparaphenylene vinylene derivative, a polythiophene derivative, and a polyfluorene derivative. Among these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.

(Dopant material)
A dopant can be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like. The thickness of such a light emitting layer is usually about 20 to 2000 mm.

(Light-emitting layer deposition method)
As a method for forming a light emitting layer containing an organic substance, a method of applying a solution containing a light emitting material on or above a substrate, a vacuum deposition method, a transfer method, or the like can be used. In the present invention, among these, a method by coating is preferable. Specific examples of the solvent used for the film formation from the solution include the same solvents as those for dissolving the hole transport material when forming the hole transport layer from the above solution.

As a method for applying a solution containing a light emitting material on or above the substrate, a printing method such as spin coating, dip coating, ink jet, flexographic printing, gravure printing, slit coating, or the like can be used as appropriate. In the case of a sublimable low-molecular compound, a vacuum deposition method can be used. Furthermore, a method of forming a light emitting layer only at a desired place by laser transfer or thermal transfer can be used.

In the above configuration, when an organic compound layer such as a hole transport layer and a light-emitting layer is formed following the hole injection layer, particularly when both layers are formed by a coating method, the coating is performed first. In some cases, the laminated layer is dissolved in a solvent contained in a solution of a layer to be applied later, making it impossible to produce a laminated structure. In this case, a method of insolubilizing the lower layer in the solvent can be used. The insolubilization method includes a method of adding a crosslinking group to the polymer compound and crosslinking to insolubilize; mixing a low molecular weight compound having a crosslinking group having an aromatic ring typified by aromatic bisazide as a crosslinking agent and crosslinking. Insolubilization method: a method of mixing a low molecular weight compound having a cross-linking group represented by an acrylate group, which does not have an aromatic ring, as a cross-linking agent, cross-linking and insolubilizing, a lower layer is exposed to ultraviolet light to cross-link, and an upper layer And a method of insolubilizing in an organic solvent used for the production of an upper layer, and a method of insolubilizing in an organic solvent used for the production of an upper layer. When the lower layer is heated, the heating temperature is usually 100 ° C. to 300 ° C., and the time is usually 1 minute to 1 hour.

Also, as another method of laminating without dissolving the lower layer other than cross-linking, there is a method of using solutions having different polarities for manufacturing adjacent layers. As such a method, for example, an ink in which a polymer compound dissolved in a polar solvent is dissolved in a polar solvent is used to form a lower layer, and a polymer compound dissolved in a nonpolar solvent is dissolved in a nonpolar solvent. There is a method in which the upper layer is formed using, and the lower layer is not dissolved when the upper layer is formed.

In the present embodiment, the electron injection layer 9 is provided on the

light emitting layers

81, 82, 83. The electron injection layer 9 may be formed directly on the

light emitting layers

81, 82, 83, or may be formed on the formed electron transport layer after forming an electron transport layer (not shown).

(Electron transport material)
Known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, Examples include fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.

Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

There are no particular restrictions on the method of forming the electron transport layer, but in the case of a low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is used. Each method is exemplified by film formation from a molten state. In the present invention, among these, a method by coating is preferable. When forming a film from a solution or a molten state, a polymer binder may be used in combination. Examples of the method for forming the electron transport layer from the solution include the same film formation method as the method for forming the hole transport layer from the above-described solution.

The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

(Electron injection layer)
The electron injection layer is provided in contact with the cathode between the light emitting layer and the cathode.
In the present invention, the electron injection layer is formed from a solution using the ionic polymer described above.

Examples of the method for forming the electron injection layer include a method of forming a film using a solution containing the ionic polymer.

