TWI528541B - Organic thin film transistor and method for making the same - Google Patents

Description

Organic thin film transistor and method of manufacturing same

The present invention relates to an organic thin film transistor and a method for producing the same, an organic thin film transistor substrate having an organic thin film transistor, and a display device including the organic thin film transistor substrate.

The thin film transistor can be roughly divided into an organic thin film transistor and an inorganic semiconductor transistor. The organic thin film electro-crystal system is provided with an organic semiconductor layer as an active layer, and the inorganic thin film electro-crystalline system is provided with an inorganic semiconductor layer as an active layer. These two types of thin film electrocrystallization systems are produced in different ways.

Inorganic thin film transistors generally form an active layer in a vacuum environment, and therefore, a vacuum environment is required in the formation of the active layer.

On the other hand, the organic thin film electro-crystal system can form an active layer by a coating method which does not require a vacuum environment, and the formation of the active layer does not necessarily require a vacuum environment. For example, an organic thin film electrocrystallization system can be formed into a film by dissolving or dispersing a material of an active layer in a coating liquid of any appropriate solvent, thereby easily forming an active layer. If the coating method is employed as described above, the manufacturing method of the organic thin film transistor does not require a vacuum environment. Further, in the method of producing an organic thin film transistor, a plurality of transistors can be formed at a time in a wide range by using a coating method. As a result, the manufacturing cost can be reduced.

Regarding the organic thin film transistor having the advantages of such a manufacturing step, various studies for improving the electrical characteristics have been carried out at present. For example, a field effect type organic thin film transistor having an n-type organic semiconductor layer in which a C60 fullerene derivative having a long-chain alkyl group is coated into a film is known (refer to Patent Document 1). Further, an organic thin film transistor in which a buffer layer made of lithium fluoride (LiF) is provided between a source electrode and a drain electrode and an active layer to improve electrical characteristics is known (refer to Non-Patent Document 1). ).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-060169

[Non-patent literature]

Non-Patent Document 1: Microelectronics Journal Volume 38, Issues 4-5, April-May 2007, Pages 632-636

Lithium fluoride or the like used in the buffer layer is easily oxidized by reacting with moisture and oxygen in an atmospheric environment. Therefore, once the buffer layer is oxidized, the electrical characteristics of the organic thin film transistor are lowered.

In order to prevent oxidation of the buffer layer in such an atmosphere, in the prior art, the organic thin film transistor is formed without being exposed to the atmosphere during and after formation of the buffer layer. For example, a buffer layer made of lithium fluoride or the like is formed by a vapor deposition method under a high vacuum atmosphere, and a source/germanium is formed on the buffer layer while maintaining the high vacuum. The electrode is sealed and sealed as needed to prevent the buffer layer from being exposed to the atmosphere. As described above, in the prior art, since a high vacuum environment is required, in the step of forming a film by the coating method, it is necessary to have a large-scale apparatus such as an unnecessary vacuum pump or a vacuum processing chamber, or It is a carry-in process which needs to be carried in a vacuum processing chamber, a carry-out process carried out by a vacuum processing chamber, a pressurization process, a pressure reduction process, etc., and a manufacturing process becomes complicated, and manufacturing cost is increased.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a charge injection layer using a material which is not easily oxidized even in an environment of a normal pressure and which is less likely to deteriorate in functionality. The organic thin film transistor having good electrical characteristics is provided, and a simple manufacturing method of the organic thin film transistor including the step of forming the charge injection layer which can be carried out even in an environment of a normal pressure is provided.

When the inventors of the present invention conducted research on an ionic polymer and an electronic component using the ionic polymer, it was found that it is not easy to produce by using not only electrical characteristics but also in an environment of normal pressure. The ionic polymer which is oxidized and which is less likely to deteriorate in functionality can solve the aforementioned problems, and the present invention has been completed.

That is, as in the present invention, the following [1] to [9] are provided.

[1] An organic thin film transistor comprising: a gate electrode, a first source/drain electrode, a second source/drain electrode, and a first source/drain electrode and a second source; An organic semiconductor layer between the pole/drain electrode and the gate electrode, and the first source/between the first source/drain electrode and the second source/drain electrode and the organic semiconductor layer An organic thin film transistor of a charge injection layer in which a drain electrode and a second source/drain electrode are in contact with each other, wherein the charge injection layer contains an ionic polymer having charge injection characteristics.

[2] The organic thin film transistor according to [1], wherein the conductive type of the conductive charge injection layer is n-type, and the conductive type of the organic semiconductor layer is n-type.

[3] The organic thin film transistor according to [2], wherein a gate insulating layer is disposed between the organic semiconductor layer and the gate electrode and is in contact with the gate electrode, and the gate electrode is It is composed of an n-type semiconductor substrate.

[4] The organic thin film transistor according to any one of [1] to [3], wherein the organic thin film transistor is provided.

[5] A display device comprising the organic thin film transistor substrate described in [4] as a drive substrate.

[6]: A method for producing an organic thin film transistor, comprising: forming a gate electrode, a first source/drain electrode, a second source/drain electrode, and the first source/drain electrode; An organic semiconductor layer between the second source/drain electrode and the gate electrode, and the first first source/drain electrode and the second source/drain electrode and the organic semiconductor layer A method for producing an organic thin film transistor in which a source/drain electrode and a charge injection layer of a second source/drain electrode are in contact with each other, comprising: a charge injection layer containing an ionic polymer having charge injection characteristics; The steps of formation.

[7] The method for producing an organic thin film transistor according to [6], in the step of forming the charge injection layer, by coating a coating liquid containing an ionic polymer in an atmospheric pressure environment The film is formed into a film to form the aforementioned charge injection layer.

[8] The method for producing an organic thin film transistor according to [7], wherein the first source/drain electrode and the second source/drain electrode are in a normal pressure environment, The coating liquid is formed by coating and forming a film.

The method for producing an organic thin film transistor according to any one of the aspects of the present invention, wherein the organic semiconductor layer is coated in a normal pressure environment by coating a coating liquid Formed by film formation.

The organic thin film electro-crystal system of the present invention has good charge injection characteristics, and uses an ionic polymer which can maintain good charge injection characteristics even in an environment of a normal pressure or even an atmosphere, as a charge injection layer. material. Therefore, the organic thin film transistor of the present invention does not easily degrade performance even in an environment of a normal pressure or even an atmospheric environment.

Further, according to the method for producing an organic thin film transistor according to the present invention, an ionic polymer which is not easily oxidized even in an environment of a normal pressure or even an atmospheric environment is used as a material of the charge injection layer. Therefore, the step of forming the charge injection layer can be carried out by a coating method in an environment of a normal pressure or even in an atmospheric environment. Therefore, the production of the organic thin film transistor can be more easily performed, and the manufacturing cost can be further reduced.

(Embodiment of the invention)

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, each drawing is a schematic representation of the shape, size, and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited to the following description, and various constituent elements can be appropriately changed without departing from the scope of the invention. In the respective drawings, the same components are denoted by the same reference numerals, and the description thereof will not be repeated. The organic thin film transistor of the present invention is not necessarily manufactured or used by the configuration of the illustrated example. Further, in the following description, there is a case where one side of the thickness direction of the substrate is referred to as the upper side or the upper side, and the other side of the thickness direction is referred to as the lower side or the lower side.

<Configuration of Organic Thin Film Transistor>

The organic thin film electro-crystal system includes a gate electrode, a first source/drain electrode, a second source/drain electrode, and is disposed between the first and second source/drain electrodes and the gate electrode The organic semiconductor layer is a charge injection layer which is disposed between the first and second source/drain electrodes and the organic semiconductor layer and is in contact with the first and second source/drain electrodes. The organic thin film electro-crystal system has a function of controlling a current flowing between the first source/drain electrode and the second source/drain electrode by adjusting a voltage applied to the gate electrode.

The charge injection layer of the organic thin film transistor of the present invention contains an ionic polymer having charge injection characteristics.

The conductivity type of the charge injection layer and the conductivity type of the organic semiconductor layer are preferably the same. That is, if the charge injection layer is n-type, the organic semiconductor layer is preferably n-type, and if the charge injection layer is p-type, the organic semiconductor layer is preferably p-type.

In the present specification, the term "source/drain electrode" means one electrode used as a source electrode or a drain electrode, and the first source/drain electrode (first electrode) used in an organic thin film transistor And one of the second source/drain electrodes (second electrodes) is used as a source electrode, and the other is used as a drain electrode.

The organic thin film electrocrystallization system of the present invention is characterized by an ionic polymer constituting a charge injection layer. Therefore, first, an ionic polymer will be described.

(ionic polymer)

The ionic polymer series which can be used in the present invention is, for example, one or more 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 of the structural unit. As a series of ionic polymers, a series consisting of a group represented by the formula (1) and a group represented by the formula (2) having 15 mol% to 100 mol% in a total structural unit A polymer of one or more selected structural units selected from the group.

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

(In the chemical formula (1), Q ¹ represents a divalent organic group, and Y ¹ represents -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^2- or -R ^a SO ₃ ^- , M ¹ represents a metal cation or an ammonium cation which may have a substituent, and Z ¹ represents F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^a SO ₃ ^- , R ^a COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , n1 represents an integer of 0 or more, a1 represents an integer of 1 or more, and b1 represents an integer of 0 or more, but a1 and b1 are selected such that the charge of the base represented by the chemical formula (1) becomes zero. R ^a represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent, and each of Q ¹ , M ¹ and Z ¹ has a plurality of In the state, a plurality of Q ¹ , M ¹ and Z ¹ systems may be the same or different.)

-(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) _b2 (2)

(In the chemical formula (2), Q ² represents a divalent organic group, and Y ² represents a carbocation, an ammonium cation, a phosphine cation or a sulfonyl cation or an iodonium cation, M ² represents F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^b SO ₃ ^- , R ^b COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , Z ² represents a metal cation or may have a substituent The ammonium cation, n2 represents an integer of 0 or more, a2 represents an integer of 1 or more, and b2 represents an integer of 0 or more. However, a2 and b2 are selected such that the charge of the group represented by the chemical formula (2) becomes zero. R ^b represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent, and has a plurality of Q ² , M ² and Z ² each In the state, a plurality of Q ² , M ^{2 ,} and Z ² systems may be the same or different.

The morphological system used in the present invention is also a polymer having a group represented by the following formula (3). In the state where the ionic polymer has a group represented by the chemical formula (3), the base system represented by the chemical formula (3) may be contained in the structural unit of the ionic polymer, or may be contained in and contained in the chemical formula (1). The structural unit represented by the group represented by the group represented by the chemical formula (2) and the group of the one or more selected from the group is the same structural unit, and may be included in other structural units. Further, as one of the ionic polymers, the morphological series includes a base represented by the chemical formula (1), a group represented by the chemical formula (2), and a chemical formula (15) in a total structural unit of 15 mol% to 100 mol%. a polymer of at least one of the structural units represented by the group.

-(Q ³ ) _n3 -Y ³ (3)

(In the chemical formula (3), Q ³ represents a divalent organic group, and Y ³ represents a group represented by -CN or any one of Chemical Formulas (4) to (12), and n3 represents 0 or more. The integer.

-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 chemical formula (4) to the chemical formula (12), R' represents a divalent hydrocarbon group which may have a substituent, and R" represents a hydrogen atom, a monovalent hydrocarbon group which may have a substituent, -COOH, -SO ₃ H, -OH, -SH, -NR ^c ₂ , -CN or -C(=O)NR ^c ₂ , R''' represents a trivalent hydrocarbon group which may have a substituent, and a3 represents an integer of 1 or more. A4 represents an integer of 0 or more, and Rc represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. In R', R" and R In the state in which each of ''' has a plurality of numbers, the plurality of R', R", and R''' can be the same or different.))

The ionic polymer is preferably a structural unit represented by the chemical formula (13), a structural unit represented by the chemical formula (15), and a chemical formula (17) in a total structural unit of 15 mol% to 100 mol%. One or more structural units selected from the group consisting of the structural unit and the structural unit represented by the chemical formula (20).

(In the chemical formula (13), R ¹ includes a monovalent group of the group represented by the chemical formula (14), and Ar ¹ represents an aromatic group of (2+n4) valence which may have a substituent other than R ¹ , n4 The system represents an integer of 1 or more. In the state in which R ¹ has a plurality of numbers, the plurality of R ¹ systems may be the same or different.

(In the chemical formula (14), R ² represents an organic group having a valence of (1+m1+m2), and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 are The meanings are the same as described above, and m1 and m2 each independently represent an integer of 1 or more, and each of Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 In a plurality of states, a plurality of Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 may be the same or different.

(In the chemical formula (15), R ³ is a monovalent group of the group represented by the chemical formula (16), and Ar ² represents an (2+n5)-valent aromatic group which may have a substituent other than R ³ , n5 The system represents an integer of 1 or more, and in the state in which R ³ has a plurality of plural, the plurality of R ³ systems may be the same or different.

(In the chemical formula (16), R ⁴ represents an organic group having a (1+m3+m4) valence, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 are The meanings are the same as described above, and m3 and m4 each independently represent an integer of 1 or more. In each of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 In a plurality of states, a plurality of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 may be the same or different.))

(In the chemical formula (17), R ⁵ is a monovalent group of the group represented by the chemical formula (18), R ⁶ is a monovalent group of the group represented by the chemical formula (19), and Ar ³ means that it may have R ⁵ And an aromatic group having a (2+n6+n7) valence of a substituent other than R ⁶ , wherein n6 and n7 each independently represent an integer of 1 or more, and each of R ⁵ and R ⁶ has a plurality of states; A plurality of R ⁵ and R ⁶ may be the same or different.

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

(In the chemical formula (18), R ⁷ represents a direct bond or a (1+m5) valence organic group, and Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1 are the same as described above. Meaning, m5 represents an integer of 1 or more, and each of Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1, and b1 has a plurality of Q ¹ , Y ¹ , and M ¹ in a plurality of states. Z ¹ , n1 , a1 and b1 may be the same or different.)

-R ⁸ -{(Q ³ ) _n3 -Y ³ } _m6 (19)

(In the chemical formula (19), R ⁸ represents a single bond or an organic group of (1+m6) valence, Y ³ and n3 represent the same meaning as described above, and m6 represents an integer of 1 or more. However, in R ⁸ is of a single bond, M6 are diagrams 1.Q ^3, Y ³ and n3 each line having a plurality of one of the state, having a plurality of Q ^3, Y ³ and n3, respectively, may be the same or different. ))

(In the chemical formula (20), R ⁹ is a monovalent group of the group represented by the chemical formula (21), R ¹⁰ is a monovalent group of the group represented by the chemical formula (22), and Ar ⁴ means that it may have R ⁹ And an aromatic group of (2+n8+n9) valence of a substituent other than R ¹⁰ , wherein n8 and n9 each independently represent an integer of 1 or more, and each of R ⁹ and R ¹⁰ has a plurality of states; There may be a plurality of R ⁹ and R ¹⁰ , which may be the same or different.

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

(In the chemical formula (21), R ¹¹ represents a single bond or an organic group of (1+m7) valence, and Q ² , Y ² , M ² , Z ² , n2, a2 and b2 represent the same meaning as described above. M7 is an integer of 1 or more. However, when R ¹¹ is a single bond, m7 represents 1. Each of Q ² , Y ² , M ² , Z ² , n2, a2, and b2 has a plurality of In the state, a plurality of Q ² , Y ² , M ² , Z ² , n2, a2, and b2 may be the same or different.

-R ¹² -{(Q ³ ) _n3 -Y ³ } _m8 (22)

(In the chemical formula (22), R ¹² represents a single bond or an organic group of (1+m8) valence, Y ³ and n3 represent the same meaning as described above, and m8 represents an integer of 1 or more. However, in R ¹² is of a single bond, m8 are diagrams 1.Q ^3, Y ³ and n3 each line having a plurality of one of the state, having a plurality of Q ^3, Y ³ and n3, respectively, may be the same or different. ))

The structural unit in the ionic polymer may include two or more kinds of groups represented by the chemical formula (1), and may include two or more kinds of groups represented by the chemical formula (2), or may contain two or more types of chemical formulas ( 3) The basis of the representation.

- the base represented by the chemical formula (1) -

In the chemical formula (1), the divalent organic group represented by Q ¹ is as follows: methylene, ethyl, 1,2-propyl, 1,3-propyl, 1,2- Butyl butyl, 1,3-butylene, 1,4-butylene, 1,5-amyl, 1,6-extension, 1,9-extension, 1,12-extension a carbon group-substituted saturated hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, such as a group substituted with at least one hydrogen atom of these groups; a vinyl group, a propenyl group, a 3-butene group a group, a 2-butenyl group, a 2-pentenyl group, a 2-extended hexenyl group, a 2-extended alkenyl group, a 2-extended dodecyl group, substituted with at least one hydrogen atom of these groups An alkenyl group having 2 to 50 carbon atoms which may have a substituent, and a divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms which may have a substituent of an exetylene group; a cyclobutyl, cyclopentenyl, cyclohexyl, fluorenyl, fluorenyl, fluorenyl, and hydrazine alkyl group substituted with at least one hydrogen atom of these groups by a substituent a cyclic saturated hydrocarbon group having a carbon number of 3 to 50, which may have a substituent; 1,3-phenylene 1,4-phenylene, 1,4-naphthyl, 1,5-anthranyl, 2,6-anthranyl, biphenyl-4,4'-didecyl substituted with a substituent a aryl group having 6 to 50 carbon atoms which may have a substituent, at least one hydrogen atom or the like; a methylene group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group a substituent having at least one hydrogen atom of the group substituted by a substituent, and an alkylene group having 1 to 50 carbon atoms which may have a substituent; and an imine having a substituent containing a carbon atom; The sulfhydryl group having a substituent containing a carbon atom is preferably 2 in terms of easiness of synthesis of a monomer which is an ionic polymer raw material (hereinafter referred to as "raw material monomer"). A saturated hydrocarbon group, an extended aryl group, or an alkoxy group.

As the series of the above substituents, for example, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group. , arylalkynyl, amine, substituted amine, fluorenyl, substituted fluorenyl, halogen atom, fluorenyl, decyloxy, imine residue, decylamino, quinone imine, monovalent heterocyclic, A hydroxyl group, a carboxyl group, a substituted carboxyl group, a cyano group, a nitro group, or the like may be present in a plurality of substituents, and a plurality of substituents may be the same or different. Among these, a substituent other than an amine group, a mercapto group, a halogen atom, a hydroxyl group, and a nitro group contains a carbon atom.

Hereinafter, the substituents will be described. In addition, the term "C _m to C _n " (m and n satisfy a positive integer of m < n) means that the number of carbon atoms of the organic group described together with the term is m to n. For example, a C _m to C _n alkyl group means that the alkyl group has a carbon number of m to n, and if it is a C _m to C _n alkyl aryl group, it means that the alkyl group has a carbon number of m to n. If it is an aryl- _Cm to _Cn alkyl group, it means that the alkyl group has a carbon number of m to n.

The alkyl group may be linear or branched, or may be a cycloalkyl group. The alkyl group has a carbon number of usually 1 to 20, preferably 1 to 10. As the alkyl series, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, anthracene Base, sulfhydryl, lauryl, etc. The hydrogen atom in the aforementioned alkyl group may be substituted by a fluorine atom. Examples of the fluorine-substituted alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Further, as the C ₁ to C ₁₂ alkyl series, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl , hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl.

The alkoxy group may be linear or branched, and may be a cycloalkoxy group or a substituent. The alkoxy group has a carbon number of usually 1 to 20, preferably 1 to 10. The series of alkoxy groups are: methoxy, ethyloxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, Hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, decyloxy, decyloxy, lauryloxy and the like. The hydrogen atom in the alkoxy group described above may be substituted by a fluorine atom. Examples of the fluorine atom-substituted alkoxy group include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group. Further, in the alkoxy group, a methoxymethyloxy group or a 2-methoxyethyloxy group is also included. Further, as the C ₁ to C ₁₂ alkoxy series, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butyl Oxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, 3,7-dimethyloctyloxy Base, lauryloxy.

The alkylthio group may be linear or branched, and may be a cycloalkylthio group or may have a substituent. The alkylthio group has a carbon number of usually 1 to 20, preferably 1 to 10. As the alkylthio series, such as: methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, Hexylthio, cyclohexylthio, heptylthio, octylthio, sulfonylthio, sulfonylthio, laurel, and the like. The hydrogen atom in the above alkylthio group may be substituted by a fluorine atom. The series of substituted alkylthio groups as fluorine atoms is, for example, a trifluoromethylthio group.

The aryl group is an atomic group remaining after the aromatic hydrocarbon is bonded to a hydrogen atom bonded to a carbon atom constituting the aromatic ring, and also includes a group having a benzene ring, a fused ring group, an independent benzene ring or a fused ring. Two or more of them are bonded via a single bond or a divalent organic group, for example, an alkyl group such as a vinyl group. The aryl group has a carbon number of usually 6 to 60, preferably 7 to 48. As the aryl series, for example, phenyl, C ₁ to C ₁₂ alkoxyphenyl, C ₁ to C ₁₂ alkylphenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-fluorenyl , 9-base, etc. The hydrogen atom in the aforementioned aryl group may be substituted by a fluorine atom. The series of aryl groups substituted as a fluorine atom is as follows: pentafluorophenyl group. Among the aryl groups, a C ₁ to C ₁₂ alkoxyphenyl group and a C ₁ to C ₁₂ alkylphenyl group are preferred.