As a solvent used for film formation from such a solution, a solvent having a solubility parameter excluding water of 9.3 or more is preferable. Examples of the solvent (values in parentheses represent solubility parameter values of each solvent) include, for example, methanol (12.9), ethanol (11.2), 2-propanol (11.5), 1-butanol (9.9), t-butyl alcohol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7), N, N-dimethylformamide (11.5), Dimethyl sulfoxide (12.8), acetic acid (12.4), nitrobenzene (11.1), nitromethane (11.0), 1,2-dichloroethane (9.7), dichloromethane (9.6), chlorobenzene (9 .6), bromobenzene (9.9), dioxane (9.8), propylene carbonate (13.3), pyridine (10.4), carbon disulfide (10.0), and mixed solutions of these solvents And the like. Here, a mixed solvent obtained by mixing two kinds of solvents (solvent 1 and solvent 2) will be described. The solubility parameter (δ _m ) of the mixed solvent is δ _m = δ ₁ × φ ₁ + δ _2. Xφ ₂ (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.)

Examples of the film forming method from a solution include spin coating, casting, micro gravure printing, gravure printing, bar coating, roll coating, wire bar coating, dip coating, slit coating, and cap coating. Examples thereof include coating methods such as a coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, and a nozzle coating method.

The film thickness of the electron injection layer varies depending on the polymer (conjugated polymer compound) used, so the driving voltage and the light emission efficiency may be selected to be appropriate values, and the thickness that does not generate pinholes. is required. From the viewpoint of lowering the driving voltage of the element, the film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and even more preferably 2 nm to 200 nm. From the viewpoint of protecting the light emitting layer, the film thickness is preferably 10 nm to 1 μm, more preferably 50 nm to 1 μm, and further preferably 100 nm to 1 μm.

The electron injection layer 9 may be formed only in a region surrounded by the second bank layer 5, and may be formed only on the

light emitting layers

81, 82, 83, for example. Further, for example, as shown in FIG. 1, the electron injection layer 9 may be formed not only in the region surrounded by the second bank layer 5, but also on the second bank layer 5, and is continuous over all pixels. You may form as follows.

As described above, after the electron injection layer 9 is formed in common for all the pixels, the cathode 10 is laminated on the common electron injection layer 9 by film formation from the solution in the same manner for all the pixels.

(Cathode material)
A material having a large work function can be used as the material of the cathode 10. For example, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, palladium, silver, tin, A metal such as tantalum, tungsten, iridium, platinum, gold, lead, or bismuth, an alloy of two or more of the above metals, or graphite or a graphite intercalation compound is used. Among metals, materials that are difficult to oxidize are preferable. Titanium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, palladium, silver, tin, tantalum, tungsten, iridium, platinum, gold, lead, bismuth Etc. are preferable. Moreover, ITO, ZnO, ZTO, IZTO, etc. which are transparent conductive oxides can be used. The cathode 10 may have a laminated structure of two or more layers.

As a method of forming the cathode 10, a method of applying a liquid material in which a cathode material is dispersed in a solvent, or a method of transferring a cathode material layer formed on another support substrate is preferable.
Moreover, the following coating type conductive materials can also be suitably used as the constituent material of the cathode.

As the conductive material, a conductive polymer material is used. As the conductive polymer material, a polymer compound containing ethylenedioxythiophene is preferable. Specifically, 3,4-polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS = 1/20), which is also a constituent material of the hole injection layer, manufactured by Bayer Co., Ltd., trade name “Bytron-p ) "] Is used in a liquid dispersion in a solvent. The liquid is obtained by dispersing 3,4-polyethylenedioxythiophene in polystyrene sulfonic acid as a dispersion medium.

Also, as the conductive material constituting the cathode, conductive fine metal particles may be used instead of the conductive polymer described above or together with the conductive polymer. When the cathode is made of a mixed material of a conductive polymer and metal fine particles, it becomes possible to ensure the conductivity of the cathode while firing the cathode at a relatively low temperature. Specifically, Au, Ag, Al or the like is used as the metal fine particles. In addition to metal fine particles such as Au and Ag, a carbon paste may be employed.