Among the above aryl groups, as a C ₁ to C ₁₂ alkoxyphenyl series, such as: methoxyphenyl, ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, butoxybenzene , isobutoxyphenyl, sec-butoxyphenyl, tert-butoxyphenyl, pentoxyphenyl, hexyloxyphenyl, cyclohexyloxyphenyl, heptyloxyphenyl, Octyloxyphenyl, 2-ethylhexyloxyphenyl, nonyloxyphenyl, nonyloxyphenyl, 3,7-dimethyloctyloxyphenyl, lauryloxyphenyl, and the like.

Among the aforementioned aryl groups, as the C ₁ to C ₁₂ alkylphenyl series, such as methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, trimethylphenyl, methylethylbenzene Base, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl, isopentylphenyl, hexylphenyl, heptylphenyl, octylphenyl , nonylphenyl, nonylphenyl, lauryl phenyl and the like.

The aryloxy group has a carbon number of usually 6 to 60, preferably 7 to 48. 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 pentafluorobenzene group. Oxyl and the like. Among the aryloxy groups, a C ₁ to C ₁₂ alkoxyphenoxy group and a C ₁ to C ₁₂ alkylphenoxy group are preferred.

Among the above aryloxy groups, as the C ₁ to C ₁₂ alkoxyphenoxy series, such as: methoxyphenoxy, ethoxyphenoxy, propoxyphenoxy, isopropoxyphenoxy , butoxyphenoxy, isobutoxyphenoxy, sec-butoxyphenoxy, tert-butoxyphenoxy, pentyloxyphenoxy, hexyloxyphenoxy, ring Hexyloxyphenoxy, heptyloxyphenoxy, octyloxyphenoxy, 2-ethylhexyloxyphenoxy, nonyloxyphenoxy, decyloxyphenoxy, 3,7- Dimethyloctyloxyphenoxy, lauryloxyphenoxy and the like.

Among the above aryloxy groups, the C ₁ to C ₁₂ alkylphenoxy series is as follows: methylphenoxy, ethylphenoxy, dimethylphenoxy, propylphenoxy, 1,3 ,5-trimethylphenoxy, methylethylphenoxy, isopropylphenoxy, butylphenoxy, isobutylphenoxy, sec-butylphenoxy, tert-butyl Phenoxy, pentylphenoxy, isopentylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, nonylphenoxy, lauryl phenoxy Base.

An arylthio group such as a sulfur element is bonded to the group of the aforementioned aryl group. The arylthio group may have a substituent on the aromatic ring of the aforementioned aryl group. The arylthio group has a carbon number of usually 6 to 60, preferably 6 to 30. Examples of the arylthio group include: phenylthio group, C ₁ to C ₁₂ alkoxyphenylthio group, C ₁ to C ₁₂ alkylphenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorobenzene. Sulfur-based, etc.

The arylalkyl group is, for example, a group in which the aforementioned alkyl group is bonded to the aforementioned aryl group. The arylalkyl group may have a substituent. The arylalkyl group has a carbon number of usually 7 to 60, preferably 7 to 30. As the arylalkyl series, for example, phenyl-C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl, 1-naphthyl-C ₁ to C ₁₂ alkyl, 2-naphthyl-C ₁ to C ₁₂ alkyl, and the like.

The arylalkoxy group is, for example, a group in which the aforementioned alkoxy group is bonded to the aforementioned aryl group. The arylalkoxy group may have a substituent. The arylalkoxy group has a carbon number of usually 7 to 60, preferably 7 to 30. As the arylalkoxy series, phenyl-C ₁ to C ₁₂ alkoxy, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkoxy, C ₁ to C ₁₂ alkylbenzene a group -C ₁ to C ₁₂ alkoxy group, 1-naphthyl-C ₁ to C ₁₂ alkoxy group, 2-naphthyl-C ₁ to C ₁₂ alkoxy group and the like.

The arylalkylthio group is, for example, a group in which the aforementioned alkylthio group is bonded to the aforementioned aryl group. The arylalkylthio group may have a substituent. The arylalkylthio group has a carbon number of usually 7 to 60, preferably 7 to 30. As the arylalkylthio series, phenyl-C ₁ to C ₁₂ alkylthio, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylthio, C ₁ to C ₁₂ alkylbenzene a group -C ₁ to C ₁₂ alkylthio group, 1-naphthyl-C ₁ to C ₁₂ alkylthio group, 2-naphthyl-C ₁ to C ₁₂ alkylthio group and the like.

An arylalkenyl group such as an alkenyl group is bonded to the group of the aforementioned aryl group. The arylalkenyl group has a carbon number of usually 8 to 60, preferably 8 to 30. As the arylalkenyl series, phenyl-C ₂ to C ₁₂ alkenyl, C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkenyl, C ₁ to C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkenyl, 1-naphthyl-C ₂ to C ₁₂ alkenyl, 2-naphthyl-C ₂ to C ₁₂ alkenyl, etc., preferably C ₁ to C ₁₂ alkoxyphenyl-C ₂ To C ₁₂ alkenyl, C ₂ to C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkenyl. Further, as the C ₂ to C ₁₂ alkenyl series, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group. , 1-hexenyl, 2-hexenyl, 1-octenyl.

An arylalkynyl group such as an alkynyl group is bonded to the group of the aforementioned aryl group. The arylalkynyl group has a carbon number of usually 8 to 60, preferably 8 to 30. As the arylalkynyl series, for example, phenyl-C ₂ to C ₁₂ alkynyl, C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl, C ₁ to C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkynyl, 1-naphthyl-C ₂ to C ₁₂ alkynyl, 2-naphthyl-C ₂ to C ₁₂ alkynyl, etc., preferably C ₁ to C ₁₂ alkoxyphenyl-C ₂ To C ₁₂ alkynyl, C ₁ to C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkynyl. Further, as the C ₂ to C ₁₂ alkynyl series, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentyl Alkynyl, 1-hexynyl, 2-hexynyl, 1-octynyl.

The substituted amine group is preferably at least one hydrogen atom selected from the group consisting of one or two selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Amino group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted amine group does not include the number of carbon atoms of the substituent which the alkyl group, the aryl group, the arylalkyl group or the monovalent heterocyclic group may have, and is usually from 1 to 60, preferably from 2 to 48. . As a series of substituted amine groups, such as: methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, isopropylamino, diisopropyl Amino, butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octyl Amino, 2-ethylhexylamino, decylamino, decylamino, 3,7-dimethyloctylamino, laurylamine, cyclopentylamino, dicyclopentylamino , cyclohexylamino, dicyclohexylamino, bis(trifluoromethyl)amino, phenylamino, diphenylamino, (C ₁ to C ₁₂ alkoxyphenyl) amine, di C ₁ to C ₁₂ alkoxyphenyl)amino, di(C ₁ to C ₁₂ alkylphenyl)amine, 1-naphthylamino, 2-naphthylamino, pentafluorophenylamino, Pyridylamino, pyridazinylamino, pyrimidinylamino, pyrazinylamino, triazinylamino, (phenyl-C ₁ to C ₁₂ alkyl)amine, (C ₁ to C ₁₂ alkane) Oxyphenyl-C ₁ to C ₁₂ alkyl)amino, (C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl)amino, di(C ₁ to C ₁₂ alkoxyphenyl) -C ₁ to C ₁₂ alkyl)amine Base, di(C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl)amino, 1-naphthyl-C ₁ to C ₁₂ alkylamino, 2-naphthyl-C ₁ to C ₁₂ Alkylamino group and the like.

As a substituted fluorenyl group, for example, at least one hydrogen atom in the fluorenyl group is substituted by one to three groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The base. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted indenyl group does not include the number of carbon atoms of the substituent which the alkyl group, the aryl group, the arylalkyl group or the monovalent heterocyclic group may have, and is usually from 1 to 60, preferably from 3 to 48. . In addition, as a substituted thiol series, such as: trimethyl decyl, triethyl decyl, tripropyl decyl, triisopropyl decyl, isopropyl dimethyl fluorenyl, isopropyl diethyl Sulfhydryl, tert-butyldimethylmethyl, pentyl dimethyl fluorenyl, hexyl dimethyl fluorenyl, heptyl dimethyl fluorenyl, octyl dimethyl fluorenyl, 2-ethylhexyl Methyl fluorenyl, decyl dimethyl fluorenyl, decyl dimethyl fluorenyl, 3,7-dimethyloctyl dimethyl fluorenyl, lauryl dimethyl fluorenyl, (phenyl-C ₁ To a C ₁₂ alkyl) fluorenyl group, (C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl) fluorenyl, (C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl矽, (1-naphthyl-C ₁ to C ₁₂ alkyl) fluorenyl, (2-naphthyl-C ₁ to C ₁₂ alkyl) fluorenyl, (phenyl-C ₁ to C ₁₂ alkyl) Dimethyl decyl, triphenyl fluorenyl, tris(p-dimethylphenyl) fluorenyl, tribenzyl fluorenyl, diphenylmethyl fluorenyl, tert-butyl diphenyl fluorenyl, dimethyl Phenyl fluorenyl and the like.

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

The carbon number of the fluorenyl group is generally from 2 to 20, preferably from 2 to 18. Examples of the sulfhydryl series include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a trimethyl ethenyl group, a benzamidine group, a trifluoroethyl fluorenyl group, a pentafluorobenzyl group, and the like.

The number of carbon atoms of the methoxy group is generally from 2 to 20, preferably from 2 to 18. Examples of the oxooxy group include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, an isobutyloxy group, a trimethyl ethoxy group, a benzyl group, a trifluoroacetoxy group, Pentafluorobenzyl methoxy group and the like.

The imine residue is a residue obtained by removing one hydrogen atom in the structure from an imine compound having a structure represented by at least one of a chemical formula: HN=C< and a chemical formula: -N=CH-. As such a series of imine compounds, for example, an aldimine, a ketimine, and a hydrogen atom bonded to a nitrogen atom in an aldimine via an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, and an aryl group A compound substituted with an alkynyl group or the like. The number of carbon atoms of the imine residue is usually from 2 to 20, preferably from 2 to 18. As a series of imine residues, for example, the formula: -CR ^β =NR ^γ or the formula: -N=C(R ^γ ) ₂ (In the chemical formula, R ^β represents a hydrogen atom, an alkyl group, an aryl group, an aryl group. An alkyl 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, but in the state in which R ^γ exists in two Next, two R ^γ systems may be bonded to each other to form a ring, and the carbon atom number 2 as a divalent group, for example, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or the like may be The base represented by the alkyl group of 18). The following groups are listed as a series of imine residues.

(In the chemical formula, Me is a methyl group and is the same in the following.)

The mercapto group has a carbon number of usually 1 to 20, preferably 2 to 18. As a series of guanamine groups, for example, amidoxime, etidamine, acrylamide, butylammonium, benzammonium, trifluoroacetamido, pentafluorobenzamide, and Amidoxime, diethylamine, dipropylamine, dibutylammonium, benzoylamino, bis(trifluoroacetamidine)amine, bis(pentafluorobenzidine)amine Wait.

The quinone imine group is a residue obtained by removing a hydrogen atom bonded to the nitrogen atom by a quinone imine, and the number of carbon atoms is usually 4 to 20, preferably 4 to 18. The following are the bases of the quinone imine series.

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

The substituted carboxyl group means a group in which a hydrogen atom in a carboxyl group is substituted by an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, that is, a chemical formula: -C(=O)OR* (in the chemical formula) Wherein R* is a group represented by an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The number of carbon atoms of the substituted carboxyl group is usually from 2 to 60, preferably from 2 to 48. The aforementioned alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Further, the number of carbon atoms does not include the number of carbon atoms of the substituent which the aforementioned alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have. As a series of substituted carboxyl groups, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxy Carbocarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, 3, 7-Dimethyloctyloxycarbonyl, lauryloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, Phenoxycarbonyl, naphthyloxycarbonyl, pyridyloxycarbonyl, and the like.

In the chemical formula (1), Y ¹ represents ^a monovalent group such as -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^-, and the like, and an ionic polymer From the viewpoint of acidity, Y ^{1 is} preferably -CO ₂ ^- , -SO ₂ ^- , -PO ₃ ^- , more preferably -CO ₂ ^- , and is most dependent on the stability of the ionic polymer. It is preferably -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- or -PO ₃ ^- .

In the chemical formula (1), M ¹ represents a metal cation or an ammonium cation which may have a substituent. The metal cation is preferably a monovalent, divalent or trivalent ion, and examples thereof include Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, Fe, Ga, The ions of Mn, Pb, Sn, Ti, V, W, Y, Yb, Zn, Zr and the like are preferably Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Ag ⁺ , Mg ²⁺ , Ca ²⁺ . Further, the substituent which the ammonium ion may have is a methyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group.

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

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

In the chemical 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 chemical formula (1) becomes zero. For example, when Y ¹ is -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^- and M ¹ is a monovalent metal cation or an ammonium cation which may have a substituent And Z ¹ is F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^a SO ₃ ^- , R ^a COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- In the state of NO ₃ ^- , HSO ₄ ^- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^-, it is selected such that a1 = b1 + 1 is satisfied. Y ¹ is -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^- and 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 ^- , ClO4 ^- , SCN ^- , CN ^- , NO ₃ ^- , HSO ₄ ^- , H _{In the state of 2} PO ₄ ^- , BF ₄ ^- or PF ₆ ^-, it is selected such that b1 = 2 × a1-1 is satisfied. Y ¹ is -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^- and M ¹ is a trivalent metal cation and Z ¹ is F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^a SO ₃ ^- , R ^a COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , HSO ₄ ^- , In the state of H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , it is selected so as to satisfy b1 = 3 × a1-1. Y ¹ is -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- , -PO ₃ ^- or -B(R ^a ) ₃ ^- and M ¹ is a monovalent metal cation or an ammonium cation which may have a substituent Further, in a state where Z ¹ is SO ₄ ^2- or HPO ₄ ^2- , it is selected so as to satisfy a1=2×b1+1. Even in any of the aforementioned mathematical expressions indicating 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 which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. The substituents which these substituents may have are the same substituents as those exemplified in the description of the above Q ¹ . When a plurality of substituents exist in a plurality of states, a plurality of substituents may be present, which may be the same or different. As the R ^a series, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl An alkyl group having 1 to 20 carbon atoms, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group or the like, an anthracenyl group, a fluorenyl group or a lauryl group. An aryl group having 6 to 30 carbon atoms or the like.

The base series represented by the above chemical formula (1) is exemplified by the following.

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

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

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

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

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

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

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

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

- the base represented by the chemical formula (2) -

In the chemical formula (2), the divalent organic group represented by Q ² is the same as those exemplified as the divalent organic group represented by the above Q ¹ , and the ease of synthesis from the raw material monomers is considered. In view of this, it is preferably a divalent saturated hydrocarbon group, an extended aryl group or an alkoxy group.

The group which is exemplified as the divalent organic group represented by the above Q ² may have a substituent, and the substituents in the series of substituents exemplified in the description of Q ¹ are the same substituents. When a plurality of substituents exist in a plurality of states, a plurality of substituents may be present, which may be the same or different.

In the chemical formula (2), the Y ² system represents a cation, an ammonium cation, a phosphine cation, a phosphonium cation or an iodonium cation.

As a series of cations, for example, -C ⁺ R ₂

(In the chemical formula, R is an alkyl group or an aryl group independently of each other).

As an ammonium cation series, for example, -N ⁺ R ₃

(In the chemical formula, R is an alkyl group or an aryl group independently of each other).

As a series of phosphine cations, for example, -P ⁺ R ₃

(In the chemical formula, R is an alkyl group or an aryl group independently of each other).

As a ruthenium cation series, for example, -S ⁺ R ₂

(In the chemical formula, R is an alkyl group or an aryl group independently of each other).

As an iodonium cation series, for example, -I ⁺ R ₂

(In the chemical formula, R is an alkyl group or an aryl group independently of each other).

In the chemical formula (2), Y ^{2 is} preferably a cation or an ammonium cation from the viewpoint of easiness of synthesis of a raw material monomer and stability of air, moisture or heat of a raw material monomer and an ionic polymer. Further, a phosphine cation or a phosphonium cation is more preferably an ammonium cation.

In the chemical formula (2), Z ² represents a metal cation or an ammonium cation which may have a substituent. The metal cation is preferably a monovalent, divalent or trivalent ion, and examples thereof include Li, Na, K, Cs, Be, Mg, Ca, Ba, Ag, Al, Bi, Cu, Fe, Ga, and Mn. , ions of Pb, Sn, Ti, V, W, Y, Yb, Zn, Zr, and the like. Further, as the ammonium cation, a series of substituents such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group or the like having 1 to 10 carbon atoms may be mentioned.

In the chemical 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 ₄₂ ^- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- .

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

In the chemical 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 chemical formula (2) becomes zero. For example, in M ² are F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^b SO ₃ ^- , R ^b COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^{- In the state} of NO ₃ ^- , HSO ₄ ^- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , if Z ² is a monovalent metal ion or an ammonium ion which may have a substituent, it satisfies a2 Selected by the method of =b2+1. If Z ² is a divalent metal ion, it is selected so as to satisfy a2=2×b2+1. If Z ² is a trivalent metal ion, it satisfies a2=3. Select from the mode of ×b2+1. In the state where M ² is SO ₄ ^2- or HPO ₄ ^2- , if Z ² is a monovalent metal ion or an ammonium ion which may have a substituent, it is selected so as to satisfy b2=2×a2-1. If Z ² is a trivalent metal ion, it is selected so as to satisfy the relationship of 2 × a2 = 3 × b 2 +1. Even in any of the aforementioned mathematical expressions indicating 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 which may have a substituent or an aryl group having 6 to 50 carbon atoms which may have a substituent. The substituents which these substituents may have are the same substituents as those exemplified in the description of the above Q ¹ . When a plurality of substituents exist in a plurality of states, a plurality of substituents may be present, which may be the same or different. As R ^b series, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl An alkyl group having 1 to 20 carbon atoms, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group or the like, an anthracenyl group, a fluorenyl group or a lauryl group. An aryl group having 6 to 30 carbon atoms or the like.

The base series represented by the above chemical formula (2) is exemplified by the following.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

- the base represented by the chemical formula (3) -

In the chemical formula (3), the divalent organic group represented by Q ³ is the same as those exemplified as the divalent organic group represented by the above Q ¹ , and the ease of synthesis from the raw material monomers is considered. In view of this, it is preferably a divalent saturated hydrocarbon group, an extended aryl group or an alkoxy group.

The base group exemplified as the divalent organic group represented by the above Q ³ may have a substituent, and the substituents exemplified in the description of the above Q ^{1 are} the same substituents as the substituent series. When a plurality of substituents exist in a plurality of states, a plurality of substituents may be present, which may be the same or different.

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

The n3 system represents an integer of 0 or more, preferably an integer of 0 to 20, and more preferably an integer of 0 to 8.

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

In the chemical formula (4) to the chemical formula (12), a series of divalent hydrocarbon groups represented by R' are, for example, a methylene group, an exoethyl group, a 1,2-extended propyl group, a 1,3-propanyl group, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-amylpentyl, 1,6-extension, 1,9-extension, 1,12 a divalent saturated hydrocarbon group having 1 to 50 carbon atoms which may have a substituent; a vinyl group, a propenyl group, and 3, which may be substituted with a substituent of at least one of these groups; - a butenyl group, a 2-butenbutenyl group, a 2-pentenyl group, a 2-extended hexenyl group, a 2-extended alkenyl group, a 2-extended dodecyl group, substituted with at least one of these groups An alkenylene group having 2 to 50 carbon atoms which may have a substituent, and a divalent unsaturated hydrocarbon group having 2 to 50 carbon atoms which may have a substituent of an exetylene group; a propyl group, a cyclopentene butyl group, a cyclopentylene group, a cyclohexylene group, a stretched fluorene group, a fluorene ring, a fluorenyl group, a hydrazine group, and a substituted alkyl group substituted with at least one of these groups. a cyclic saturated hydrocarbon group having a carbon atom number of 3 to 50, which may have a substituent, such as a hydrogen atom group 1,3-phenylene, 1,4-phenylene, 1,4-naphthyl, 1,5-anthranyl, 2,6-anthranyl, biphenyl-4,4'- a diaryl group substituted with a substituent at least one of the hydrogen atoms of the group, etc., which may have a substituent having 6 to 50 carbon atoms; a methylene group, an ethoxy group, a propoxy group And a decyloxy group having a carbon number of from 1 to 50 which may have a substituent, such as a butyloxy group, a pentyloxy group, a hexyloxy group, and a substituent of at least one hydrogen atom of the group.

The substituents described in the above description of Q ¹ and the substituents exemplified in the description are the same substituents. When a plurality of substituents exist in a plurality of states, a plurality of substituents may be present, which may be the same or different.

In the chemical formula (4) to the chemical formula (12), the monovalent hydrocarbon group represented by R" is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group substituted with at least one hydrogen atom of these groups An aryl group having 6 to 30 carbon atoms and the like which may have a substituent, etc. From the viewpoint of solubility of the ionic polymer, a methyl group, an ethyl group, a phenyl group, a 1-naphthyl group, or the like is preferable. 2-naphthyl group. The substituents exemplified in the description of the above Q ¹ are the same substituents as the substituent series. When a plurality of substituents are present, a plurality of substituents may be present, and the same may be used. It can also be different.

In the chemical formula (5), a series of trivalent hydrocarbon groups represented by R''' are as follows: methane triyl, ethane triyl, 1,2,3-propanetriyl, 1,2,4-butane Tris, 1,2,5-pentanetriyl, 1,3,5-pentanetriyl, 1,2,6-hexanetriyl, 1,3,6-hexanetriyl substituted by substituent An alkyltriyl group having 1 to 20 carbon atoms which may have a substituent, such as at least one of these groups; 1,2,3-benzenetriyl, 1,2,4-benzenetriyl, The 1,3,5-benzenetriyl group is substituted with a substituent such as a group of at least one hydrogen atom of these groups, and the like may have an aryl group having 6 to 30 carbon atoms which may have a substituent. From the viewpoint of solubility of the ionic polymer, a methane triyl group, an ethane triyl group, a 1,2,4-benzenetriyl group, and a 1,3,5-benzenetriyl group are preferable. As the substituent series, the substituents exemplified in the description of the above Q ¹ are the same substituents. When a plurality of substituents exist in a plurality of states, a plurality of substituents may be present, which may be the same or different.

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

From the viewpoint of the ease of synthesis of the raw material monomers, the Y ³ system is preferably a group represented by -CN, a formula (4), a group represented by the chemical formula (6), or a group represented by the chemical formula (10). The group represented by the chemical formula (11) is more preferably a group represented by the chemical formula (4), a group represented by the chemical formula (6), or a group represented by the chemical formula (11), and particularly preferably the following group.

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

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

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

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

- a structural unit in an ionic polymer -

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

‧Structural unit represented by chemical formula (13)

In the chemical formula (13), R ¹ is a monovalent group of the group represented by the chemical formula (14), and Ar ¹ represents an (2+n4)-valent aromatic group which may have a substituent other than R ¹ , and the n 4 system Indicates an integer of 1 or more.

The group represented by the formula (14) may be directly bonded to Ar ¹ or through: methylene, ethyl, propyl, butyl, pentyl, hexyl, decyl, ten Dicarbyl, cyclopropyl, cyclobutene, cyclopentyl, cyclohexyl, fluorenyl, fluorenyl, decyl, and alkyl substituted alkyl a group of at least one hydrogen atom in the group, such as an alkyl group having 1 to 50 carbon atoms which may have a substituent; an oxymethylene group, an oxygen extended ethyl group, an oxygen extended propyl group, an oxygen extended butyl group, and an oxygen extension group; Pentyl, oxyhexyl, oxo, oxydecafluoro, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, ring a dodecacarboxy group having a carbon number of from 1 to 50 which may have a substituent, such as a group having at least one hydrogen atom substituted by a substituent, or a substituted alkoxy group; An alkyl group; an imide group which may have a substituent; a mercapto group which may have a substituent; a vinyl group which may have a substituent; an exetylene group; a methane triyl group which may have a substituent; an oxygen atom The different atom a nitrogen atom, a sulfur atom and the like and Ar ^1.

The Ar ¹ system may have a substituent other than R ¹ . As the substituent series, the substituents exemplified in the description of the above Q ¹ are the same substituents. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

From the viewpoint of easiness of synthesis of the raw material monomer, the substituent other than R ^{1 of the} above Ar ¹ is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group.

In the chemical 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.

The series of aromatic groups represented by (2+n4) valence represented by Ar ¹ in the chemical formula (13) are: an aromatic hydrocarbon group of (2+n4) valence, and an aromatic heterocyclic ring of (2+n4) valence. The group is preferably an aromatic group having a (2+n4) valence consisting of only one carbon atom or a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom. The series of aromatic groups of the (2+n4) valence are as follows: a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, 1,3 , (3-n4) valence of (2+n4) hydrogen atoms by a monocyclic aromatic ring such as 5-triazine ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring or oxadiazole ring a condensed polycyclic aromatic ring of two or more rings selected from the group consisting of condensed monocyclic aromatic rings to remove (2+n4) valence groups of (2+n4) hydrogen atoms; a single bond, a vinyl group or an ethynyl group is bonded to the aromatic ring set consisting of two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring; (2+n4) valent group of 2+n4) hydrogen atoms; cross-linking the condensed polycyclic aromatic ring or the aromatic ring group by having a divalent group such as a methylene group, an ethyl group, a carbonyl group or the like The crosslinked polycyclic aromatic ring in which two adjacent aromatic rings are crosslinked removes (2+n4) valence groups of (2+n4) hydrogen atoms and the like.

As a single ring type aromatic ring series, for example, the following ring.

As a series of condensed polycyclic aromatic rings, for example, the following rings are mentioned.

As a series of aromatic rings, for example, the following rings are mentioned.

As a series of crosslinked polycyclic aromatic rings, for example, the following rings are mentioned.

The aromatic group of the (2+n4) valence is preferably from the chemical formula 1 to the chemical formula 14, the chemical formula 26 to the chemical formula 29, the chemical formula 37 to the chemical formula 39 or the chemical formula 41 from the viewpoint of easiness of synthesis of the raw material monomer. The ring represented by the ring removes (2+n4) hydrogen atoms, and is more preferably removed by a ring represented by Chemical Formula 1 to Chemical Formula 6, Chemical Formula 8, Chemical Formula 13, Chemical Formula 26, Chemical Formula 27, Chemical Formula 37 or Chemical Formula 41 (2). +n4) a group of hydrogen atoms, even preferably a group of (2+n4) hydrogen atoms removed by a ring represented by Chemical Formula 1, Chemical Formula 37 or Chemical Formula 41.

In the chemical formula (14), as the organic group of the (1+m1+m2) valence represented by R ² , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m1+m2) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m1+m2) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group, a group substituted with at least one hydrogen atom of these groups by a substituent, etc., and an alkoxy group having 1 to 50 carbon atoms which may have a substituent (m1) +m2) a group of hydrogen atoms; The amine group of the substituent of the subunit removes (m1+m2) hydrogen atom groups; the basis of the (m1+m2) hydrogen atom removed from the mercapto group having a substituent containing a carbon atom, and the ease of synthesis from the raw material monomer From the viewpoint of the above, it is preferred to remove (m1+m2) hydrogen atoms from the alkyl group, remove (m1+m2) hydrogen atoms from the aryl group, and remove (m1+m2) hydrogen from the alkoxy group. The base of the atom.

As the substituent series, the substituents exemplified in the description of the above Q ¹ are the same substituents. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

‧Structural unit represented by chemical formula (15)

In the chemical formula (15), R ³ is a monovalent group of the group represented by the chemical formula (16), and Ar ² represents an (2+n5)-valent aromatic group which may have a substituent other than R ³ , and the n5 system Indicates an integer of 1 or more.

The base represented by the formula (16) may be directly bonded to Ar ² or may be transmitted through: methylene, ethyl, propyl, butyl, pentyl, hexyl, decyl, and ten. Dicarbyl, cyclopropyl, cyclobutene, cyclopentyl, cyclohexyl, fluorenyl, fluorenyl, decyl, and alkyl substituted alkyl a group of at least one hydrogen atom in the group, such as an alkyl group having 1 to 50 carbon atoms which may have a substituent; an oxymethylene group, an oxygen extended ethyl group, an oxygen extended propyl group, an oxygen extended butyl group, and an oxygen extension group; Pentyl, oxyhexyl, oxo, oxydecafluoro, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, ring a dodecacarboxy group having a carbon number of from 1 to 50 which may have a substituent, such as a group having at least one hydrogen atom substituted by a substituent, or a substituted alkoxy group; An alkyl group; an imide group which may have a substituent; a mercapto group which may have a substituent; a vinyl group which may have a substituent; an exetylene group; a methane triyl group which may have a substituent; an oxygen atom A nitrogen atom, a sulfur atom and the Ar ² different atoms bonded.

The Ar ² system may have a substituent other than R ³ . As the substituent series, the substituents exemplified in the description of the above Q1 are the same substituents. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

From the viewpoint of easiness of synthesis of the raw material monomer, the substituent other than R ³ which the Ar ² has is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group.

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

The (2+n5)-valent aromatic group represented by Ar ² in the chemical formula (15) is preferably a (2+n5)-valent aromatic hydrocarbon group or a (2+n5)-valent aromatic heterocyclic group. It is an (2+n5)-valent aromatic group composed of only one or more atoms selected from the group consisting of a carbon atom or a carbon atom and a hydrogen atom, a nitrogen atom and an oxygen atom. The series of aromatic radicals of the (2+n5) valence: from a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, 1,3, (2-n5) valence groups of (2+n5) hydrogen atoms by a monocyclic aromatic ring such as 5-triazine ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring or oxadiazole ring Removing (2+n5) valence groups of (2+n5) hydrogen atoms by condensed condensed polycyclic aromatic rings selected from two or more rings selected from the group consisting of monocyclic aromatic rings; The aromatic ring assembly consisting of two or more aromatic rings selected from the group consisting of a monocyclic aromatic ring and the condensed polycyclic aromatic ring is bonded (2+n5) by a bond, a vinyl group or an ethynyl group. a (2+n5) valence group of a hydrogen atom; having two aromatic groups adjacent to the condensed polycyclic aromatic ring or the aromatic ring group by a divalent group such as a methylene group, an ethyl group, a carbonyl group or the like The cross-linked polycyclic aromatic ring of the ring crosslinks removes (2+n5) valence groups of (2+n5) hydrogen atoms and the like.

The ring represented by Chemical Formula 1 to Chemical Formula 12 exemplified in the description of the structural unit represented by Chemical Formula (13) is used as the monocyclic aromatic ring series.

The condensed polycyclic aromatic ring series is a ring represented by Chemical Formula 13 to Chemical Formula 27 exemplified in the description of the structural unit represented by the chemical formula (13).

The ring represented by Chemical Formula 28 to Chemical Formula 36 exemplified in the description of the structural unit represented by Chemical Formula (13) is a series of aromatic ring collections.

The ring represented by Chemical Formula 37 to Chemical Formula 44 exemplified in the description of the structural unit represented by Chemical Formula (13) is a series of crosslinked polycyclic aromatic rings.

The aromatic group of the (2+n5) valence is preferably from the chemical formula 1 to the chemical formula 14, the chemical formula 26 to the chemical formula 29, the chemical formula 37 to the chemical formula 39 or the chemical formula 41 from the viewpoint of easiness of synthesis of the raw material monomers. The ring represented by the ring removes (2+n5) hydrogen atoms, and is more preferably removed by a ring represented by Chemical Formula 1 to Chemical Formula 6, Chemical Formula 8, Chemical Formula 13, Chemical Formula 26, Chemical Formula 27, Chemical Formula 37 or Chemical Formula 41 (2). +n5) a group of hydrogen atoms, even preferably a group of (2+n5) hydrogen atoms removed by a ring represented by Chemical Formula 1, Chemical Formula 37 or Chemical Formula 41.

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

In the chemical formula (16), as the organic group of the (1+m3+m4) valence represented by R ⁴ , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m3+m4) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m3+m4) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group, a group substituted with at least one hydrogen atom of these groups by a substituent, etc., and an alkoxy group having 1 to 50 carbon atoms which may have a substituent (m3) +m4) a group of hydrogen atoms; The amino group of the substituent of the substituent removes the group of (m3+m4) hydrogen atoms; the basis for the removal of the (m3+m4) hydrogen atom from the mercapto group having a substituent containing a carbon atom, and the ease of synthesis from the raw material monomer From the viewpoint of the removal, it is preferred to remove (m3+m4) hydrogen atoms from the alkyl group, remove (m3+m4) hydrogen atoms from the aryl group, and remove (m3+m4) hydrogen from the alkoxy group. The base of the atom.

The substituents exemplified in the description of the above Q1 are the same substituents as the substituent series. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

‧ structural unit represented by chemical formula (17)

In the chemical formula (17), R ⁵ is a monovalent group of the group represented by the chemical formula (18), R ⁶ is a monovalent group of the group represented by the chemical formula (19), and Ar ³ is a group which may have R ⁵ and The (2+n6+n7)-valent aromatic group of the substituent other than R ⁶ , and n6 and n7 each independently represent 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 or may be transmitted through a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, or Stretching base, stretching base, stretching twelve carbon base, stretching cyclopropyl, cyclopentene butyl, cyclopentyl, cyclohexyl, fluorene, fluorene, tetradecyl, thiol The alkyl group of the gold steel is substituted with a substituent such as a group of at least one hydrogen atom of these groups, and the alkyl group having 1 to 50 carbon atoms which may have a substituent; oxymethylene, oxygen extended ethyl, oxygen extended Base, oxybutylene, oxopentyl, oxyhexanyl, oxo, oxydecaxenylene, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group having a substituent, a cyclopentadecyloxy group, a fluorenyloxy group, a pendant decyloxy group, a metal alkoxy group, and a substituent of at least one hydrogen atom of these groups may have a substituent. An alkylene group having 1 to 50 carbon atoms; an imido group which may have a substituent; an anthracene group which may have a substituent; a vinyl group which may have a substituent; an exetylene group; -Methanetriyltris the group; isobutyl oxygen atom, a nitrogen atom, a sulfur atom and the Ar ³ and bonded.

The Ar ³ system may have a substituent other than R ⁵ and R ⁶ . As the substituent series, the substituents exemplified in the description of the above Q1 are the same substituents. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

From the viewpoint of easiness of synthesis of the raw material monomers, the substituents other than R ⁵ and R ^{6 of the} above Ar ³ are preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group. .

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

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

The aromatic group in the (2+n6+n7) valence represented by Ar ³ in the chemical formula (17) is an aromatic hydrocarbon group of (2+n6+n7) valence, and an aromatic (2+n6+n7) valence. The heterocyclic group is preferably composed of a carbon atom or a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom (2+n6+n7). Aromatic group. The aromatic group of the (2+n6+n7) valence is as follows: a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan a monocyclic aromatic ring such as a ring, a pyrrole ring, a pyrazole ring, an imidazole ring or an oxazole ring, which removes (2+n6+n7) valence groups of (2+n6+n7) hydrogen atoms; a condensed polycyclic aromatic ring selected from two or more rings selected from the group consisting of (2+n6+n7) valent groups of (2+n6+n7) hydrogen atoms; by a single bond, ethylene a group of aromatic rings consisting of two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring is removed by a group or an ethynyl group (2+n6+n7) (2+n6+n7) valence of one hydrogen atom; cross-linking the condensed polycyclic aromatic ring or the adjacent of the aromatic ring set by a divalent group having a methylene group, an ethyl group, a carbonyl group or the like The crosslinked polycyclic aromatic ring of the two aromatic rings removes (2+n6+n7) valence groups of (2+n6+n7) hydrogen atoms.

The monocyclic aromatic ring series is, for example, a ring represented by Chemical Formula 1 to Chemical Formula 5 and Chemical Formula 7 to Chemical Formula 10 exemplified in the description of the structural unit represented by Chemical Formula (13).

The condensed polycyclic aromatic ring series is, for example, a ring represented by Chemical Formula 13 to Chemical Formula 27 exemplified in the description of the structural unit represented by Chemical Formula (13).

As the aromatic ring collection, for example, the ring represented by Chemical Formula 28 to Chemical Formula 36 exemplified in the description of the structural unit represented by Chemical Formula (13).

The series of the cross-linked polycyclic aromatic ring is represented by the chemical formula 37 to the chemical formula 44 exemplified in the related description of the structural unit represented by the chemical formula (13).

The aromatic group of (2+n6+n7) valence is preferably from the chemical formula 1 to the chemical formula 5, the chemical formula 7 to the chemical formula 10, the chemical formula 13, the chemical formula 14, from the viewpoint of easiness of synthesis of the raw material monomers. The ring represented by Chemical Formula 26 to Chemical Formula 29, Chemical Formula 37 to Chemical Formula 39 or Chemical Formula 41 removes (2+n6+n7) hydrogen atoms, and is more preferably removed by a ring represented by Chemical Formula 1, Chemical Formula 37 or Chemical Formula 41 ( The group of 2+n6+n7) hydrogen atoms is even more preferably a group of (2+n6+n7) hydrogen atoms removed by a ring represented by Chemical Formula 1, Chemical Formula 38 or Chemical Formula 42.

In the chemical formula (18), R ⁷ represents a single bond or an organic group of a (1+m5) valence, preferably an organic group of a (1+m5) valence.

In the chemical formula (18), the organic group of the (1+m5) valence represented by R ⁷ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of m5 hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent. a group of at least one hydrogen atom or the like which may have a substituent of 6 to 30 aryl groups, and a group of m 5 hydrogen atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyl group Oxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, norbornoxy, The alkoxy group of the gold steel is substituted with a substituent such as a group of at least one hydrogen atom of these groups, etc. The alkoxy group having 1 to 50 carbon atoms which may have a substituent removes a group of m 5 hydrogen atoms; Substituent The amine group removes a group of m5 hydrogen atoms; the group of m5 hydrogen atoms is removed from a mercapto group having a substituent containing a carbon atom, and from the viewpoint of easiness of synthesis of the raw material monomer, it is preferable to remove m5 from the alkyl group. A group of a hydrogen atom, a group of m5 hydrogen atoms removed from an aryl group, and a group of m5 hydrogen atoms removed from an alkoxy group.

The substituents exemplified in the description of the above Q1 are the same substituents as the substituent series. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

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

In the chemical formula (19), R ⁸ represents a single bond or an organic group of a (1+m6) valence, preferably an organic group of a (1+m6) valence.

In the chemical formula (19), the organic group of the (1+m6) valence represented by R ⁸ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of m6 hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent. a group of at least one hydrogen atom or the like which may have a substituent of 6 to 30 aryl groups, and a group of m6 hydrogen atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyl group Oxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, norbornoxy, The alkoxy group of the gold steel is substituted with a substituent such as a group of at least one hydrogen atom of these groups, etc. The alkoxy group having 1 to 50 carbon atoms which may have a substituent removes a group of m6 hydrogen atoms; Substituent The amine group removes the group of m6 hydrogen atoms; the group of m6 hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and it is preferable to remove m6 from the alkyl group from the viewpoint of easiness of synthesis of the raw material monomer. A group of a hydrogen atom, a group of m6 hydrogen atoms removed from an aryl group, and a group of m6 hydrogen atoms removed from an alkoxy group.

The substituents exemplified in the description of the above Q1 are the same substituents as the substituent series. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

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

‧Structural unit represented by chemical formula (20)

In the chemical formula (20), R ⁹ is a monovalent group of the group represented by the chemical formula (21), R ¹⁰ is a monovalent group of the group represented by the chemical formula (22), and Ar ⁴ means that it may have R ⁹ and The (2+n8+n9)-valent aromatic group of the substituent other than R ¹⁰ , and n8 and n9 each independently represent 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 or may be transmitted through a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, or Stretching base, stretching base, stretching twelve carbon base, stretching cyclopropyl, cyclopentene butyl, cyclopentyl, cyclohexyl, fluorene, fluorene, tetradecyl, thiol The alkyl group of the gold steel is substituted with a substituent such as a group of at least one hydrogen atom of these groups, and the alkyl group having 1 to 50 carbon atoms which may have a substituent; oxymethylene, oxygen extended ethyl, oxygen extended Base, oxybutylene, oxopentyl, oxyhexanyl, oxo, oxydecaxenylene, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy a group having a substituent, a cyclopentadecyloxy group, a fluorenyloxy group, a pendant decyloxy group, a metal alkoxy group, and a substituent of at least one hydrogen atom of these groups may have a substituent. An alkylene group having 1 to 50 carbon atoms; an imido group which may have a substituent; an anthracene group which may have a substituent; a vinyl group which may have a substituent; an exetylene group; -Methanetriyltris the group; isobutyl oxygen atom, a nitrogen atom, a sulfur atom and the Ar ⁴ and bonded.

The Ar ⁴ system may have a substituent other than R ⁹ and R ¹⁰ . As the substituent series, the substituents exemplified in the description of the above Q1 are the same substituents. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

From the viewpoint of easiness of synthesis of the raw material monomers, the substituents other than R ⁹ and R ^{10 of the} above Ar ⁴ are preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a carboxyl group or a substituted carboxyl group. .

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

The series of aromatic groups of (2+n8+n9) valence represented by Ar ⁴ in the chemical formula (20) are: (2+n8+n9) valence aromatic hydrocarbon group, (2+n8+n9) valence The aromatic heterocyclic group is preferably composed of a carbon atom or a carbon atom and one or more atoms selected from the group consisting of a hydrogen atom, a nitrogen atom and an oxygen atom (2+n8+n9). The aromatic base of the price. The series of aromatic groups of the (2+n8+n9) valence are as follows: a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a furan. a monocyclic aromatic ring such as a ring, a pyrrole ring, a pyrazole ring or an imidazole ring, which removes (2+n8+n9) valence groups of (2+n8+n9) hydrogen atoms; consists of condensing the monocyclic aromatic ring a condensed polycyclic aromatic ring selected from two or more rings in the group to remove (2+n8+n9) valence groups of (2+n8+n9) hydrogen atoms; by a single bond, a vinyl group or a stretch An acetylene group which is bonded to an aromatic ring composed of two or more aromatic rings selected from the group consisting of the monocyclic aromatic ring and the condensed polycyclic aromatic ring to remove (2+n8+n9) hydrogen atoms (2+n8+n9) valent group; cross-linking the condensed polycyclic aromatic ring or the adjacent one of the aromatic ring set by a divalent group having a methylene group, an ethyl group, a carbonyl group or the like The cross-linked polycyclic aromatic ring of the aromatic ring removes (2+n8+n9) valence groups of (2+n8+n9) hydrogen atoms.

The monocyclic aromatic ring series is, for example, a ring represented by Chemical Formula 1 to Chemical Formula 5 and Chemical Formula 7 to Chemical Formula 10 exemplified in the description of the structural unit represented by Chemical Formula (13).

The condensed polycyclic aromatic ring series is, for example, a ring represented by Chemical Formula 13 to Chemical Formula 27 exemplified in the description of the structural unit represented by Chemical Formula (13).

As the aromatic ring collection, for example, the ring represented by Chemical Formula 28 to Chemical Formula 36 exemplified in the description of the structural unit represented by Chemical Formula (13).

The series of the cross-linked polycyclic aromatic ring is represented by the chemical formula 37 to the chemical formula 44 exemplified in the related description of the structural unit represented by the chemical formula (13).