The film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

Note that an auxiliary cathode may be provided on the surface of the cathode in order to increase the conductivity of the entire cathode. The auxiliary cathode also has a function of covering the cathode and protecting it from oxygen, moisture, and the like. The auxiliary cathode is composed of conductive fine metal particles. Such a metal fine particle is not particularly limited as long as it is a chemically stable conductive material. For example, a metal or an alloy such as Al (aluminum), Au (gold), or Ag (silver) can be used. is there. The thickness of the auxiliary cathode is preferably 100 nm to 500 nm, particularly about 200 nm. If the thickness is less than 100 nm, a sufficient protective function may not be obtained. If the thickness exceeds 500 nm, the thermal load during production increases, and the light emitting layer may be adversely affected such as deterioration or alteration. In particular, in the case of a top emission type organic EL device, it is possible to form a sufficiently thin auxiliary cathode so as to have translucency, or to provide conductivity such as ITO having translucency. The auxiliary cathode may be formed using a material.

In the above-described configuration, when each layer such as an electron transport layer, an electron injection layer, and a cathode is formed by a coating method following the light emitting layer, the lower layer is dissolved in a solvent contained in a liquid material of a layer to be applied later. When doing so, the lower layer can be made insoluble in the same manner as exemplified in the method for forming an organic compound layer such as a hole injection layer.

[Method for Manufacturing Organic EL Display Device]
Next, a method for manufacturing the organic EL display device of this embodiment will be described with reference to FIG.

First, a substrate 1 having a plurality of pixel electrodes 2 formed on its surface is prepared. The pixel electrode (anode) 2 is usually made of a conductive material such as ITO.

Next, a first bank layer 4 is formed on the surface of the substrate 1 on which the pixel electrodes 2 are formed so as to surround each pixel electrode 2, and then a plurality of continuous plurality of pixel electrodes 2 are adjacent to each other. A second bank layer 5 is formed. The plurality of second bank layers are arranged substantially parallel to each other in a direction perpendicular to the plane of FIG.

The first bank layer 4 is formed such that a part of the first bank layer 4 is open to each pixel electrode 2 and the surface of each pixel electrode 2 is exposed. Next, a plurality of second bank layers 5 that are continuous between adjacent pixel electrodes 2 surrounded by the first bank layer 4 are formed. The arrangement pattern of the plurality of second bank layers 5 is substantially parallel to each other in a direction perpendicular to the plane of FIG.

As a method for forming the first bank layer 4 and the second organic bank layer 5, when using an inorganic material, it is formed by vapor deposition, and when using an organic material, for example, a resist such as an acrylic resin or a polyimide resin. Is dissolved in a solvent by a coating method such as spin coating or dip coating to form a bank layer. The constituent material of the bank layer may be any material as long as it does not dissolve in the ink solvent described later and is easily patterned by etching or the like.

The first bank layer 4 is formed, for example, by depositing an inorganic material on the entire surface and patterning it using a photolithography technique and an etching technique.

The second bank layer 5 is, for example, coated with an organic material continuously by ink jet between adjacent ones of the plurality of pixel electrodes 2, or patterned using a photolithography technique or an etching technique after the organic material is coated on one surface. Formed by.

Next, a region showing lyophilicity and a region showing liquid repellency are formed on the surface of the bank layer. In this embodiment, the case where each region is formed by plasma processing will be described. The plasma treatment includes a preheating step, a lyophilic step for making the upper surface of the second bank layer 5 and the wall surface of the opening, the exposed surface of the pixel electrode 2 and the upper surface of the first bank layer 4 lyophilic, The second bank layer 5 includes a liquid repellent process for making the upper surface of the second bank layer 5 and the wall surface of the opening liquid repellent, and a cooling process.

Specifically, the base material (substrate 1 including the bank layer) is heated to a predetermined temperature, for example, about 70 to 80 ° C., and then plasma treatment using oxygen as a reactive gas under atmospheric pressure (O 2 plasma) as a lyophilic process. Process). Next, as a lyophobic process, plasma treatment using CF ₄ as a reactive gas (CF ₄ plasma treatment) is performed under atmospheric pressure, and then the substrate heated for the plasma treatment is cooled to room temperature. In the plasma treatment using tetrafluoromethane as a reaction gas, the second bank layer 502 made of an organic substance is selectively made liquid repellent. This imparts lyophilicity and liquid repellency to the desired portion.