The aromatic group of the (2+n8+n9) valence is preferably from the chemical formula 1 to the chemical formula 5, the chemical formula 7 to the chemical formula 10, the chemical formula 13, and the chemical formula 14, from the viewpoint of easiness of synthesis of the raw material monomers. The ring represented by Chemical Formula 26 to Chemical Formula 29, Chemical Formula 37 to Chemical Formula 39 or Chemical Formula 41 removes (2+n8+n9) hydrogen atoms, and more preferably from Chemical Formula 1 to Chemical Formula 6, Chemical Formula 8, Chemical Formula 14, Chemical Formula 27 The ring represented by Chemical Formula 28, Chemical Formula 38 or Chemical Formula 42 removes (2+n8+n9) hydrogen atoms, and is even preferably removed by a ring represented by Chemical Formula 1, Chemical Formula 37 or Chemical Formula 41 (2+n8+). N9) The base of a hydrogen atom.

In the chemical formula (21), R ¹¹ represents a single bond or an organic group of a (1+m7) valence, preferably an organic group of a (1+m7) valence.

In the chemical formula (21), the organic group of the (1+m7) valence represented by R ¹¹ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of m7 hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent. a group of at least one hydrogen atom or the like which may have a substituent having 6 to 30 carbon atoms and a group of m7 hydrogen atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyl group Oxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, norbornoxy, The alkoxy group of the gold steel is substituted with a substituent such as a group of at least one hydrogen atom of these groups, and the alkoxy group having 1 to 50 carbon atoms which may have a substituent, and a group of m7 hydrogen atoms; Substituent The amine group removes a group of m7 hydrogen atoms; the group of m7 hydrogen atoms is removed from a mercapto group having a substituent containing a carbon atom, and from the viewpoint of easiness of synthesis of the raw material monomer, it is preferable to remove m7 from the alkyl group. A group of a hydrogen atom, a group of m7 hydrogen atoms removed from an aryl group, and a group of m7 hydrogen atoms removed by an alkoxy group.

The substituents exemplified in the description of the above Q1 are the same substituents as the substituent series. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

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

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

In the chemical formula (22), the organic group of the (1+m8) valence represented by R ¹² is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of m8 hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent. a group of at least one hydrogen atom or the like which may have a substituent having 6 to 30 carbon atoms and a group of m8 hydrogen atoms; methoxy group, ethoxy group, propoxy group, butoxy group, pentyl group Oxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, norbornoxy, The alkoxy group of the gold steel is substituted with a substituent such as a group of at least one hydrogen atom of these groups, and the alkoxy group having 1 to 50 carbon atoms which may have a substituent, and a group of m8 hydrogen atoms; Substituent The amine group removes the group of m8 hydrogen atoms; the group of m8 hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and it is preferable to remove m8 from the alkyl group from the viewpoint of easiness of synthesis of the raw material monomer. A group of a hydrogen atom, a group of m8 hydrogen atoms removed from the aryl group, and a group of m8 hydrogen atoms removed from the alkoxy group.

The substituents exemplified in the description of the above Q1 are the same substituents as the substituent series. In the case where a plurality of the substituents are present, a plurality of substituents may be present, and they may be the same or different.

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

An example of a structural unit represented by the chemical formula (13)

The structural unit represented by the chemical formula (13) is preferably a structural unit represented by the chemical formula (23) or a structural unit represented by the chemical formula (24) from the viewpoint of electron transportability of the obtained ionic polymer. More preferably, it is a structural unit represented by the chemical formula (24).

(In the chemical formula (23), R ¹³ represents an organic group having a valence of (1+m9+m10), and R ¹⁴ represents an organic group having a monovalent group, Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 are the same as described above, and m9 and m10 each independently represent an integer of 1 or more, and are in Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , Each of n1, a1, b1, and n3 has a plurality of Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 in a plurality of states, respectively The same, it can be different.)

In the chemical formula (23), the organic group of the (1+m9+m10) valence represented by R ¹³ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-. a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m9+m10) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m9+m10) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group substituted with a substituent at least one of these groups, and the like, or alkoxy group having 1 to 50 carbon atoms which may have a substituent (m9) +m10) a base of hydrogen atoms; The amine group of the substituent of the carbon atom removes a group of (m9+m10) hydrogen atoms; the base of the (m9+m10) hydrogen atom is removed from the sulfhydryl group having a substituent containing a carbon atom, and is easily synthesized from a raw material monomer From the viewpoint of degree, it is preferred to remove (m9+m10) hydrogen atoms from the alkyl group, remove (m9+m10) hydrogen atoms from the aryl group, and remove (m9+m10) from the alkoxy group. The base of a hydrogen atom.

In the chemical formula (23), the monovalent organic group represented by R ¹⁴ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl. a group having 1 or more carbon atoms which may have a substituent, such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a substituent substituted by at least one of these groups, and the like. a group of up to 1 hydrogen atom; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group substituted with at least one of these groups by a substituent a group of a hydrogen atom or the like which may have a substituent of 6 to 30 carbon atoms to remove one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyl group Oxyl, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, norbornoxy, gold alkoxy a group in which an alkoxy group having 1 to 50 carbon atoms which may have a substituent and a substituent such as at least one hydrogen atom in the group is substituted by a substituent; and a substituent having a carbon atom; Amine A group in which one hydrogen atom is removed; a group in which one hydrogen atom is removed from a mercapto group having a substituent containing a carbon atom, and from the viewpoint of easiness of synthesis of a raw material monomer, it is preferred to remove one hydrogen from the alkyl group. A group of an atom, a group in which one hydrogen atom is removed from an aryl group, and a group in which one hydrogen atom is removed from an alkoxy group.

The structural unit series represented by the chemical formula (23) is exemplified by the following structural unit.

(In the chemical formula (24), R ¹³ represents an organic group of (1+m11+m12) valence, and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 are The meanings are the same as described above, and m11 and m12 each independently represent an integer of 1 or more, in R ¹³ , m11 , m12 , Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1. Each of b1 and n3 has a plurality of R ¹³ , m11 , m12 , Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and N3, respectively, can be the same or different.)

In the chemical formula (24), as an organic group of (1+m11+m12) valence represented by ^R13 , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m11+m12) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m11+m12) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group substituted with a substituent at least one of these groups, and the like, and alkoxy group having 1 to 50 carbon atoms which may have a substituent (m11) +m12) a group of hydrogen atoms; The amine group of the substituent containing a carbon atom removes a group of (m11+m12) hydrogen atoms; the group of (m11+m12) hydrogen atoms is removed from a mercapto group having a substituent containing a carbon atom, and is synthesized from a raw material monomer From the viewpoint of easiness, it is preferred to remove (m11+m12) hydrogen atoms from the alkyl group, remove (m11+m12) hydrogen atoms from the aryl group, and remove them by the alkoxy group (m11+m12). The base of a hydrogen atom.

The following structural unit is given as a series of structural units represented by the chemical formula (24).

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

(In the chemical formula (25), R ¹⁵ represents an organic group having a valence of (1+m13+m14), and Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 are It is the same as the above-described meaning, and m13, m14, and m15 each independently represent an integer of 1 or more, and are in R ¹⁵ , m13 , m14 , Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , and n1. Each of a1, b1, and n3 has a plurality of R ¹⁵ , m13 , m14 , Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1 in a plurality of states. B1 and n3 can be the same or different.)

In the chemical formula (25), the organic group of (1+m13+m14) valence represented by R ¹⁵ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m13+m14) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m13+m14) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group, a group of at least one hydrogen atom of these groups substituted with a substituent, etc., and an alkoxy group having 1 to 50 carbon atoms which may have a substituent (m13) +m14) a group of hydrogen atoms; The amine group of the substituent containing a carbon atom removes a group of (m13+m14) hydrogen atoms; the group of (m13+m14) hydrogen atoms is removed from a mercapto group having a substituent containing a carbon atom, and is synthesized from a raw material monomer From the viewpoint of easiness, it is preferred to remove (m13+m14) hydrogen atoms from the alkyl group, remove (m13+m14) hydrogen atoms from the aryl group, and remove it by the alkoxy group (m13+m14). The base of a hydrogen atom.

The following structural unit is given as a series of structural units represented by the chemical formula (25).

An example of a structural unit represented by the chemical formula (15)

The structural unit represented by the chemical formula (15) is preferably a structural unit represented by the chemical formula (26) or a structural unit represented by the chemical formula (27) from the viewpoint of electron transportability of the obtained ionic polymer. More preferably, it is a structural unit represented by the chemical formula (27).

(In the chemical formula (26), R ¹⁶ represents an organic group having a (1+m16+m17) valence, and 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 are the same as described above, and m16 and m17 each independently represent an integer of 1 or more, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2 Each of a2, b2, and n3 has a plurality of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n ² , a ² , b ² , and n ³ in a plurality of states, which may be the same , can also be different.)

In Chemical Formula (26), as represented by the R ¹⁶ (1 + m16 + m17) the divalent organic radical such as Series Examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m16+m17) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m16+m17) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group, a group substituted with at least one hydrogen atom of these groups by a substituent, etc., and an alkoxy group having 1 to 50 carbon atoms which may have a substituent (m16) +m17) a group of hydrogen atoms; The amine group of the substituent containing a carbon atom removes a group of (m16+m17) hydrogen atoms; the group of (m16+m17) hydrogen atoms is removed from a mercapto group having a substituent containing a carbon atom, and is synthesized from a raw material monomer From the viewpoint of easiness, it is preferred to remove (m16+m17) hydrogen atoms from the alkyl group, remove (m16+m17) hydrogen atoms from the aryl group, and remove them by the alkoxy group (m16+m17). The base of a hydrogen atom.

In the chemical formula (26), the monovalent organic group represented by R ¹⁷ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl. a group having 1 or more carbon atoms which may have a substituent, such as a group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, a substituent substituted by at least one of these groups, and the like. a group of up to 1 hydrogen atom; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group substituted with at least one of these groups by a substituent a group of a hydrogen atom or the like which may have a substituent of 6 to 30 carbon atoms to remove one hydrogen atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyl group Oxyl, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, norbornoxy, gold alkoxy a group in which an alkoxy group having 1 to 50 carbon atoms which may have a substituent and a substituent such as at least one hydrogen atom in the group is substituted by a substituent; and a substituent having a carbon atom; Amine A group in which one hydrogen atom is removed; a group in which one hydrogen atom is removed from a mercapto group having a substituent containing a carbon atom, and from the viewpoint of easiness of synthesis of a raw material monomer, it is preferred to remove one hydrogen from the alkyl group. A group of an atom, a group in which one hydrogen atom is removed from an aryl group, and a group in which one hydrogen atom is removed from an alkoxy group.

The following structural unit is given as a series of structural units represented by the chemical formula (26).

(In the chemical formula (27), R ¹⁶ represents an organic group of (1+m16+m17) valence, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 are The meanings are the same as described above, and m16 and m17 each independently represent an integer of 1 or more, R ¹⁶ , m16, m17, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2. Each of b2 and n3 has a plurality of R ¹⁶ , m16, m17, Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 in a plurality of states. , they can be the same or different.)

In Chemical Formula (27), as represented by the R ¹⁶ (1 + m16 + m17) the divalent organic radical such as Series Examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m16+m17) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a substituent of at least one of these groups, a group of (m16+m17) hydrogen atoms removed; a methoxy group, an ethoxy group , propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, a cyclopentyloxy group, a norbornyloxy group, a gold alkoxy group, a group substituted with at least one hydrogen atom of these groups by a substituent, etc., and an alkoxy group having 1 to 50 carbon atoms which may have a substituent (m16) +m17) a group of hydrogen atoms; The amine group of the substituent containing a carbon atom removes a group of (m16+m17) hydrogen atoms; the group of (m16+m17) hydrogen atoms is removed from a mercapto group having a substituent containing a carbon atom, and is synthesized from a raw material monomer From the viewpoint of easiness, it is preferred to remove (m16+m17) hydrogen atoms from the alkyl group, remove (m16+m17) hydrogen atoms from the aryl group, and remove them by the alkoxy group (m16+m17). The base of a hydrogen atom.

The following structural unit is given as a series of structural units represented by the chemical formula (27).

The structural unit represented by the chemical formula (15) is preferably a structural unit represented by the chemical formula (28) from the viewpoint of durability of the obtained ionic polymer.

(In the chemical formula (28), R ¹⁸ represents an organic group of (1+m18+m19) valence, and Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2, and n3 are The meanings are the same as described above, and m18, m19, and m20 each independently represent an integer of 1 or more, and R ¹⁸ , m18 , m19 , Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , and n2. Each of a2, b2, and n3 has a plurality of R ¹⁸ , m18 , m19 , Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n ² , a ² , b ² in a plurality of states. And n3, respectively, can be the same or different.)

In the chemical formula (28), the organic group of the (1+m18+m19) valence represented by R ¹⁸ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-. a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a lauryl group, or a substituent may be substituted with a substituent such as at least one of these groups. The alkyl group having 1 to 20 carbon atoms of the group removes a group of (m18+m19) hydrogen atoms; phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 2-indenyl, 9-fluorenyl An aryl group having 6 to 30 carbon atoms which may have a substituent substituted by a substituent such as a group of at least one of these groups, and a group of (m18+m19) hydrogen atoms removed; methoxy group, ethoxy group Base, propoxy, butoxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy And a cycloalkoxy group, a decyloxy group, a fluorenyloxy group, a gold alkoxy group, a group of at least one hydrogen atom of these groups substituted with a substituent, etc., and an alkoxy group having 1 to 50 carbon atoms which may have a substituent ( M18+m19) a group of hydrogen atoms; An amine group containing a substituent of a carbon atom removes a group of (m18+m19) hydrogen atoms; a group of (m18+m19) hydrogen atoms removed from a mercapto group having a substituent containing a carbon atom, synthesized from a raw material monomer From the viewpoint of easiness, it is preferable to remove (m18+m19) hydrogen atoms from the alkyl group, remove (m18+m19) hydrogen atoms from the aryl group, and remove them by the alkoxy group (m18+m19). The base of a hydrogen atom.

The structural unit series represented by the chemical formula (28) is exemplified by the following structural unit.

An example of a structural unit represented by the chemical formula (17)

The structural unit represented by the chemical formula (17) is preferably a structural unit represented by the chemical formula (29) from the viewpoint of electron transportability of the obtained ionic polymer.

(In the chemical formula (29), R ¹⁹ represents a single bond or an organic group of a (1+m21) valence, and R ²⁰ represents a single bond or an organic group of a (1+m22) valence, Q ¹ , Q ³ , Y ¹ M ¹ , Z ¹ , Y ³ , n1 , a1 , b1 and n3 are the same as those described above, and m21 and m22 each independently represent an integer of 1 or more. However, when R ¹⁹ is a single bond, m21 It means 1, when R ²⁰ is a single bond, m22 represents 1. Each of Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1 and n3 has a plurality of In the state, a plurality of Q ¹ , Q ³ , Y ¹ , M ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3 may be the same or different.

In the chemical formula (29), the organic group of the (1+m21) valence represented by R ¹⁹ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m21) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent a group of at least one hydrogen atom of these groups, etc., which may have a substituent of 6 to 30 carbon atoms, and an alkyl group of (m21) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower a group in which an alkoxy group having 1 to 50 carbon atoms which may have a substituent and a substituent of at least one hydrogen atom in the group, such as a substituent of at least one hydrogen atom of the group, such as a hydroxyl group; By having carbon atoms The amine group of the substituent removes (m21) groups of hydrogen atoms; the group of (m21) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m21) hydrogen atoms is removed from the alkyl group, the (m21) hydrogen atom group is removed from the aryl group, and the (m21) hydrogen atom group is removed from the alkoxy group.

In the chemical formula (29), the organic group of the (1+m22) valence represented by R ²⁰ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m22) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent An aryl group having 6 to 30 carbon atoms which may have a substituent of at least one of these groups, and a group of (m22) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower a group in which an alkoxy group having 1 to 50 carbon atoms which may have a substituent and a substituent of at least one hydrogen atom in the group, such as a substituent of at least one hydrogen atom of the group, such as a substituent; By having carbon atoms The amine group of the substituent removes (m22) groups of hydrogen atoms; the group of (m22) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m22) hydrogen atoms is removed from the alkyl group, the (m22) hydrogen atom group is removed from the aryl group, and the (m22) hydrogen atom group is removed from the alkoxy group.

The structural unit series represented by the chemical formula (29) is exemplified by the following structural unit.

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

(In the chemical formula (30), R ²¹ represents a single bond or an organic group of a (1+m23) valence, and R ₂₂ represents a single bond or an organic group of a (1+m24) valence, Q ¹ , Q ³ , Y ¹ M ¹ , Z ¹ , Y ³ , n1 , a1 , b1 and n3 are the same as those described above, and m23 and m24 each independently represent an integer of 1 or more. However, when R ²¹ is a single bond, m23 1 indicates that when R ²² is a single bond, m24 represents 1. m25 and m26 each independently represent an integer of 1 or more, m23, m24, R ²¹ , R ²² , Q ¹ , Q ³ , Y ¹ , M ¹ , each of Z ¹ , Y ³ , n1 , a1 , b1 and n3 has a plurality of m23, m24, R ²¹ , R ²² , Q ¹ , Q ³ , Y ¹ , M in a plurality of states. ¹ , Z ¹ , Y ³ , n1, a1, b1, and n3, respectively, may be the same or different.)

In the chemical formula (30), the organic group of the (1+m23) valence represented by R ²¹ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m23) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent a group of at least one hydrogen atom of these groups, etc., which may have a substituent of 6 to 30 carbon atoms, and an alkyl group of (m23) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower a group in which an alkoxy group having 1 to 50 carbon atoms which may have a substituent and a substituent of at least one hydrogen atom in the group, such as a substituent of at least one of these groups, is substituted by a substituent, and a group of (m23) hydrogen atoms is removed. By having carbon atoms The amine group of the substituent removes a group of (m23) hydrogen atoms; the group of (m23) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m23) hydrogen atoms is removed from the alkyl group, the (m23) hydrogen atom group is removed from the aryl group, and the (m23) hydrogen atom group is removed from the alkoxy group.

In the chemical formula (30), the organic group of the (1+m24) valence represented by R ²² is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m24) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent a group of at least one hydrogen atom of these groups, etc., which may have a substituent of 6 to 30 carbon atoms, and an alkyl group of (m24) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower The alkoxy group having 1 to 50 carbon atoms which may have a substituent, such as a group of at least one hydrogen atom of the group, substituted by a substituent, or alkoxy group of the gold alkoxy group, and the (m24) hydrogen atom group By having carbon atoms The amine group of the substituent removes (m24) groups of hydrogen atoms; the group of (m24) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m24) hydrogen atoms is removed from the alkyl group, the (m24) hydrogen atom group is removed from the aryl group, and the (m24) hydrogen atom group is removed from the alkoxy group.

The following structural unit is given as a series of structural units represented by the chemical formula (30).

An example of a structural unit represented by the chemical formula (20)

The structural unit represented by the chemical formula (20) is preferably a structural unit represented by the chemical formula (31) from the viewpoint of the electron transport property obtained.

(In the chemical formula (31), R ²³ represents a single bond or an organic group of a (1+m27) valence, and R ²⁴ represents a single bond or an organic group of a (1+m28) valence, Q ² , Q ³ , Y ² M ² , Z ² , Y ³ , n2, a2, b2 and n3 are the same as described above, and m27 and m28 each independently represent an integer of 1 or more. However, when R ²³ is a single bond, m27 It means 1, when R ²⁴ is a single bond, m28 means 1. Each of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , n2, a2, b2 and n3 has a plurality of In the state, a plurality of Q ² , Q ³ , Y ² , M ² , Z ² , Y ³ , _n 2, a2, b2, and n3 may be the same or different.

In the chemical formula (31), the organic group of the (1+m27) valence represented by R ²³ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m27) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent a group of at least one hydrogen atom of these groups, etc., which may have a substituent of 6 to 30 carbon atoms, and an alkyl group of (m27) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower The alkoxy group having 1 to 50 carbon atoms which may have a substituent and the alkoxy group having at least one hydrogen atom in the group substituted with a substituent such as a methoxy group or a gold alkoxy group to remove (m27) hydrogen atoms By having carbon atoms The amine group of the substituent removes (m27) hydrogen atom groups; the (m27) hydrogen atom group is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomer Preferably, the group of (m27) hydrogen atoms is removed from the alkyl group, the (m27) hydrogen atom group is removed from the aryl group, and the (m27) hydrogen atom group is removed from the alkoxy group.

In the chemical formula (31), the organic group of the (1+m28) valence represented by R ²⁴ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m28) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent a group of at least one hydrogen atom of these groups, etc., which may have a substituent of 6 to 30 carbon atoms, and an alkyl group of (m28) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower The alkoxy group having 1 to 50 carbon atoms which may have a substituent, such as a group of at least one hydrogen atom of the group, substituted by a substituent such as a methoxy group or a gold alkoxy group, and the (m28) hydrogen atom group is removed. By having carbon atoms The amine group of the substituent removes (m28) groups of hydrogen atoms; the group of (m28) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m28) hydrogen atoms is removed from the alkyl group, the (m28) hydrogen atom group is removed from the aryl group, and the (m28) hydrogen atom group is removed from the alkoxy group.

The structural unit series represented by the chemical formula (31) is exemplified by the following structural unit.

The structural unit represented by the chemical formula (20) is preferably a structural unit represented by the chemical formula (32) from the viewpoint of durability of the obtained ionic polymer.

(In the chemical formula (32), R ²⁵ represents a single bond or an organic group of (1+m29) valence, and R ²⁶ represents a single bond or an organic group of (1+m30) valence, Q ² , Q ³ , Y ² M ² , Z ² , Y ³ , n2, a2, b2 and n3 are the same as described above, and m29 and m30 each independently represent an integer of 1 or more. However, when R ²⁵ is a single bond, m29 1 indicates that when R ²⁶ is a single bond, m30 represents 1. m31 and m32 each independently represent an integer of 1 or more, m29, m30, R ²⁵ , R ²⁶ , Q ² , Q ³ , Y ² , M ² , each of Z ² , Y ³ , n2, a2, b2, and n3 has a plurality of m29, m30, R ²⁵ , R ²⁶ , Q ² , Q ³ , Y ² , M in a plurality of states. ² , Z ² , Y ³ , n2, a2, b2, and n3, respectively, may be the same or different.)

In the chemical formula (32), the organic group of the (1+m29) valence represented by R ²⁵ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m29) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent a group of at least one hydrogen atom of these groups, etc., which may have a substituent of 6 to 30 carbon atoms, and an alkyl group of (m29) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower The alkoxy group having 1 to 50 carbon atoms which may have a substituent and the alkoxy group having a substituent of at least one of these groups may have a substituent of (m29) a hydrogen atom. By having carbon atoms The amine group of the substituent removes (m29) groups of hydrogen atoms; the group of (m29) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m29) hydrogen atoms is removed from the alkyl group, the (m29) hydrogen atom group is removed from the aryl group, and the (m29) hydrogen atom group is removed from the alkoxy group.

In the chemical formula (32), the organic group of the (1+m30) valence represented by R ²⁶ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl. And a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, a lauryl group, a substituent such as a group substituted by at least one of these groups, or the like may have a substituent. An alkyl group having 1 to 20 carbon atoms removes a group of (m30) hydrogen atoms; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group are substituted with a substituent An aryl group having 6 to 30 carbon atoms which may have a substituent at least one of these groups, and a group of (m30) hydrogen atoms; methoxy group, ethoxy group, propoxy group, butyl group Oxy, pentyloxy, hexyloxy, decyloxy, lauryloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclodecyloxy, cyclolauroyloxy, lower The alkoxy group having 1 to 50 carbon atoms which may have a substituent, such as a group of at least one hydrogen atom of the group, substituted by a substituent such as a methoxy group or a gold alkoxy group, and the (m30) hydrogen atom group is removed. By having carbon atoms The amine group of the substituent removes (m30) groups of hydrogen atoms; the group of (m30) hydrogen atoms is removed from the sulfhydryl group having a substituent containing a carbon atom, and the most convenient from the viewpoint of the synthesis of the raw material monomers Preferably, the group of (m30) hydrogen atoms is removed from the alkyl group, the (m30) hydrogen atom group is removed from the aryl group, and the (m30) hydrogen atom group is removed from the alkoxy group.

The following structural unit is given as a series of structural units represented by the chemical formula (32).

‧Other structural units

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

(In the chemical formula (33), Ar ⁵ represents a divalent aromatic group which may have a substituent or a divalent aromatic amine residue which may have a substituent, and X' represents an imine which may have a substituent a fluorenylene group which may have a substituent, a vinyl group or an ethynyl group which may have a substituent, and m33 and m34 each independently represent 0 or 1, and at least one of m33 and m34 is 1.

The divalent aromatic group represented by Ar ⁵ in the chemical formula (33) is a divalent aromatic hydrocarbon group or 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, and a 1,3,5-triazine. a monocyclic aromatic ring such as a ring, a furan ring, a pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, an oxadiazole ring or an oxadiazole ring, which removes a divalent group of two hydrogen atoms; a condensed polycyclic aromatic ring selected from the group consisting of a monocyclic aromatic ring to remove a divalent group of two hydrogen atoms; linked by a single bond, a vinyl group or an ethynyl group The aromatic ring set consisting of two or more aromatic rings selected from the group consisting of a monocyclic aromatic ring and the condensed polycyclic aromatic ring is removed from the divalent group of two hydrogen atoms; Crosslinking a bicyclic group such as an ethyl group, a carbonyl group, or an imido group to crosslink the condensed polycyclic aromatic ring or a crosslinked polycyclic aromatic ring of two adjacent aromatic rings of the aromatic ring set to remove two hydrogen atoms The 2 price base and so on.

In the above condensed polycyclic aromatic ring, the number of condensed monocyclic aromatic rings is preferably from 2 to 4, more preferably from 2 to 3, even more preferably from the viewpoint of solubility of the ionic polymer. It is 2. In the above aromatic ring set, the number of linked aromatic rings is preferably from 2 to 4, more desirably from 2 to 3, and even more preferably 2 from the viewpoint of solubility. In the above crosslinked polycyclic aromatic ring, the number of crosslinked aromatic rings is preferably from 2 to 4, more preferably from 2 to 3, even more preferably from the viewpoint of solubility of the ionic polymer. 2.

As the series of the above-mentioned monocyclic aromatic ring, for example, the following ring is mentioned.

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

As the series of the above-mentioned aromatic rings, for example, the following rings are mentioned.

The series of the above-mentioned crosslinked polycyclic aromatic ring is exemplified by the following ring.

From the viewpoint of either or both of the electron acceptability and the hole acceptability of the ionic polymer, the divalent aromatic group represented by Ar ⁵ is preferably from the chemical formula 45 to the chemical formula 60, and the chemical formula 61 to The ring represented by the chemical formula 71, the chemical formula 77 to the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 93 or the chemical formula 96 removes the divalent group of two hydrogen atoms, and more preferably from the chemical formula 45 to the chemical formula 50, the chemical formula 59, the chemical formula 60, The ring represented by Chemical Formula 77, Chemical Formula 80, Chemical Formula 91, Chemical Formula 92 or Chemical Formula 96 removes the divalent group of two hydrogen atoms.

The divalent aromatic group may have a substituent. As the substituent series, the substituents exemplified in the description of the above Q1 are the same substituents.

The series of divalent aromatic amine residues represented by Ar ⁵ in the chemical formula (33) is a group represented by the chemical formula (34).

(In the chemical formula (34), Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ each independently represent an extended aryl group which may have a substituent or a divalent heterocyclic group which may have a substituent, Ar ¹⁰ , Ar ¹¹ and Ar ¹² each independently represent an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent, and n10 and m35 each independently represent 0 or 1.)

The above-mentioned aryl group, aryl group, divalent heterocyclic group and monovalent heterocyclic group may have a series of substituents such as a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group or an aryloxy group. , arylthio, arylalkyl, arylalkoxy, arylalkylthio, alkenyl, alkynyl, arylalkenyl, arylalkynyl, fluorenyl, decyloxy, decylamino,醯imino, imine residue, substituted amine, substituted fluorenyl, substituted methoxy, substituted thiol, substituted guanyl, cyano, nitro, monovalent heterocyclic, heteroaryloxy, a heteroarylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylalkoxycarbonyl group, a heteroaryloxycarbonyl group, a carboxyl group or the like. The substituent may be a vinyl group, an ethynyl group, a butenyl group, an acryl group, an acrylate group, an acrylamide group, a methacryl group, a methacrylate group, a methacrylamide group, a vinyl ether group. a vinylamino group, a stanol group, a group having a small member ring (cyclopropyl group, cyclobutyl group, epoxy group, oxetane group, diketene group, episulfide group, etc.), a lactone group, The indole amine group or a crosslinking group such as a group containing a structure of a halogenated alkane derivative.

In the state where 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 the monovalent heterocyclic group which are represented by Ar ¹⁰ , Ar ¹¹ and Ar ¹² are the same as those described above, and the aryl group and the monovalent heterocyclic group which are exemplified as the substituent are described.

The aryl group represented by Ar ⁶ , Ar ⁷ , Ar ⁸ , and Ar ⁹ is an atomic group in which two hydrogen atoms bonded to a carbon atom constituting the aromatic ring are removed by an aromatic hydrocarbon, and a benzene ring is exemplified. The base, the condensed ring group, the independent benzene ring or the fused ring are bonded to the base by a single bond or a divalent organic group, for example, an extended alkenyl group such as a vinyl group. The number of carbon atoms of the aryl group is generally from 6 to 60, preferably from 7 to 48. As a specific example series of exoaryl groups, phenyl, exophenyl, C ₁ to C ₁₇ alkoxyphenyl, C ₁ to C ₁₇ alkylphenyl, 1-anthranyl, 2-naphthyl , 1-extension base, 2-extension base, 9-extension base. The hydrogen atom in the aforementioned aryl group may be substituted by a fluorine atom. The fluorine-substituted aryl group is a tetrafluorophenylene group. Among the aryl groups, it is preferred to extend a phenyl group, a biphenyl group, a C ₁ to C ₁₂ alkoxyphenyl group, and a C ₁ to C ₁₂ alkyl group.

The divalent heterocyclic group represented by Ar ⁶ , Ar ⁷ , Ar ⁸ or Ar ⁹ is a group of atoms remaining after removing two hydrogen atoms from a heterocyclic compound. Here, the heterocyclic compound refers to an organic compound having a cyclic structure, and not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, or a ruthenium as an element constituting the ring. An organic compound of a hetero atom such as an atom, a selenium atom, a helium atom or an arsenic atom. The divalent heterocyclic group may have a substituent. The divalent heterocyclic group has a carbon number of usually 4 to 60, preferably 4 to 20. Further, the number of carbon atoms of the divalent heterocyclic group does not include the number of carbon atoms of the substituent. Examples of such a divalent heterocyclic group include a thiophenediyl group, a C ₁ to C ₁₂ alkylthiophenediyl group, a pyrrole diyl group, a furanyl group, a pyridyldiyl group, and a C ₁ to C ₁₂ alkylpyridinediyl group. , pyridazine diyl, pyrimidine diyl, pyrazinediyl, triazinediyl, pyrrolidinediyl, piperidinyldiyl, quinolinediyl, isoquinolinyldiyl, wherein more preferred is thiophenediyl, C ₁ to C ₁₂ alkylthiophenediyl, pyridinyl and C ₁ to C ₁₂ alkylpyridinyl.

The ionic polymer containing a divalent aromatic amine residue as a structural unit may have other structural units. As other series of structural units, such as stretching phenyl, stretching bismuth, etc. Further, among these ionic polymers, those which contain a crosslinking group are preferred.

In addition, the divalent aromatic amine residue represented by the chemical formula (34) is exemplified by a group in which two hydrogen atoms are removed by an aromatic amine represented by the following Chemical Formula 101 to Chemical Formula 110.

The aromatic amine represented by the chemical formula 101 to the chemical formula 110 may have a substituent in the range in which a divalent aromatic amine residue can be formed, and the substituent exemplified in the description of the above Q1 as the substituent series is In the same substituent, the substituent is present in a plurality of states, and a plurality of substituents may be present in the same or different.

In the chemical formula (33), X' represents an imido group which may have a substituent, an anthracene group which may have a substituent, a vinyl group or an ethynyl group which may have a substituent. The series of substituents which may be an imido group, a mercapto group or a vinyl group may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, An alkyl group having 1 to 20 carbon atoms; a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a decyl group, a 3,7-dimethyloctyl group, a lauryl group or the like; a phenyl group having 6 to 30 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group or the like, and the substituent is in a state in which a plurality of substituents are present There are a plurality of substituents which may be the same or different.

From the viewpoint of the stability of the above ionic polymer by air, moisture or heat, X' is preferably an imido group, a vinyl group, or an ethynyl group.

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

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

(In the chemical formula (35), Ar ¹³ represents a pyridyl group which may have a substituent, a pyrazinediyl group which may have a substituent, a pyrimidinediyl group which may have a substituent, a pyridazine diyl group which may have a substituent, or Is a triazine diyl group which may have a substituent.)

The substituent which the pyridinediyl group may have is the same substituent as the substituent exemplified in the description of the above Q1. The substituent is a plurality of substituents in a plurality of states, and may be the same or different.

The substituents which the pyrazinediyl group may have are the same substituents as those exemplified in the description of the above Q1. The substituent is a plurality of substituents in a plurality of states, and may be the same or different.

The substituent which the pyrimidine dimercapto group may have is the same substituent as the substituent exemplified in the description of the above Q1. The substituent is a plurality of substituents in a plurality of states, and may be the same or different.

The substituents which the procarbazinediyl group may have are the same substituents as those exemplified in the description of the above Q1. The substituent is a plurality of substituents in a plurality of states, and may be the same or different.

The substituent which the triazinediyl group may have is the same substituent as the substituent exemplified in the description of the above Q1. The substituent is a plurality of substituents in a plurality of states, and may be the same or different.

‧ proportion of structural units

The structural unit represented by the chemical formula (13), the structural unit represented by the chemical formula (15), the structural unit represented by the chemical formula (17), and the structure represented by the chemical formula (20) contained in the ionic polymer used in the present invention. The total ratio of the units is preferably 30 mol% to 100 mol% of the total structural unit contained in the ionic polymer excluding the structural unit at the end.

‧Structural unit at the end

Further, as a structural unit (terminal group) of the terminal of the ionic polymer used in the present invention, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a sec- Butyl, tert-butyl, pentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, decyl, lauryl, methoxy, ethyloxy, propoxy, isopropoxy , butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy Base, decyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio , sec-butylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, sulfonylthio, sulfonylthio, laurel, methoxybenzene Base, ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, butoxyphenyl, isobutoxyphenyl, sec-butoxyphenyl, tert-butoxyphenyl, Pentyloxyphenyl, hexyloxyphenyl, cyclohexyloxyphenyl, heptyloxyphenyl, Oxyphenyl, 2-ethylhexyloxyphenyl, nonyloxyphenyl, nonyloxyphenyl, 3,7-dimethyloctyloxyphenyl, lauryloxyphenyl, methylphenyl , ethylphenyl, dimethylphenyl, propylphenyl, trimethylphenyl, methylethylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylbenzene , pentylphenyl, isopentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, nonylphenyl, laurylphenyl, methylamino, dimethyl Amino, ethylamino, diethylamino, propylamino, dipropylamino, isopropylamino, diisopropylamino, butylamino, isobutylamino, sec -butylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, decylamino, Merylamino, 3,7-dimethyloctylamino, laurylamine, cyclopentylamino, dicyclopentylamino, cyclohexylamino, dicyclohexylamino, di(trifluoro) Methyl)amino, phenylamino, diphenylamino, (C ₁ to C ₁₂ alkoxyphenyl) amine, di (C ₁ to C ₁₂ Alkoxyphenyl)amino, di(C ₁ to C ₁₂ alkylphenyl)amino, 1-naphthylamino, 2-naphthylamino, pentafluorophenylamino, pyridylamino, Pyridazinylamino, pyrimidinylamino, pyrazinylamino, triazinylamino, (phenyl-C ₁ to C ₁₂ alkyl)amino, (C ₁ to C ₁₂ alkoxyphenyl - C ₁ to C ₁₂ alkyl)amino, (C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl)amino, di(C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl)amino, di(C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl)amino, 1-naphthyl-C ₁ to C ₁₂ alkylamino, 2-naphthyl- C ₁ to C ₁₂ alkylamino, trimethyl decyl, triethyl decyl, tripropyl decyl, triisopropyl decyl, isopropyl dimethyl decyl, isopropyl diethyl Sulfhydryl, tert-butyldimethylmethyl, pentyl dimethyl fluorenyl, hexyl dimethyl fluorenyl, heptyl dimethyl fluorenyl, octyl dimethyl fluorenyl, 2-ethylhexyl Methyl fluorenyl, decyl dimethyl fluorenyl, decyl dimethyl fluorenyl, 3,7-dimethyloctyl dimethyl fluorenyl, lauryl dimethyl fluorenyl, (phenyl-C ₁ to C ₁₂ alkyl) silicon based, (C ₁ to C ₁₂ alkoxyphenyl--C ₁ to C ₁₂ alkyl) silicon , (C ₁ to C ₁₂ alkylphenyl group -C ₁ to C ₁₂ alkyl) silicon based, (1-naphthyl -C ₁ to C ₁₂ alkyl) of silicon-based, (2-naphthyl -C ₁ to C ₁₂ alkyl) fluorenyl, (phenyl-C ₁ to C ₁₂ alkyl) dimethyl fluorenyl, triphenyl fluorenyl, tris(p-dimethylphenyl) fluorenyl, tribenzyl fluorenyl, diphenyl Methyl fluorenyl, tert-butyl diphenyl fluorenyl, dimethylphenyl fluorenyl, thienyl, C ₁ to C ₁₂ alkyl thiophenyl, pyrrolyl, furyl, pyridyl, C ₁ to C ₁₂ alkyl pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolyl, isoquinolinyl, hydroxy, fluorenyl, fluorine, chlorine, bromine And iodine atoms and the like. The terminal structure unit is a plurality of end structure units in a plurality of states, and may be the same or different.

- Characteristics of ionic polymers -

The ionic polymer used in the present invention is preferably a conjugated compound. The ionic polymer used in the present invention is a conjugated compound, and means that the ionic polymer is contained, and in the main chain, a plurality of bonds (for example, a double bond or a triple bond) or a nitrogen atom or an oxygen atom are not shared. An area where an unshared electron pair is connected by a single button. When the ionic polymer is a conjugated compound, it is preferable that the conjugated compound is sandwiched by an unshared electron pair having a bond or a nitrogen atom or an oxygen atom from the viewpoint of electron transportability of the conjugated compound. The number of atoms in the main chain of the region where one single bond is connected) / (the total number of atoms in the main chain)} × 100%, and the ratio calculated is 50% or more, more preferably 60% or more, even the most Fortunately, 70% or more, especially preferably 80% or more, more ideally 90% or more.

Further, the ionic polymer used in the present invention is preferably a polymer compound, and more preferably a conjugated polymer compound. Here, the polymer compound means a compound having a number average molecular weight of 1 × 10 ³ or more in terms of polystyrene. In addition, the ionic polymer used in the present invention is a conjugated polymer compound, and the ionic polymer is a conjugated compound and is a polymer compound.

The number average molecular weight of the ionic polymer in terms of polystyrene is preferably from 1 × 10 ³ to 1 × from the viewpoint of film formability by coating of the ionic polymer used in the present invention. 10 ^{8 is} more preferably 2 × 10 ³ to 1 × 10 ⁷ , even more preferably 3 × 10 ³ to 1 × 10 ⁷ , particularly preferably 5 × 10 ³ to 1 × 10 ⁷ . Further, from the viewpoint of the purity of the ionic polymer, the weight average molecular weight in terms of polystyrene is preferably from 1 × 10 ³ to 5 × 10 ⁷ , more preferably from 1 × 10 ³ to 1 × 10 ⁷ , and even most Good is 1 × 10 ³ to 5 × 10 ⁶ . Further, from the viewpoint of solubility of the ionic polymer, the number average molecular weight in terms of polystyrene is preferably from 1 × 10 ³ to 5 × 10 ⁵ , more preferably from 1 × 10 ³ to 5 × 10 ⁴ , even It is preferably 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, for example, by gel chromatography (GPC).

From the viewpoint of the purity of the ionic polymer used in the present invention, the number of all structural units (that is, the degree of polymerization) contained in the ionic polymer excluding the structural unit of the terminal is preferably 1 or more and 20 or less. More preferably, it is 1 or more, 10 or less, and even 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 non-occupied molecular orbital (LUMO) of the ionic polymer is preferably -5.0 eV or more, -2.0. Below eV, it is more preferably -4.5 eV or more and -2.0 eV or less. Further, from the same viewpoint, the orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer is preferably -6.0 eV or more and -3.0 eV or less, more preferably -5.5 eV or more and -3.0 eV or less. . However, the orbital energy of HOMO is lower than the orbital energy of LUMO. Further, the orbital energy of the highest occupied molecular orbital (HOMO) of the ionic polymer is obtained by measuring the ionization potential of the ionic polymer to obtain the 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 determining the energy difference between HOMO and LUMO, and the sum of the values and the ionization potential measured in the foregoing. And find it. A photoelectron spectroscopic device is used in the measurement of the ionization potential. Further, the energy difference between HOMO and LUMO was measured by using an ultraviolet ray ‧ visible ‧ near-infrared spectrophotometer to measure the absorption spectrum of the ionic polymer, and the absorption end was obtained.

Further, in the state in which the polymer used in the present invention is used in an electric field light-emitting element, it is preferable that it is substantially non-light-emitting. Here, the fact that a certain polymer is substantially non-luminescent is as follows. First, an electric field light-emitting element A having a layer containing a certain polymer is produced. On the other hand, an electric field light-emitting element 2 which does not have a layer containing a polymer is produced. The electric field light-emitting element A and the electric field light-emitting element 2 are different only in the case where the electric field light-emitting element A has a layer containing a polymer but the electric field light-emitting element 2 does not have a layer containing a polymer. Next, a forward voltage of 10 V was applied to the electric field light-emitting element A and the electric field light-emitting element 2, and the emission spectrum was measured. The wavelength λ at which the maximum peak is given is obtained from the luminescence spectrum obtained for the electric field light-emitting element 2. The illuminance spectrum of the wavelength λ is set to 1, and the luminescence spectrum obtained for the electric field light-emitting element 2 is normalized, and the wavelength is integrated to calculate the normalized luminescence amount S ₀ . On the other hand, the illuminance intensity of the wavelength λ is set to 1, and the luminescence spectrum obtained for the electric field light-emitting element A is normalized, and the wavelength is integrated to calculate the normalized luminescence amount S. In a state where the value calculated by (SS ₀ )/S ₀ ×100% is 30% or less, that is, it is included in comparison with the normalized luminescence amount of the electric field light-emitting element 2 having no polymer-containing layer. In the state where the increase in the normalized luminescence amount of the electric field light-emitting element A of the polymer layer is 30% or less, the polymer to be used is substantially non-light-emitting, preferably by (SS ₀ )/S ₀ × The value calculated by 100% is 15% or less, and more preferably 10% or less.