Next, the hole injection layer 6 is formed by a hole injection layer forming step. In this hole injection layer forming step, the hole injection layer 6 is formed by film formation from a solution. As film formation from a solution, for example, coating by an ink jet method is preferably used. The hole injection layer forming material described above is selectively applied onto the exposed surface of each pixel electrode 2 by an inkjet method. Thereafter, drying treatment and heat treatment are performed to form the hole injection layer 6 on the pixel electrode 2.

In forming the hole injection layer 6 by the inkjet method, first, an inkjet head (not shown) is filled with a hole injection layer forming material, and the inkjet head and the substrate 1 are moved relative to each other while the inkjet head and the substrate 1 are moved relative to each other. Is opposed to the electrode exposed surface located in the opening of the first bank layer 4. Then, a droplet whose liquid amount per droplet is controlled is discharged from the discharge nozzle to the electrode exposed surface. Next, the discharged droplets are dried, and the hole injection layer 6 is formed by evaporating the dispersion medium and solvent contained in the hole injection layer material.

Next, the hole transport layer 7 is formed in the same manner as the above-described method for forming the hole injection layer 6 using the solution of the hole transport material described above.

Next, the light emitting layer 81, the light emitting layer 82, and the light emitting layer 83 are formed by the light emitting layer forming step. In this light emitting layer formation step, the hole injection layer 6 and the hole transport layer 7 are formed by film formation from a solution as in the case of the hole injection layer 6 and the hole transport layer 7. As the film formation from a solution, for example, a coating method using any of various printing methods including an ink jet method is used. An opening formed in the second organic bank layer 5 by applying a light emitting layer forming material on the hole transport layer 7 by any one of various printing methods including an inkjet method, and then performing a drying process and a heat treatment.

Light emitting layers

81, 82, and 83 are formed in the portion. This light emitting layer is formed for each color. In the light emitting layer forming step, it is preferable to use a nonpolar solvent that is insoluble in the hole transporting layer 70 as the solvent used for the light emitting layer forming material in order to prevent re-dissolution of the hole transporting layer 7. Alternatively, the solvent insolubilization treatment described above is preferably performed on the hole transport layer 7. The same applies to the hole injection layer 6 before the hole transport layer 7 is formed.

(Formation of electron injection layer)
In the present embodiment, the electron injection layer 9 is provided on the

light emitting layers

81, 82, 83. The electron injection layer 9 may be formed directly on the

light emitting layers

81, 82, and 83, or may be formed on the formed electron transport layer after forming the electron transport layer.
In the present embodiment, the electron injection layer 9 is formed so as to cover the light emitting layer 81, the light emitting layer 82, the light emitting layer 83, and the second bank layer 5. The electron injection layer 9 is formed by applying a solution containing the above-described ionic polymer, which is an electron injecting material, to all the pixels in a lump. The above ionic polymer is dissolved in a solvent to prepare a solution to be applied. If a polar solvent such as methanol or ethanol is employed as a solvent for preparing the solution, it becomes possible to suppress re-dissolution of the light emitting layer in the applied solution.

The ionic polymer solution is applied to the surface of the light emitting layer and the second bank layer 5 collectively for all pixels. A spin coating method or the like can be employed as the coating method, but a printing method can also be employed in the same manner as the light emitting layer, the hole injection layer 6 and the hole transport layer 7. Furthermore, the electron injection layer 9 is formed by drying and baking the coating film of the applied ionic polymer solution. The deposition temperature of the electron injection layer 9 is desirably 150 ° C. or lower. When heat treatment is performed at a temperature exceeding 150 ° C., the function of the light emitting layer formed of an organic substance may be deteriorated.

(Formation of cathode)
Next, the cathode 10 is formed on the surface of the electron injection layer 9 in common for all pixels by film formation from a solution. The cathode 10 is formed by applying a liquid material such as the above-described material having a high work function or a solution or dispersion containing a conductive material. As another embodiment, the cathode may be formed only in a region surrounded by the second bank layer 5, or the cathode may be formed by, for example, a sputtering method or a vapor deposition method.