An ionic polymer comprising a group represented by the above formula (1) and a group represented by the above formula (3): an ionic polymer composed only of a group represented by the chemical formula (23); (23) The group represented by the formula and the chemical formula 45 to the chemical formula 50, the chemical formula 59, the chemical formula 60, the chemical formula 77, the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 96, and the chemical formula 101 to the chemical formula 110 are removed by two hydrogen atoms. An ionic polymer composed of one or more selected groups selected from the group consisting of: an ionic polymer composed only of the group represented by the chemical formula (24); a group represented by the chemical formula (24); The group consisting of the chemical formula 45 to the chemical formula 50, the chemical formula 59, the chemical formula 60, the chemical formula 77, the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 96, and the chemical formula 101 to the chemical formula 110 is selected from the group consisting of two hydrogen atoms. An ionic polymer composed of one or more kinds of bases; an ionic polymer composed only of a group represented by the chemical formula (25); a group represented by the chemical formula (25) and a chemical formula 45 to a chemical formula 5 0 or more selected from the group consisting of the chemical formula 59, the chemical formula 80, the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 96, and the chemical formula 101 to the chemical formula 110, and the group of the two hydrogen atoms is removed. An ionic polymer composed of a base; an ionic polymer composed only of a group represented by the chemical formula (29); a group represented by the chemical formula (29); and a chemical formula 45 to a chemical formula 50, a chemical formula 59, and a chemical formula 60, Ionic polymerization consisting of one or more selected from the group consisting of a group of two hydrogen atoms removed by a group represented by Chemical Formula 77, Chemical Formula 80, Chemical Formula 90, Chemical Formula 96, Chemical Formula 96, and Chemical Formula 101 to Chemical Formula 110 An ionic polymer composed only of the group represented by the chemical formula (30); a group represented by the chemical formula (30); and a chemical formula 45 to a chemical formula 50, a chemical formula 59, a chemical formula 60, a chemical formula 77, a chemical formula 80, and a chemical formula 91 An ionic polymer composed of a group selected from the group consisting of a group of two hydrogen atoms and having a group represented by the chemical formula (92) and the chemical formula (96).

Examples of the ionic polymer containing the group represented by the above chemical formula (1) and the group represented by the above chemical formula (3) include the following polymer compounds. Among these, in the polymer compound represented by the chemical formula of the two structural units by the oblique line "/", the ratio of the structural unit on the left side is p mol%, and the ratio of the structural unit on the right side is (100-p). Molex%, these structural units are randomly arranged. Further, in the following chemical formula, n represents the degree of polymerization.

(In the chemical formula, p is a number from 15 to 100.)

An ionic polymer comprising a group represented by the above formula (2) and a group represented by the above formula (3): an ionic polymer composed only of a group represented by the chemical formula (26); (26) The group represented by the formula and the chemical formula 45 to the chemical formula 50, the chemical formula 59, the chemical formula 60, the chemical formula 77, the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 96, and the chemical formula 101 to the chemical formula 110 are removed by two hydrogen atoms. An ionic polymer composed of one or more selected groups selected from the group consisting of: an ionic polymer composed only of the group represented by the chemical formula (27); a group represented by the chemical formula (27); The group consisting of the chemical formula 45 to the chemical formula 50, the chemical formula 59, the chemical formula 60, the chemical formula 77, the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 96, and the chemical formula 101 to the chemical formula 110 is selected from the group consisting of two hydrogen atoms. An ionic polymer composed of one or more kinds of bases; an ionic polymer composed only of a group represented by the chemical formula (28); a group represented by the chemical formula (28) and a chemical formula 45 to a chemical formula 5 0 or more selected from the group consisting of the chemical formula 59, the chemical formula 80, the chemical formula 80, the chemical formula 91, the chemical formula 92, the chemical formula 96, and the chemical formula 101 to the chemical formula 110, and the group of the two hydrogen atoms is removed. An ionic polymer composed of the base; an ionic polymer composed only of the group represented by the chemical formula (31); a group represented by the chemical formula (31); and a chemical formula 45 to a chemical formula 50, a chemical formula 59, and a chemical formula 60, Ionic polymerization consisting of one or more selected from the group consisting of a group of two hydrogen atoms removed by a group represented by Chemical Formula 77, Chemical Formula 80, Chemical Formula 90, Chemical Formula 96, Chemical Formula 96, and Chemical Formula 101 to Chemical Formula 110 An ionic polymer composed only of the group represented by the chemical formula (32); a group represented by the chemical formula (32); and a chemical formula 45 to a chemical formula 50, a chemical formula 59, a chemical formula 60, a chemical formula 77, a chemical formula 80, and a chemical formula 91 An ionic polymer composed of one or more selected from the group consisting of a group consisting of two hydrogen atoms and a group represented by Chemical Formula 92, Chemical Formula 96, and Chemical Formula 101.

Examples of the ionic polymer containing the group represented by the above chemical formula (2) and the group represented by the above chemical formula (3) include the following polymer compounds. Among these, the polymer compound represented by the chemical formula of the two structural units by the slash "/", the ratio of the structural unit on the left side is p mol%, and the ratio of the structural unit on the right side is (100-p) Mole%, these structural units are randomly arranged. Further, in the following chemical formula, n represents the degree of polymerization.

(In the chemical formula, p is a number from 15 to 100.)

-Method for producing ionic polymer -

Next, a method of 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 formula (36) can be used, and one selected as a raw material, which also contains the compound of the formula (36) -A _a - is a compound of the structural unit represented by the chemical formula (13), the compound of -A _a - is _a structural unit represented by the chemical formula (15), and the -A _a - is _a structural unit represented by the chemical formula (17) The compound and the compound in which -A _a - is _a structural unit represented by the chemical formula (20) are used as a necessary raw material, and this is a method of polycondensation.

Y ⁴ -A _a -Y ⁵ (36)

(In the chemical formula (36), A _a represents one or more selected from the group consisting of the group represented by the chemical formula (1) and the group represented by the chemical formula (2), and the chemical formula (3) The repeating unit of the one or more kinds of groups, and the Y ⁴ and Y ⁵ groups each independently represent a group to which the polycondensation is carried out.)

In addition, the ionic polymer used in the present invention, by containing, together in the aforementioned chemical formula (36) -A _a - in a state other than the structural unit of the can - and the structural units represented by the sum -A _a The compound represented by the above formula (36) is coexisted with a compound which is a substituent which is a structural unit other than the above -A _a - and which has two substituents, and is subjected to polycondensation.

The compound represented by the chemical formula (37) is exemplified as the compound having two polycondensable substituents used to contain such other structural unit. By adding the compound represented by the above Y ⁴ -A _a -Y ⁵ to the above, in the state where the compound represented by the chemical formula (37) is polycondensed, it is possible to produce a compound having a -A _b - The ionic polymer used in the present invention is a structural unit.

Y ⁶ -A _b -Y ⁷ (37)

(In the chemical formula (37), A _b is a structural unit represented by the above formula (33) or a structural unit represented by the formula (35), and Y ⁶ and Y ⁷ each independently represent a group of the polycondensation. .)

The series of such polycondensation (Y ⁴ , Y ⁵ , Y ⁶ and Y ⁷ ) are as follows: hydrogen atom, halogen atom, alkyl sulfonate group, aryl sulfonate group, arylalkyl sulfonate. An acid ester group, a boronic acid ester residue, a fluorenylmethyl group, a fluorenylmethyl group, a phosphonate methyl group, a monohalomethyl group, a -B(OH) ₂ group, a decyl group, a cyano group, a vinyl group or the like.

Examples of the halogen atom which can be selected as the group for the above-mentioned participation in polycondensation include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Further, as the alkylsulfonate group which may be selected as the base for the aforementioned polycondensation, a methanesulfonate group, an ethanesulfonate group, a trifluoromethanesulfonate group, as the arylsulfonic acid is exemplified. The ester group is exemplified by a benzenesulfonate group and a p-tosylate group.

The arylalkylsulfonate group which may be selected as the base for the aforementioned polycondensation is exemplified by a benzyl sulfonate group.

Further, as the boronic acid ester residue which can be selected as the base for the aforementioned polycondensation, a group represented by the following chemical formula is exemplified.

Further, as the methyl group which can be selected as the basis for the aforementioned polycondensation, the following chemical formula is exemplified:

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

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

Further, as the methyl group which can be selected as the basis for the aforementioned polycondensation, the following chemical formula is exemplified:

-CH ₂ P ⁺ Ph ₃ E ^-

(In the chemical formula, E is a halogen atom).

Further, as the phosphonate methyl group which can be selected as the base for the aforementioned polycondensation, the following chemical formula is exemplified:

-CH ₂ PO(OR ^d ) ₂

(In the formula, R ^d represents a group represented by an alkyl group, an aryl group or an arylalkyl group.).

Further, examples of the monohalomethyl group which can be selected as the group for the aforementioned polycondensation include fluoromethyl group, chloromethyl group, bromomethyl group and iodomethyl group.

Further, an ideal base suitable for being a base for the polycondensation differs depending on the kind of the polymerization reaction. An ideal base suitable for the basis of the polycondensation is, for example, a halogen atom, an alkylsulfonate group, an arylsulfonate group, or an arylalkyl group in the state of using a zero-valent nickel complex such as a Yamamoto coupling reaction. Base sulfonate group. Further, in the state of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, for example, an alkylsulfonate group, a halogen atom, a boronic acid ester residue, -B(OH) ₂ or the like is exemplified by In the state of the oxidizing agent or the electrochemical oxidative polymerization, a hydrogen atom is cited.

In the production of the ionic polymer used in the present invention, a compound represented by the above formula (36) or formula (37) having a plurality of groups which are involved in the polycondensation may be used, for example, for the purpose of blending. A polymerization method in which the reaction is carried out at a temperature below the melting point of the organic solvent at a temperature equal to or higher than the melting point of the organic solvent by using an alkali or a suitable catalyst. As such a polymerization method, for example, "Organic Reactions", Vol. 14, pp. 270-490, (John Wiley & Sons, Inc.), 1965, "Organic Syntheses" can be used. , Collective Volume VI, pp. 407-411, (John Wiley & Sons, Inc.), 1988, Chem. Rev., Vol. 95, p. 2457, (1995) J. Organomet. Chem., vol. 576, p. 147, (1999), Macromol. Chem., Macromol. Symp., Vol. 12, 292 pages, the traditional method of (1987).

Further, in the production of the ionic polymer used in the present invention, a conventional polycondensation reaction can be employed in conjunction with the base to which the polycondensation is carried out. Examples of such a polymerization method include a method of polymerizing the monomer by a Suzuki coupling reaction, a method of performing polymerization by a Grignard reaction, a method of polymerizing by a Ni(O) complex, and a method of using FeCl _{3 ,} etc. A method of performing polymerization by an oxidizing agent, a method of electrochemical oxidative polymerization, a method of decomposing an intermediate polymer having a suitable decomposing group, and the like. Even in such a polymerization reaction, a method of performing polymerization by a Suzuki coupling reaction, a method of performing polymerization by a Grignard reaction, and a method of performing polymerization by a nickel zero-valent complex are easily controlled. The construction of the ionic polymer is therefore preferred.

One of the preferred manufacturing methods of the ionic polymer used in the present invention is a group having a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and an arylalkyl sulfonate group. The selected one is a raw material monomer which is a base of the polycondensation, and is subjected to polycondensation in the presence of a nickel zero-valent complex to produce an ionic polymer. As a series of raw material monomers used in such a method, for example, a dihalogenated compound, a bis(alkylsulfonate) compound, a bis(arylsulfonate) compound, a bis(arylalkylsulfonate) compound, Halo-alkyl sulfonate compound, halogen-aryl sulfonate compound, halogen-aryl alkyl sulfonate compound, alkyl sulfonate-aryl sulfonate compound, alkyl sulfonate-aryl Alkyl sulfonate compounds and aryl sulfonate-arylalkyl sulfonate compounds.

Other forms of the preferred method of manufacture of the foregoing ionic polymer will have a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, -B(OH) ₂ and The group selected from the group consisting of borate residues serves as a base for the polycondensation and the whole raw material monomer has a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonic acid The ratio of the total number of moles of the ester group (J) to the total number of moles of the B- (OH) ₂ and the number of moles of the boronate residue (K) is substantially 1 (the range of the general K/J range of 0.7 to 1.2) The raw material monomer is subjected to polycondensation in the presence of a nickel catalyst or a palladium catalyst to produce an ionic polymer.

The organic solvent is also used depending on the compound or reaction to be used. However, in general, in order to suppress side reactions, it is preferred to use an organic solvent which is sufficiently subjected to deoxidation treatment. In the production of an ionic polymer, it is preferred to carry out the reaction in an inert environment using such an organic solvent. Further, in the above organic solvent, it is preferred to carry out a dehydration treatment which is the same as the above-described deoxidation treatment. However, in the state of the reaction with the two-phase system of water such as the Suzuki coupling reaction, there is no limitation.

Examples of such an organic solvent include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; and carbon tetrachloride. Halogenated saturated hydrocarbons such as chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc. a halogenated unsaturated hydrocarbon such as dichlorobenzene or trichlorobenzene; an alcohol such as methanol, ethanol, propanol, isopropanol, butanol or tert-butyl alcohol; a carboxylic acid such as formic acid, acetic acid or propionic acid; Ethers such as dimethyl ether, diethyl ether, methyl-tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, etc., trimethylamine, triethylamine, N, N, N' , N'-tetramethylethylenediamine, amines such as pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide And an amide such as N-methylmorpholine oxide. These organic solvents may be used alone or in combination of two or more. Further, even in such an organic solvent, from the viewpoint of reactivity, it is more preferably an ether, even more preferably tetrahydrofuran or diethyl ether, and from the viewpoint of the reaction rate, it is preferably toluene or two. Toluene.

In the production of the aforementioned ionic polymer, in order to react the raw material monomers, it is preferred to add a base or a suitable catalyst. Such a base or a catalyst may be selected depending on the polymerization method or the like employed. The base or catalyst is preferably a solvent which is sufficiently dissolved in the reaction. Further, as a method of mixing the above-mentioned alkali or catalyst, the reaction solution is stirred under an inert atmosphere such as argon or nitrogen, and a solution of a base or a catalyst is slowly added, or a solution in an alkali or a catalyst. A method of slowly adding a reaction solution.

In the ionic polymer used in the present invention, when the polymerization active group remains in the terminal group, the light-emitting characteristics or lifetime characteristics of the obtained light-emitting element are lowered. Therefore, the terminal group can be protected by a stable group. When the ionic polymer used in the present invention is a conjugated compound in a state in which the terminal group is protected by a stable group as described above, it is preferable to have a conjugated structure with respect to the main chain of the ionic polymer. The conjugated bond, as a series of structures thereof, is bonded to an aryl group or a heterocyclic group, for example, through a carbon-carbon bond. The stabilizing group which is such a protective terminal group is a substituent such as a monovalent aromatic compound group represented by the structural formula of Chemical 10 listed in Japanese Laid-Open Patent Publication No. Hei 9-45478.

Another series of other desirable methods for producing an ionic polymer comprising a structural unit represented by the chemical formula (1): polymerizing an ionic polymer having no cation in the first step, and ionic in the second step A method of making a cationic ion-containing polymer from a polymer. As a method of polymerizing an ionic polymer having no cation in the first step, the above polycondensation reaction is carried out. The reaction series of the second step is a hydrolysis reaction by a metal hydroxide, an alkylammonium hydroxide or the like.

Another series of other desirable methods for producing an ionic polymer comprising a group represented by the chemical formula (2): polymerizing an ionic polymer having no ions in the first step, and ionic polymer in the second step A method of making an ion-containing ionic polymer. As a method of polymerizing the ionic polymer having no ion as the first step, the above polycondensation reaction is carried out. The reaction series of the second step is a 4-stage ammonium chlorination reaction using a halogenated alkyl group, a halogen removal reaction by SbF ₅ or the like.

The ionic polymer used in the present invention is excellent in charge generation, and therefore, for example, in an organic electroluminescence device, an element having high luminance light emission can be obtained.

As a series of methods for forming a layer containing an ionic polymer, for example, a method of forming a film using a solution containing an ionic polymer is used.

As a solvent used for forming a film from such a solution, in addition to water, alcohols, ethers, esters, nitrile compounds, nitro compounds, halogenated alkanes, aryl halides, and mercaptans Among the solvents such as thioethers, sulfoxides, thiones, guanamines, and carboxylic acids, a solvent having a solubility parameter of 9.3 or more is preferred. Examples of the solvent (the values in the respective brackets indicate the values of the solubility parameters of the respective solvents) are as follows: methanol (12.9), ethanol (11.2), 2-propanol (11.5), 1-butanol (9.9). ), tert-butyl alcohol (10.5), acetonitrile (11.8), 1,2-ethanediol (14.7), N,N-dimethylformamide (11.5), dimethyl alum (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), propyl carbonate (13.3), pyridine (10.4), carbon disulfide (10.0), and a mixed solvent of these solvents. Here, when describing a mixed solvent in which two kinds of solvents (which are a solvent 1 and a solvent 2) are mixed, the solubility parameter (δ _m ) of the mixed solvent is δ _m = δ ₁ × ψ ₁ + δ ₂ x ψ ₂ was obtained (the solubility parameter of δ ₁ based solvent 1 , the volume ratio of ψ ₁ based solvent 1 , the solubility parameter of δ _{2 -} based solvent 2, and the volume ratio of ψ _{2 -} based solvent 2).

<First embodiment> (Organic thin film transistor)

An example of the structure of the organic thin film transistor of the first embodiment will be described with reference to Fig. 1 . Fig. 1 is a cross-sectional view schematically showing a structural example of an organic thin film transistor of the first embodiment. The organic thin film transistor 10 of the first embodiment is a structural example of an organic thin film transistor of a bottom gate type.

As shown in Fig. 1, the organic thin film transistor 10 of the first embodiment is formed on the gate electrode 20, and the gate insulating layer 30 and the organic semiconductor layer 40 are laminated in this order, and in the organic On the semiconductor layer 40, the first charge injection layer 50A and the first source/drain electrode 60A are laminated in this order, and the second charge injection layer 50B and the second source are formed on the organic semiconductor layer 40. The pole/drain electrodes 60B are laminated in this order. Next, on the organic semiconductor layer 40, a laminate composed of the first charge injection layer 50A and the first source/drain electrode 60A, and a second charge injection layer 50B and a second source/drain electrode The layered system composed of 60B is arranged at intervals.

In another embodiment, a charge injection layer in which the first source/drain electrode 60A and the second source/drain electrode 60B are laminated may be connected to the organic semiconductor layer 40. Further, from the viewpoint of electrical characteristics, the charge injection layer is preferably disposed at intervals as in the present embodiment. In the following, in the state in which the first charge injection layer 50A and the second charge injection layer 50B which are not particularly distinguishable are displayed, this is only referred to as the charge injection layer 50.

A conductor or a semiconductor can be used at the gate electrode 20. The gate electrode 20 requires a predetermined conductivity, and therefore, an intrinsic semiconductor can be used. As the gate electrode 20, it is preferable to use an n-type semiconductor or a p-type semiconductor doped with impurities from the viewpoint of conductivity, and it is more preferable to use an n-type semiconductor. For example, a substrate of a desired conductivity type may be arbitrarily doped with a suitable p-type ion or n-type ion in the germanium substrate to be used as the gate electrode 20. The thickness Z of the gate electrode 20 has a thickness of about 0.05 μm to 100 μm.

The gate insulating layer 30 can be formed using an insulating material such as hafnium oxide or tantalum nitride. For example, the gate insulating layer 30 may be formed on the surface portion of the germanium substrate by oxidizing the surface portion of the germanium substrate as the gate electrode 20. A gate insulating layer 30 can be formed over the gate electrode 20 by this. The thickness Z of the gate insulating layer 30 has a thickness of about 50 nm to 1000 nm.

In the state in which the organic semiconductor layer 40 is a p-type organic semiconductor layer, examples of the material of the organic semiconductor layer 40 include: ruthenium, fused tetraphenyl, pentacene, benzo pentacene, dibenzo pentacene, Polystyrene compounds such as tetrabenzopyroquinone, naphthacene pentacene, hexabenzene, hexabenzene, condensed nonabenzene, etc.; phenanthrene, anthracene, benzopyrene, hydrazine, hydrazine, diphenyl And 苝 (peropyrene), coronene, benzopyrene, dibenzopyrene, hexabenzopyrene, benzodiazepine, vinyl anthracene, etc.; hydrazine, terylene, diterpene, tetraphthalene Anthraquinone compounds such as Quaterrylene; Trinaphthylene, heptaphene, ovale, rubicene, violanthrone, isoviolanthrone , chrysene, cyclic oxime, bisanthene, 7,14-diphenyldibenzo[de,mn]zethrene, seven 7,14-diphenyldiphenyl And [de, mn] heptazethrene, pyranthrene, viollanthrene, isoviolanthrene, biphenyl, terphenyl, triphenyl, terphenyl, Benzene (c A copolymer of ircobiphenyl), Kekulene, phthalocyanine, and a polymer organic semiconductor compound composed therefrom.

In the state in which the organic semiconductor layer 40 is an n-type organic semiconductor layer, examples of the material of the organic semiconductor layer 40 include: perfluoro-fused pentacene, perfluorocopper phthalocyanine, and TCNQ (tetracyano-p-benzoquinone dimethane). , PTCDA (3,4,9,10-tetracarboxylic acid dianhydride), NTCDA (naphthalene tetracarboxylic anhydride), PTCDI-C8 (N,N'-dioctyl-3,4,9,10-苝4 Dimethyleneimine), C60, C60MC12 (C60-melt pyrrolidine-m-C12 phenyl), C70 fullerene, PCBM (phenyl C61 butyric acid methyl ester), cyano PPV (polycyano-p-phenylene) Methylene), F4TCNQ (tetrafluoro-tetracyano-p-benzoquinone dimethane), poly[(2,5-dimethoxy-1,4-phenylene) (2,4,6-triisopropyl) Phenylborane)], diphenyl terminated, poly[(1,4-diethylene extended phenyl) (2,4,6-triisopropylphenylborane)], poly(benzoic double Imidazobenzophenanthroline), trifluoromethylphenyl substituted bithiazole NTCDA (naphthalene tetracarboxylic dianhydride), TCNNQD (11,11,12,12-tetracyanophthalona-2,6-quinodimethane )Wait. The thickness of the organic semiconductor layer 40 is about 1 nm to 100 μm.

The charge injection layer 50 functions as an electron injection layer in a state in which the conductivity type is an n-type, and functions as a hole injection layer in a state where the conductivity type is a p-type.

The charge injection layer 50 is preferably composed of an ionic polymer as described above, and is substantially composed of the ionic polymer. In the state in which the charge injection layer 50 functioning as an electron injection layer is formed, an n-type ionic polymer having electron injection characteristics can be used as the material. Further, in a state in which the charge injection layer 50 functioning as a hole injection layer is formed, a p-type ionic polymer having a hole injection property can be used as a material.

As described above, the charge injection layer 50 of the present embodiment is on the organic semiconductor layer 40, and the first charge injection layer 50A and the second charge injection layer 50B are arranged at intervals.

The thickness Z of the charge injection layer 50 has a thickness of about 0.5 nm to 100 nm. Further, the interval L1 (corresponding to the channel length) of the first charge injection layer 50A and the second charge injection layer 50B is about 0.1 μm to 1000 μm. In addition, the width L2 of the first charge injection layer 50A and the second charge injection layer 50B in the direction X (the horizontal direction in the first drawing) in which the first charge injection layer 50A and the second charge injection layer 50B are spaced apart is 0.1. Μm to 1000μm. In addition, in the direction X (the horizontal direction in the first drawing) in which the first charge injection layer 50A and the second charge injection layer 50B are spaced apart, and the thickness direction Z of the charge injection layer 50 (the vertical direction in the first drawing), The width (corresponding to the channel width) of the charge injection layer 50 in the vertical direction Y (the direction perpendicular to the sheet in Fig. 1) is about 0.1 μm to 1000 μm.

The first source/drain electrode 60A is provided in contact with the first charge injection layer 50A, and the second source/drain electrode 60B is provided in contact with the second charge injection layer 50B. In the present embodiment, the first charge injection layer 50A and the first source/drain electrode 60A are viewed from one side in the thickness direction Z of the gate electrode 20 (hereinafter also referred to as "in plan view"). It is set such that its peripheral shape is slightly uniform. Further, in the plan view, the second charge injection layer 50B and the second source/drain electrode 60B are arranged such that their peripheral shapes are slightly uniform. The thicknesses of the first and second source/drain electrodes 60A and 60B in the thickness direction Z are each about 0.05 μm to 1000 μm.

As the material of the first source/drain electrode 60A and the second source/drain electrode 60B, a suitable conductive material can be used arbitrarily, but it is formed by a coating method using a coating liquid. Next, it is suitable to use metal particles having conductivity. As the metal fine particles, gold, silver, and aluminum are suitably used. Further, in addition to metal particles of gold, silver, and aluminum, a carbon paste and a mixture of a carbon paste and metal particles are preferably used.

The conductivity type of the charge injection layer 50, the organic semiconductor layer 40, and the gate electrode 20 may be appropriately selected from the most appropriate combination, and may be all the same or different from each other. The conductivity types of the organic semiconductor layer 40 and the gate electrode 20 are preferably the same. Further, since the conductivity of the gate electrode 20 is preferably high, the conductivity type is not particularly limited. The n-type germanium semiconductor substrate generally has high conductivity, and therefore, it is preferable to use an n-type germanium semiconductor substrate in the gate electrode 20. For example, the charge injection layer 50, the organic semiconductor layer 40, and the gate electrode 20 are preferably all of the conductivity type n-type. Further, in the state in which the charge injection layer 50 is spaced apart from the first charge injection layer 50A and the second charge injection layer 50B, the conductivity types of the first charge injection layer 50A and the second charge injection layer 50B may be different from each other.

(Manufacturing method of organic thin film transistor)

Hereinafter, a method of manufacturing an organic thin film transistor having a structure will be described with reference to Fig. 1.

The method for producing an organic thin film transistor is to form a gate electrode, a first source/drain electrode, a second source/drain electrode, and a first source/drain electrode and a second source/汲An organic semiconductor layer between the electrode and the gate electrode, and the first source/drain electrode between the first source/drain electrode and the second source/drain electrode and the organic semiconductor layer A method of producing an organic thin film transistor of a charge injection layer in which a second source/drain electrode is in contact with each other includes a step of forming a charge injection layer containing an ionic polymer having charge injection characteristics. That is, the method for producing an organic thin film transistor includes a step of forming a gate electrode, a step of forming a first source/drain electrode, a step of forming a second source/drain electrode, and forming the first source. a step of a pole/drain electrode and a second source/drain electrode and an organic semiconductor layer disposed between the gate electrodes; and a first source/drain electrode and a second source/drain electrode A step of forming a charge injection layer disposed in contact with the first source/drain electrode and the second source/drain electrode between the organic semiconductor layers is formed. Further, the order of the respective steps is appropriately set in accordance with the configuration of the organic thin film transistor. In the present embodiment, the step of forming a gate electrode, the step of forming an organic semiconductor layer, the step of forming a charge injection layer, and the steps of forming the first source/drain electrode and the second source/drain electrode And proceed.

First, the gate electrode 20 is formed. In this step, a substrate functioning as a gate electrode can be obtained from the market, and, for example, an ion implantation step, an ion diffusion step, or the like can be performed by preparing a germanium substrate, so that the entire region of the substrate or Part of the area becomes an arbitrary conductivity type and forms a gate electrode.

Next, a gate insulating layer 30 is formed on the surface portion of the prepared substrate. This step can be carried out as a film forming step using an insulating material which has been described by a CVD method (chemical vapor phase growth method) or the like.

Further, in a state where the tantalum substrate is used as the substrate 20, the surface portion of the substrate prepared by the thermal oxidation step can be oxidized to form a thermal oxide film on the surface portion of the tantalum substrate, and formed on the gate electrode 20. A gate insulating layer 30 formed of the thermal oxide film. The gate insulating layer 30 can be easily formed by a simple step of thermally oxidizing the germanium substrate by using a germanium substrate as a gate electrode as described above.

Next, an organic semiconductor layer 40 is formed over the gate insulating layer 30. This step can be carried out by any suitable method. This step can be carried out by a coating method using a coating liquid in which a material is dissolved or dispersed in any appropriate solvent. The step of filtering using a membrane filter or the like can be carried out as needed in the preparation of the coating liquid.

The organic semiconductor layer 40 is formed by applying the obtained coating liquid onto the gate insulating layer 30 and performing any appropriate heat treatment corresponding to the material.

In the method for producing the organic thin film transistor 10 of the present invention, in a state in which a layer constituting the organic thin film transistor 10 is formed by a coating method using a coating liquid, the coating step is in an environment of a normal pressure or Implemented in an atmospheric environment.

The term "atmospheric environment" as used herein refers to an environment that allows the inclusion of water and oxygen. The "atmospheric environment" specifically includes an environment in which the ambient temperature and the normal pressure are not adjusted, and the environment in which water, oxygen, and temperature, pressure, composition, and the like are adjusted. The "adjusted environment" is a process of adjusting the composition of nitrogen, hydrogen, oxygen, carbon dioxide, or the like as a condition by performing a manufacturing method of the present invention including "coating", and adjusting the composition ratios. The cleanliness of the floating particles and the floating microorganisms is adjusted, and the environment in which the environmental conditions such as temperature, humidity, pressure, and the like can be adjusted under the condition that the manufacturing method of the present invention including "coating" can be performed is included. Further, in the present specification, the so-called normal pressure is generally a pressure of 1013 hPa ± 100 hPa. In an environment of normal pressure, if it is normal pressure, it also contains an inert gas atmosphere such as nitrogen or argon.

Examples of the coating method are: spin coating method, die casting method, micro gravure coating method, gravure coating method, bar coating method, press roll coating method, wire bar coating Method, dip coating method, spray coating method, screen printing method, flexographic printing method, lithography method, inkjet printing method, and the like.

When a layer is formed by a coating method, the coating liquid can be applied in a predetermined pattern shape by a coating step in a state where an organic semiconductor layer must be formed in a predetermined pattern shape. The organic semiconductor layer is formed in a predetermined pattern shape, and may be subjected to any appropriate patterning step such as performing a photolithography step and a subsequent etching step after forming the layer by full coating. An organic semiconductor layer is formed in a predetermined pattern shape.

Next, on the organic semiconductor layer 40, a first charge injection layer 50A and a second charge injection layer 50B including an ionic polymer having charge injection characteristics are formed. In the present embodiment, the first charge injection layer 50A is formed in the same pattern as the first source/drain electrode 60A formed later. In the present embodiment, the second charge injection layer 50B is formed in the same pattern as the second source/drain electrode 60B formed later. This step is the same as the step of forming the organic semiconductor layer 40, and can be carried out by a coating method using a coating liquid in which a material is dissolved in any appropriate solvent. Further, in a state in which the charge injection layer 50 is an n-type electron injection layer, an n-type ionic polymer is selected as a material type, and in a state in which the charge injection layer 50 is a p-type hole injection layer, A coating liquid is prepared by selecting an ionic polymer having a conductivity type of p-type as a material. The coating liquid is applied to the surface of the organic semiconductor layer 40, and any appropriate heat treatment corresponding to the material is performed to form the charge injection layer 50.

Then, on the first charge injection layer 50A, the first source/drain electrode 60A having the same pattern shape as that of the first charge injection layer 50A is formed, and the pattern shape is the same on the second charge injection layer 50B. The second source/drain electrode 60B of the second charge injection layer 50B.

This step is suitable for forming a conductive layer using a coating liquid prepared by using conductive metal particles such as gold, silver or aluminum and any appropriate solvent. In the state in which the metal fine particles are used as the conductive material, a polar solvent such as water, methanol, ethanol, propanol, isopropanol (IPA) or dimethyl ketone can be suitably used.

The formation of the first source/drain electrode 60A and the second source/drain electrode 60B by the coating method is performed by coating the prepared coating liquid. The application of the coating liquid is suitably carried out by a spin coating method, an inkjet method, or the like. Next, the formed source film can be heat-treated by any appropriate conditions corresponding to the material to form the first source/drain electrode 60A and the second source/drain electrode 60B.

As described above, according to the method for producing the organic thin film transistor 10 of the present invention, an ionic polymer which is not easily oxidized even in an environment of a normal pressure or even an atmospheric environment is used as a material of the charge injection layer. Therefore, the steps of forming the charge injection layer 50 and the steps of forming the first source/drain electrode 60A and the second source/drain electrode 60B can be performed in an environment of a normal pressure or even an atmosphere. The step of applying the coating liquid is included. Further, even in the step of forming the organic semiconductor layer 40, the coating liquid may be applied in an environment containing a normal pressure or even in an atmospheric environment.

<Second embodiment> (Organic thin film transistor)

The structure example of the organic thin film transistor of the second embodiment will be described with reference to Fig. 2 . In the same layer as the layer described in the first embodiment, the same reference numerals will be given, and the description thereof will be omitted.

Fig. 2 is a cross-sectional view schematically showing a structural example of an organic thin film transistor of a second embodiment. The organic thin film transistor 10 of the second embodiment is a structural example of a top gate type organic thin film transistor.

As shown in Fig. 2, the organic thin film transistor 10 of the second embodiment is provided on the substrate 70. The substrate 70 may be a rigid substrate such as a glass substrate, a flexible substrate such as a plastic substrate, or even a thin film. It is also possible to use a flexible substrate or a film to make the entire organic thin film transistor flexible.

The first source/drain electrode 60A and the second source/drain electrode 60B are provided on the surface of one side in the thickness direction Z of the substrate 70. The first source/drain electrode 60A and the second source/drain electrode 60B are arranged to be spaced apart from each other.

On the surface of the first source/drain electrode 60A, a first charge injection layer 50A having the same shape as the first source/drain electrode 60A is patterned. On the surface of the second source/drain electrode 60B, a second charge injection layer 50B having the same shape as the second source/drain electrode 60B is patterned.

The charge injection layer 50 is formed of the illustrated ionic polymer. In the state in which the charge injection layer 50 functioning as an electron injection layer is formed, an n-type ionic polymer having electron injection characteristics can be used as the material. Further, in a state in which the charge injection layer 50 functioning as a hole injection layer is formed, a p-type ionic polymer having a hole injection property can be used as a material.

The charge injection layer 50 functions as an electron injection layer in a state in which the conductivity type is an n-type, and functions as a hole injection layer in a state where the conductivity type is a p-type.

On the substrate 70, an organic semiconductor layer 40 is provided so as to cover the first source/drain electrode 60A and the second source/drain electrode 60B and the charge injection layer 50 formed on these electrodes. The organic semiconductor layer 40 corresponds to an active layer.

On the organic semiconductor layer 40, the gate insulating layer 30 and the gate electrode 20A are laminated in this order.

The size of each layer and the electrode constituting the organic thin film transistor of the second embodiment is, for example, the same as that of the organic thin film transistor of the first embodiment. If the structure of the organic thin film transistor is made to be the top gate type as described above, the germanium substrate is not required. Therefore, since the flexible substrate can be used, it is possible to form a flexible organic thin film transistor as a whole. Moreover, since it can be an inexpensive substrate, the manufacturing cost can be reduced.

(Manufacturing method of organic thin film transistor)

The method for producing the organic thin film transistor of the second embodiment having the structure shown in Fig. 2 will be described. In the state similar to the manufacturing steps described in the first embodiment, the detailed description thereof will be omitted.

In the method of manufacturing the organic thin film transistor 10 of the second embodiment, a gate electrode, a first source/drain electrode, a second source/drain electrode, and the first source/drain electrode are provided. An organic semiconductor layer between the second source/drain electrode and the gate electrode, and between the first source/drain electrode and the second source/drain electrode and the organic semiconductor layer A method for producing an organic thin film transistor of a charge injection layer in which a source/drain electrode and a second source/drain electrode are in contact with each other, comprising: injecting a charge containing an ionic polymer having charge injection characteristics The step in which the layers are formed. That is, the method for producing an organic thin film transistor includes a step of forming a gate electrode, a step of forming a first source/drain electrode, a step of forming a second source/drain electrode, and forming the first source. a step of a pole/drain electrode and a second source/drain electrode and an organic semiconductor layer disposed between the gate electrodes; and a first source/drain electrode and a second source/drain electrode A step of forming a charge injection layer disposed in contact with the first source/drain electrode and the second source/drain electrode is formed between the organic semiconductor layers. Further, the order of the respective steps is appropriately set in accordance with the configuration of the organic thin film transistor. In the present embodiment, the steps of forming the first source/drain electrode and the second source/drain electrode, the step of forming the charge injection layer, the step of forming the organic semiconductor layer, and the step of forming the gate electrode are In order.

First, the substrate 70 is prepared, and the first source/drain electrode 60A and the second source/drain electrode 60B are formed on the substrate 70. This step is suitable for forming a conductive layer or a conductive electrode pattern using a coating liquid prepared by using conductive metal particles such as gold, silver or aluminum and any appropriate solvent. In the state in which the metal fine particles are used as the conductive material, a polar solvent such as water, methanol, ethanol, propanol, isopropanol (IPA) or dimethyl ketone can be suitably used. The application of the coating liquid is suitably carried out by a spin coating method, an inkjet method, or the like.

Next, the first charge injection layer 50A is formed on the surface of the first source/drain electrode 60A, and the second charge injection layer 50B is formed on the surface of the second source/drain electrode 60B. The first charge injection layer 50A and the second charge injection layer 50B include an ionic polymer having charge injection characteristics. This step, as explained, can be carried out by a coating method using a coating liquid. In addition, in the state in which the charge injection layer 50 which functions as an electron injection layer is formed, an n-type ionic polymer is selected as a material type, and a charge injection layer which functions as a hole injection layer is formed. In the state of 50, a coating liquid was prepared by selecting an ionic polymer having a conductivity type of p-type as a material.

The prepared coating liquid is applied onto the surfaces of the formed first source/drain electrode 60A and second source/drain electrode 60B, and any appropriate heat treatment corresponding to the material is performed to form a charge. The layer 50 is injected.

Next, the organic semiconductor layer 40 is formed on the substrate 70 so as to cover the first source/drain electrode 60A and the second source/drain electrode 60B and the charge injection layer 50 exposed by the charge injection layer 50. This step can be carried out by any suitable heat treatment corresponding to the material by a coating film formed by a coating method using a coating liquid.

Next, a gate insulating layer 30 is formed over the organic semiconductor layer 40, and a gate electrode 20A is further formed over the gate insulating layer 30. In the step of forming the gate insulating layer 30, the film forming step can be carried out by using a prescribed insulating material by a CVD method (chemical vapor phase growth method) or the like. Further, the step of forming the gate electrode 20A is the same as the step of forming the first source/drain electrode 60A and the second source/drain electrode 60B, and the conductivity can be made by using gold, silver, aluminum or the like. The step of forming a conductive layer by the coating liquid prepared by the metal fine particles and any appropriate solvent. The formation of the gate electrode 20A by the coating method is performed by applying a coating liquid to the gate insulating layer 30. The gate electrode 20A can be formed by heat-treating the formed coating film.

According to the method for producing the organic thin film transistor 10 of the present invention, an ionic polymer which is not easily oxidized even in an environment of a normal pressure or even an atmospheric environment is used as a material of the charge injection layer, and therefore, The step of forming the charge injection layer 50, the step of forming the gate electrode 20A, and the formation of the first source/drain electrode 60A and the second source/drain electrode 60B are performed in an atmosphere of a normal pressure or even in an atmosphere. Each of the steps is performed as a step including coating the coating liquid. Further, the step of forming the organic semiconductor layer 40 may be a step of coating the coating liquid in an atmosphere.

The organic thin film transistor 10 of the first embodiment and the second embodiment can be configured as an _n -type organic thin film transistor or a p-type organic thin film transistor by appropriately selecting the conductivity type of each layer.

Further, the organic thin film transistor 10 of the present invention can also constitute a complementary organic thin film transistor by combining an n-type organic thin film transistor and a p-type organic thin film transistor.

In the state in which the complementary organic thin film transistor is formed in the structural example of the first embodiment, the n-type organic thin film transistor and the p-type organic thin film can be selected by selecting the conductivity type of the material constituting the organic semiconductor layer and the charge injection layer. The transistor is selectively fabricated into a single substrate 20 to form a complementary organic thin film transistor.

In the state in which the complementary organic thin film transistor is formed in the structural example of the second embodiment, the n-type organic thin film transistor and the p-type organic thin film can be selected by selecting the conductivity type of the material constituting the organic semiconductor layer and the charge injection layer. The transistor is fabricated into a single substrate 70 to form a complementary organic thin film transistor.

If a complementary organic thin film transistor is formed, various logic circuits can be constructed. The logic circuit formed by the complementary organic thin film transistor can be suitably used for an electronic tag such as an RF (Radio Frequency) tag.

The organic thin film electro-crystal system of the present invention can be an organic thin film transistor which can be formed, for example, by forming a plurality of organic thin film transistors on a substrate, and combining a plurality of organic thin film transistors and the like to perform a predetermined electrical function.

When it is used as an organic thin film transistor substrate, it can be suitably used as a drive substrate for a display device such as a liquid crystal display device or an organic electroluminescence display device.

Hereinafter, the present invention will be more specifically described based on experimental examples and the like. The present invention is not limited to the following experimental examples and the like.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were determined by gel permeation chromatography (GPC) (manufactured by TOSOH Co., Ltd.: HLC-8220GPC) to determine the weight average molecular weight in terms of polystyrene. And the number average molecular weight. Further, the sample to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 50 μL of GPC was injected. Further, tetrahydrofuran was used as a mobile phase of GPC, and flowed at a flow rate of 0.5 mL/min. The structural analysis of the polymer was carried out by ¹ H-NMR analysis using a 300 MHz NMR spectrometer manufactured by Varian. Further, the measurement system sample was dissolved in a soluble ruthenium solvent (a solvent in which a hydrogen atom in the solvent molecule was replaced by a deuterium) to have a concentration of 20 mg/mL. The orbital energy of the highest occupied molecular orbital (HOMO) of a polymer is obtained by measuring the ionization potential of a polymer to obtain an ionization potential as the orbital energy. On the other hand, the orbital energy of the lowest non-occupied molecular orbital (LUMO) of the polymer is obtained by determining the energy difference between HOMO and LUMO by the sum of the values and the ionization potential determined in the foregoing description. Find out. In the measurement of the ionization potential, a photoelectron spectroscopic device (manufactured by Riken Keiki Co., Ltd.: AC-2) was used. Further, the energy difference between HOMO and LUMO was determined by using an ultraviolet ray ‧ visible ‧ near-infrared spectrophotometer (manufactured by Varian Co., Ltd.: Cary 5E) to measure the absorption spectrum of the polymer, and the end of the absorption was obtained.