When the PEDOT / PSS is used as the conductive material, 3,4-polyethylenedioxythiophene is dispersed in polystyrene sulfonic acid as a dispersion medium, and further dissolved in a solvent such as water or isopropyl alcohol. When metal fine particles are employed as the conductive material, a solvent such as water, methanol, ethanol, propanol, isopropyl alcohol (IPA), or dimethyl ketone is used as the dispersion medium.

The liquid material for forming the cathode is applied to the surface of the electron injection layer 9 in common for all pixels. The application of the solution can be performed by a printing method such as a spin coating method or an ink jet method, similarly to the formation of the electron injection layer 9. Further, the coated liquid is dried and baked to form a film of the cathode 10. The film forming temperature of the cathode 10 is desirably 150 ° C. or lower, similarly to the film forming temperature of the electron injection layer 9. When PEDOT / PSS is used as the conductive material, it can be fired under conditions of about 100 ° C. × 10 minutes, and damage to the light emitting layer can be suppressed.

Next, an auxiliary cathode may be formed so as to cover the surface of the cathode 10. The auxiliary cathode is formed by applying a liquid material containing a conductive material. The liquid is prepared by dispersing fine metal particles such as Au and Ag in a dispersion medium such as water, methanol, ethanol, propanol, isopropyl alcohol (IPA), and dimethyl ketone. As in the formation of the cathode 10, a printing method such as a spin coating method or an ink jet method can be used for applying the liquid material. The applied liquid material is dried and fired to form a film of the auxiliary cathode. As with the film formation temperature of the cathode 10, the film formation temperature of the auxiliary cathode is desirably set to 150 ° C. or lower.

Thus, the organic EL display device of this embodiment is formed.

As described in detail above, in the manufacturing method of the organic EL display device according to the present embodiment, it has electron injectability, is stable in an atmosphere of normal pressure, and is stable in the air, and is made into a solution with a solvent. It is characterized in that the electron injection layer is formed from an ionic polymer that can be formed and the cathode is formed by film formation from a solution. According to such a characteristic configuration, the organic layer including the cathode of the organic EL element constituting the organic EL display device can be formed by film formation from a solution in the air, thereby simplifying the manufacturing process. Thus, the manufacturing cost can be reduced. In addition, since there is no limitation on the substrate size, a large screen display can be manufactured.

[Configuration and Manufacturing Method of Organic EL Display Device (Second Embodiment)]
Next, a second embodiment of the configuration and manufacturing method of the organic EL display device according to the present invention will be described with reference to FIG.

In the second embodiment, a plurality of pixels are composed of a blue organic EL element that emits blue light and another organic EL element that emits light having a spectrum different from that of the blue light, and the light emitting layer is In the forming step, a solution containing a light-emitting material to be a light-emitting layer of the other organic EL element is applied to a region where the other organic EL element is provided, formed into a film, and further, the blue organic EL element emits light. A plurality of light-emitting layers are formed by applying a solution containing a light-emitting material to be a layer to a region where the blue organic EL element and the other organic EL element are provided and forming a film.

In the second embodiment, as in the above-described embodiment, a red organic EL element that emits red light and a green organic EL element that emits green light are provided as other organic EL elements. In the second embodiment, a layer made of the same material as the B light emitting layer of the blue organic EL element is also provided in the organic EL elements of other colors, but this layer does not emit light in the organic EL elements of other colors. It has been known. That is, when a layer made of the same material as the B light emitting layer is simultaneously present in the R light emitting layer or the G light emitting layer which is another organic EL element, the other organic EL element does not emit light. Therefore, even if the same layer as the B light emitting layer of the blue organic EL element is provided in another organic EL element, only the R light emitting layer emits light in the red organic EL element, and only the G light emitting layer emits light in the green organic EL element. , Respectively, emit red and green light.

The second embodiment is the same as the first embodiment except that the laminated structure of the light emitting layer 81, the light emitting layer 82, and the light emitting layer 83 and the method for forming the same are different. Therefore, in order to avoid duplication, in the following description, the structure and the formation method between the hole transport layer 7 from the preparation of the substrate 1 are omitted, and the subsequent light emitting layer 81, light emitting layer 82, light emitting layer are omitted. The structure and forming method 83 will be described, and the structure and forming method of the electron injection layer 9 and the cathode 10 after forming the light emitting layer 81, the light emitting layer 82, and the light emitting layer 83 are also omitted.

(Light emitting layer)
The configurations and formation methods of the R light emitting layer 81 and the G light emitting layer 82 are the same as those in the first embodiment.
After the R light emitting layer 81 and the G light emitting layer 82 are formed, a solution containing a light emitting material that becomes the B light emitting layer 83 of the blue organic EL element is applied to a region where the blue organic EL element and other color organic EL elements are provided. Then, the B light emitting layer 83 is formed by forming a film. When the B light emitting layer 83 is formed, a layer extending from the B light emitting layer 83 and continuing to all pixels is formed. Therefore, a layer made of the same material as that of the B light emitting layer 83 is also formed in the red organic EL element and the green organic EL element. However, as described above, the layer made of the same material as the B light emitting layer 83 formed in the red organic EL element and the green organic EL element does not emit light and does not function as a light emitting layer.

The solution containing the light emitting material that will become the B light emitting layer 83 of the blue organic EL element may be formed on the entire surface of the substrate so as to be collectively formed on all pixels. In this way, when forming a film in common for all pixels, compared to the method of applying a solution pattern, there are less difficulties in film formation such as alignment and control of film thickness uniformity within the pixel. A simple film forming method can be used. Manufacturing can be simplified more when viewed in the entire display manufacturing process.

After forming the light emitting layer 81, the light emitting layer 82, and the light emitting layer 83, the electron injection layer 9 having the same configuration and the cathode 10 having the same configuration are sequentially formed by the same method as in the first embodiment. In contrast, an auxiliary electrode is preferably formed.
Thus, the organic EL display device of the second embodiment is formed.

Claims

An organic device comprising a plurality of pixels each composed of an organic electroluminescence element including a pair of electrodes composed of an anode and a cathode, a light emitting layer positioned between the electrodes, and an electron injection layer positioned between the cathode and the light emitting layer A method for manufacturing an electroluminescent display device, comprising:
Applying a solution containing a light emitting material on the substrate on which the anode is formed, and forming a light emitting layer by forming a film;
Applying a solution containing an ionic polymer on the light emitting layer and forming a film to form an electron injection layer;
Forming a cathode on the electron injection layer;
A method for producing an organic electroluminescence display device, comprising:
In the step of forming the electron injection layer, a solution containing an ionic polymer is commonly applied to all the pixels on the substrate on which the light emitting layer is formed, and the electron injection layer continuous over all the pixels is formed. The manufacturing method of the organic electroluminescent display apparatus of Claim 1.
2. The method of manufacturing an organic electroluminescence display device according to claim 1, wherein in the step of forming the cathode, the cathode is formed by applying a liquid material containing a conductive material and forming a film.
The plurality of pixels are composed of a blue organic electroluminescence element that emits blue light and an organic electroluminescence element of another color that emits light having a spectrum different from that of the blue light,
In the step of forming the light emitting layer, a solution containing a light emitting material to be a light emitting layer of the organic electroluminescent element of the other color is applied to a region where the organic electroluminescent element of the other color is provided and formed into a film. Furthermore, a solution containing a light emitting material to be a light emitting layer of the blue organic electroluminescent element is applied to a region where the blue organic electroluminescent element and the organic electroluminescent element of the other color are provided to form a film. The method of manufacturing an organic electroluminescence display device according to claim 1, wherein the method is characterized in that:
An organic electroluminescence display device manufactured by the manufacturing method according to claims 1 to 4.