[Reference Example 1]

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

2,7-dibromo-9-one (52.5 g), ethyl salicylate (154.8 g) and thioglycolic acid (1.4 g) were placed in a 300 mL flask, and the environment in the flask was subjected to nitrogen substitution (below , "The environment in the flask is replaced by nitrogen", and it is only described as "substituted with nitrogen".). Here, methanesulfonic acid (630 mL) was added, and the mixture was stirred overnight at 75 °C. The mixture was allowed to cool, added to ice water and stirred for 1 hour. The resulting solid was removed by filtration and washed with heated acetonitrile. The solid which was completely washed was dissolved in acetone, and the solid was recrystallized from the obtained acetone solution and removed by filtration. The solid (62.7 g), 2-[2-(2-methoxyethoxy)ethoxy]-p-tosylate (86.3 g), potassium carbonate (62.6 g) and 18-crown Ether-6 (7.2 g) was dissolved in N,N-dimethylformamide (DMF) (670 mL), and the solution was transferred to a flask and stirred overnight at 105 °C. The obtained mixture was allowed to cool to room temperature, and ice water was added to the flask, followed by stirring for 1 hour. The mixture was extracted by adding chloroform (300 mL) to the reaction mixture, and the solution was concentrated to give 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-[2- (2-Methoxyethoxy)ethoxy]ethoxy]phenyl]-thin (Compound A) (51.2 g).

[Reference Example 2]

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

Mixing compound A (15g), bis(pinacol) diboron (8.9g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) under nitrogen atmosphere Methylene chloride complex (0.8 g), 1,1'-bis(diphenylphosphino)ferrocene (0.5 g), potassium acetate (9.4 g) and dioxane (400 mL), heated to 110 ° C , heating under reflux for 10 hours. After allowing to cool, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The reaction mixture was washed three times with methanol. The precipitate was dissolved in toluene, and activated carbon was added to the solution to stir. Then, the filtrate was concentrated under reduced pressure by filtration 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]-thin (Compound B) (11.7g).

[Reference Example 3]

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

Compound A (0.55 g), Compound B (0.61 g), triphenylphosphine palladium (0.01 g), methyltrioctyl ammonium chloride (manufactured by Aldrich, trade name: Aliquat 336 (registered trademark) under an inert atmosphere )) (0.20 g) and toluene (10 mL) were heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture to reflux for 8 hours. 4-tert-butylphenylboronic acid (0.01 g) was added to the reaction solution to reflux for 6 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 2 hours. After the mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was stirred for 1 hour, and then the deposited precipitate was filtered to dissolve in 20 mL of tetrahydrofuran. After the solution obtained in this manner was added dropwise to 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran, and purified by passing through an alumina column and a ceria gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was dropped into methanol (200 mL), and the precipitated solid was filtered and dried. The resulting poly[9,9-bis[3-ethoxycarbonyl-4-bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-thin] The yield of (Polymer A) was 520 mg.

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

[Experimental Example 1]

Synthesis of bismuth salt of polymer A

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (20 mL) and ethanol (20 mL) were added and the mixture was warmed to 55 °C. Here, an aqueous solution of cesium hydroxide (200 mg) dissolved in water (2 mL) was added, and the mixture was stirred at 55 ° C for 6 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (150 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer A was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer A is referred to as a conjugated polymer compound 1. The conjugated polymer compound 1 is a group consisting of a structural unit represented by the chemical formula (B) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 100% by mole.). The orbital energy system of HOMO of conjugated polymer compound 1 is -5.5 eV, and the orbital energy system of LUMO is -2.7 eV.

[Experimental Example 2] Synthesis of Potassium Salt of Polymer A

Polymer A (200 mg) was placed in a 100 mL flask for nitrogen substitution. Tetrahydrofuran (20 mL) and methanol (10 mL) were added, and potassium hydroxide (400 mg) dissolved in water (2 mL) was added to the mixture, and the mixture was stirred at 65 ° C for 1 hour. 50 mL of methanol was added to the reaction solution, and the mixture was stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (131 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer A was completely disappeared by NMR spectroscopy. The potassium salt of the obtained polymer A is referred to as a conjugated polymer compound 2. The conjugated polymer compound 2 is a group consisting of a structural unit represented by the chemical formula (C) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 100% by mole.). The orbital energy system of HOMO of conjugated polymer compound 2 is -5.5 eV, and the orbital energy system of LUMO is -2.7 eV.

[Experimental Example 3] Synthesis of sodium salt of polymer A

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (20 mL) and methanol (10 mL) were added, and a solution of sodium hydroxide (260 mg) dissolved in water (2 mL) was added to the mixture, and the mixture was stirred at 65 ° C for 1 hour. In the reaction solution, 30 mL of methanol was added, and the mixture was 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 give a pale yellow solid (123 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer A was completely disappeared by NMR spectroscopy. The sodium salt of the obtained polymer A is referred to as a conjugated polymer compound 3. The conjugated polymer compound 3 is composed of a structural unit represented by the chemical formula (D) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 100% by mole.). The orbital energy system of HOMO of conjugated polymer compound 3 is -5.6 eV, and the orbital energy system of LUMO is -2.8 eV.

[Experimental Example 4] Synthesis of ammonium salt of polymer A

Polymer A (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (20 mL) and methanol (15 mL) were added, and tetramethylammonium hydroxide (50 mg) was added to a mixed aqueous solution of water (1 mL), and stirred at 65 ° C for 6 hours. An aqueous solution of tetramethylammonium hydroxide (50 mg) dissolved in water (1 mL) was added to the reaction solution, and stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (150 mg). It was confirmed by NMR spectroscopy that the signal of the ethyl group derived from the ethyl ester moiety in the polymer A disappeared by 90%. The obtained ammonium salt of the polymer A is referred to as a conjugated polymer compound 4. The conjugated polymer compound 4 is a group consisting of a structural unit represented by the chemical formula (E) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 90% by mole.). The orbital energy system of HOMO of conjugated polymer compound 4 is -5.6 eV, and the orbital energy system of LUMO is -2.8 eV.

[Reference Example 4]

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

Compound A (0.52 g), 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.29 g) was mixed under an inert atmosphere. ), triphenylphosphine palladium (0.0087 g), methyltrioctyl ammonium chloride (manufactured by Aldrich Co., Ltd., trade name: Aliquat 336 (registered trademark)) (0.20 g), toluene (10 mL), and 2 M sodium carbonate aqueous solution (10 mL) ), heated to 80 ° C. The reaction solution was allowed to react for 3.5 hours. Then, p-bromotoluene (0.68 g) was added thereto, and the reaction was further carried out for 2.5 hours. After the reaction, the reaction liquid was cooled to room temperature, and 50 mL of ethyl acetate 50 mL / distilled water was added to remove water layer. After 50 mL of distilled water was further added to remove the aqueous layer, magnesium sulfate was added as a desiccant, and the insoluble matter was filtered, and the organic solvent was removed. Then, the obtained residue was dissolved again in 10 mL of THF, and 2 mL of a saturated aqueous solution of sodium diethyldithiocarbamate was added thereto, and after stirring for 30 minutes, the organic solvent was removed. Purification was carried out by an alumina column (developing solvent hexane: ethyl acetate = 1:1, v/v), and the deposited precipitate was filtered, decompressed, and dried for 12 hours to obtain 524 mg of 2,7-bis [ 7-(4-Methylphenyl)-9,9-dioctylindol-2-yl]-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-A) Oxyethoxyethoxy)ethoxy]ethoxy]phenyl]-indole (Polymer B).

The polystyrene-converted number average molecular weight of the polymer B was 2.0 × 10 ³ . Further, the polymer B is represented by the chemical formula (F).

[Experimental Example 5] Synthesis of bismuth salt of polymer B

Polymer B (262 mg) was placed in a 100 mL flask and replaced with nitrogen. Here, tetrahydrofuran (10 mL) and methanol (15 mL) were added, and the mixture was warmed to 55 °C. Here, an aqueous solution of cesium hydroxide (341 mg) dissolved in water (1 mL) was added, and the mixture was stirred at 55 ° C for 5 hours. After the obtained 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 give a pale yellow solid (250 mg). The signal from the ethyl group at the ethyl ester site was completely disappeared by NMR spectroscopy. The obtained bismuth salt of the polymer B is referred to as a conjugated polymer compound 5. The conjugated polymer compound 5 is selected from the group consisting of a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit represented by the chemical formula (G). The ratio of the above-mentioned base and the structural unit of one or more kinds of bases represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula (20) in the entire structural unit The ratio of the structural unit indicated is rounded to the nearest third place and becomes 33.3 mol%.). The orbital energy system of HOMO of conjugated polymer compound 5 is -5.6 eV, and the orbital energy system of LUMO is -2.6 eV.

[Reference Example 5] Synthesis of polymer C

Compound A (0.40 g), Compound B (0.49 g), N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2, were mixed under an inert atmosphere. 6-Dimethylphenyl) 1,4-phenylenediamine (35 mg), triphenylphosphine palladium (8 mg), methyltrioctyl ammonium chloride (manufactured by Aldrich, trade name: Aliquat 336 (registered trademark) (0.20 g) and toluene (10 mL) were heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, followed by reflux for 8 hours. Phenylboronic acid (0.01 g) was added to the reaction mixture, and the mixture was refluxed for 6 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 2 hours. After the mixed solution was dropped into 300 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered and dried under reduced pressure for 2 hours to dissolve in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was stirred for 1 hour, and then the precipitate was filtered and dissolved in 20 mL of tetrahydrofuran. After the solution obtained in this manner was added dropwise to 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran, and purified through an alumina column and a ceria gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was dropped into methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer C was 526 mg.

The polystyrene-converted number average molecular weight of the polymer C was 3.6 × 10 ⁴ . The polymer C is a structural unit represented by the chemical formula (H).

In addition, N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylene diamine can be used. The synthesis is carried out by, for example, the method described in JP-A-2008-74917.

[Experimental Example 6] Synthesis of bismuth salt of polymer C

Polymer C (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (20 mL) and methanol (20 mL) were added and mixed. An aqueous solution of cesium hydroxide (200 mg) dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C for 1 hour. 30 mL of methanol was added to the reaction solution, and the mixture was stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was distilled off under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (150 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer C was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer C is referred to as a conjugated polymer compound 6. The conjugated polymer compound 6 is composed of a structural unit represented by the chemical formula (I) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 95% by mole.). The orbital energy system of HOMO of conjugated polymer compound 6 is -5.3 eV, and the orbital energy system of LUMO is -2.6 eV.

[Reference Example 6] Synthesis of polymer D

Mixing Compound A (0.55g), Compound B (0.67g), N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2, under an inert environment 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 Co., Ltd., trade name: Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL) were heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 2 hr. Phenylboronic acid (0.004 g) was added to the reaction mixture, and the mixture was refluxed for 6 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 2 hours. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour. Then, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was stirred for 1 hour, and then the precipitate was filtered and dissolved in 20 mL of tetrahydrofuran. After the solution obtained in this manner was dropped to 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in tetrahydrofuran, and purified through an alumina column and a ceria gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was dropped into methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer D was 590 mg.

The polystyrene-converted number average molecular weight of the polymer D was 2.7 × 10 ⁴ . The polymer D is a structural unit represented by the chemical formula (J).

Further, 3,7-dibromo-N-(4-n-butylphenyl)phenoxazine is a method described in JP-A-2007-70620 (or a reference is disclosed in JP-A-2004-137456). The synthesis is carried out by the method of the publication.

[Experimental Example 7] Synthesis of bismuth salt of polymer D

Polymer D (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (15 mL) and methanol (10 mL) were combined. An aqueous solution of cesium hydroxide (360 mg) dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C for 3 hours. 10 mL of methanol was added to the reaction solution, and the mixture was stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (210 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer D was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer D is referred to as a conjugated polymer compound 7. The conjugated polymer compound 7 is composed of a structural unit represented by the chemical formula (K) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 90% by mole.). The orbital energy system of HOMO of conjugated polymer compound 7 is -5.3 eV, and the orbital energy system of LUMO is -2.4 eV.

[Reference Example 7] Synthesis of polymer E

Mixing Compound A (0.37 g), Compound B (0.82 g), 1,3-dibromobenzene (0.09 g), triphenylphosphine palladium (0.01 g), methyltrioctyl ammonium chloride under an inert atmosphere (manufactured by Aldrich Co., Ltd., trade name: Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL), and heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture, and the mixture was refluxed for 7 hr. Phenylboronic acid (0.002 g) was added to the reaction mixture, and the mixture was refluxed for 10 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 1 hour. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour. Then, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was stirred for 1 hour, and then the precipitate was filtered to dissolve in 20 mL of tetrahydrofuran. After the solution thus obtained was added dropwise to 200 mL of methanol and stirred for 30 minutes, the precipitate precipitated was filtered to give a solid. The obtained solid was dissolved in tetrahydrofuran, and purified through an alumina column and a ceria gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was dropped into methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer E was 293 mg.

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

[Experimental Example 8] Synthesis of bismuth salt of polymer E

Polymer E (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (10 mL) and methanol (5 mL) were combined. An aqueous solution of cesium hydroxide (200 mg) dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C for 2 hours. 10 mL of methanol was added to the reaction solution, and the mixture was stirred at 65 ° C for 5 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (170 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer E was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer E is referred to as a conjugated polymer compound 8. The conjugated polymer compound 8 is composed of a structural unit represented by the chemical formula (M) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is "75 mol%.". The orbital energy system of HOMO of conjugated polymer compound 8 is -5.6 eV, and the orbital energy system of LUMO is -2.6 eV.

[Reference Example 8]

Synthesis of polymer F

Compound B (1.01 g), 1,4-dibromo-2,3,5,6-tetrafluorobenzene (0.30 g), triphenylphosphine palladium (0.02 g), methyltrisine were mixed under an inert atmosphere. A quaternary ammonium chloride (manufactured by Aldrich Co., Ltd., trade name: Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL) were heated to 105 °C. A 2 M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction mixture to reflux for 4 hours. Phenylboronic acid (0.002 g) was added to the reaction mixture, and the mixture was refluxed for 4 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 1 hour. The mixed solution was dropped into 300 mL of methanol and stirred for 1 hour. Then, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of tetrahydrofuran. The obtained solution was added dropwise to a mixed solvent of 120 mL of methanol and 50 mL of a 3 wt% aqueous acetic acid solution, and the mixture was stirred for 1 hour, and then the precipitate precipitated was filtered to dissolve in 20 mL of tetrahydrofuran. After the solution obtained in this manner was dropped to 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered to obtain a solid. The obtained solid was dissolved in a mixed solvent of tetrahydrofuran/ethyl acetate (1/1 (volume ratio)), and purified by passing through an alumina column or a ceria gel column. After concentrating the tetrahydrofuran solution recovered from the column, it was dropped to methanol (200 mL), and the precipitated solid was filtered and dried. The yield of the obtained polymer E was 343 mg.

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

[Experimental Example 9]

Synthesis of bismuth salt of polymer F

Polymer F (150 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (10 mL) and methanol (5 mL) were combined. An aqueous solution of cesium hydroxide (260 mg) dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C for 2 hours. 10 mL of methanol was added to the reaction solution, and the mixture was stirred at 65 ° C for 5 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (130 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer E was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer F is referred to as a conjugated polymer compound 9. The conjugated polymer compound 9 is composed of a structural unit represented by the chemical formula (O) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is "75 mol%.". The orbital energy system of HOMO of conjugated polymer compound 9 is -5.9 eV, and the orbital energy system of LUMO is -2.8 eV.

[Reference Example 9]

2-[2-(2-methoxyethoxy)ethoxy]-p-toluenesulfonate (11.0 g), triethylene glycol (30.0 g) and potassium hydroxide were mixed under an inert atmosphere. (3.3 g), heating and stirring at 100 ° C for 18 hours. After allowing to cool, the reaction solution was added to water (100 mL), and the mixture was concentrated by trichloromethane. 2-(2-(2-(2-(2-methoxyethoxy))) was obtained by subjecting the concentrated solution to Kugelrohr distillation (10 mm Torr, 180 ° C). Ethoxy)-ethoxy)-ethoxy)-ethoxy)ethanol (6.1 g).

[Reference Example 10]

Mix 2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy) in an inert atmosphere Ethanol (8.0 g), sodium hydroxide (1.4 g), distilled water (2 mL) and tetrahydrofuran (2 mL) were ice-cooled. A solution of p-toluenesulfonium chloride (5.5 g) in tetrahydrofuran (6.4 mL) was added dropwise to the mixed solution over 30 minutes, and after the dropwise addition, the reaction solution was stirred at room temperature and stirred for 15 hours. Distilled water (50 mL) was added to the reaction solution, and after neutralizing the reaction solution by 6 M sulfuric acid, liquid separation was carried out by chloroform. By concentrating the solution to give 2-(2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy) P-tosylate (11.8 g).

[Reference Example 11]

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

2,7-dibromo-9-one (127.2 g), ethyl salicylate (375.2 g) and thioglycolic acid (3.5 g) were placed in a 300 mL flask to carry out nitrogen substitution. Methanesulfonic acid (1420 mL) was added here, and the mixture was stirred overnight at 75 °C. The mixture was allowed to cool, and added to ice water and stirred for 1 hour. The resulting solid was removed by filtration and washed with heated acetonitrile. The washed solid was dissolved in acetone, and the obtained acetone solution was recrystallized and filtered to give a solid (167.8 g). The solid (5g), 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). The solution was transferred to a flask and stirred at 105 ° C for 4 hours. The resulting mixture was allowed to cool to room temperature, added to ice water and stirred for 1 hour. Trichloromethane (300 mL) was added to the reaction mixture to carry out liquid separation extraction, and the solution was concentrated. By dissolving the concentrate in ethyl acetate, passing through a column of alumina, and concentrating the solution to obtain 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2- (2-(2-(2-(2-(2-methoxyethoxy)-ethoxy)-ethoxy)-ethoxy)-ethoxy)ethoxy]phenyl]-茀 (Compound C) (4.5 g).

[Reference Example 12]

Synthesis of polymer G

Compound C (1.0 g), 4-tert-butylphenyl bromide (0.9 mg), 2,2'-bipyridine (0.3 g) and dehydrated tetrahydrofuran (50 mL) were added to a 200 mL flask under an inert atmosphere. Mix. After the mixture was heated to 55 ° C, bis(1,5-cyclooctadiene)nickel (0.6 g) was added and stirred at 55 ° C for 5 hours. After cooling the mixture to room temperature, the reaction solution was added dropwise to a mixture of methanol (200 mL) and 1 N diluted hydrochloric acid (200 mL). After the resulting precipitate was collected by filtration, it was redissolved in tetrahydrofuran. A mixture of methanol (200 mL) and 15% aqueous ammonia (100 mL) was added dropwise, and the resulting precipitate was collected by filtration. The precipitate was redissolved in tetrahydrofuran, and a mixture of methanol (200 mL) and water (100 mL) was added, and the resulting precipitate was collected by filtration. The polymer G (360 mg) was obtained by drying under reduced pressure on the collected precipitate.

The polystyrene-converted number average molecular weight of the polymer G was 6.0 × 10 ⁴ . The polymer G is a structural unit represented by the chemical formula (P).

[Experimental Example 10]

Synthesis of bismuth salt of polymer G

Polymer G (150 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (15 mL) and methanol (5 mL) were combined. An aqueous solution of cesium hydroxide (170 mg) dissolved in water (2 mL) was added to the mixed solution, and the mixture was stirred at 65 ° C for 6 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The solid which was produced by washing with water was dried under reduced pressure to give a pale yellow solid (95 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer G was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer G is referred to as a conjugated polymer compound 10. The conjugated polymer compound 10 is composed of a structural unit represented by the chemical formula (Q) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 100% by mole.). The orbital energy system of HOMO of conjugated polymer compound 10 is -5.7 eV, and the orbital energy system of LUMO is -2.9 eV.

[Reference Example 13]

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

3,5-dibromosalicylic acid (20 g), ethanol (17 mL), concentrated sulfuric acid (1.5 mL) and toluene (7 mL) were mixed under an inert atmosphere, and the mixture was stirred under heating at 130 ° C for 20 hours. After allowing to cool, the reaction solution was added to ice water (100 mL), and the mixture was concentrated by chlorobenzene. The obtained solid was dissolved in isopropanol, and the solution was dropped to distilled water. The precipitate obtained by filtration was removed to give a solid (18 g). The solid (1 g), 2-[2-(2-methoxyethoxy)ethoxy]-p-tosylate (1.5 g), potassium carbonate (0.7 g) were mixed under an inert atmosphere. It was stirred with heating at 100 ° C for 4 hours with DMF (15 mL). After allowing to cool, chloroform was added to carry out liquid separation extraction, and the solution was concentrated. The concentrate is dissolved in chloroform and passed to a cerium oxide gel column for purification. By concentrating the solution, 1,3-dibromo-5-ethoxycarbonyl-6-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene (1.0 g) was obtained. ).

[Reference Example 14]

Synthesis of polymer H

Mixing compound A (0.20 g), compound B (0.5 g), 1,3-dibromo-5-ethoxycarbonyl-6-[2-[2-(2-methoxyethoxy) under an inert atmosphere Ethyl]ethoxy]benzene (0.1 g), triphenylphosphine palladium (30 mg), tetrabutylammonium chloride (4 mg) and toluene (19 mL) were heated to 105 °C. A 2 M aqueous sodium carbonate solution (5 mL) was added dropwise to the reaction mixture, followed by reflux for 5 hours. Phenylboronic acid (6 mg) was added to the reaction mixture, and the mixture was refluxed for 14 hours. Next, an aqueous solution of sodium diethyldithiocarbamate (10 mL, concentration: 0.05 g/mL) was added, and the mixture was stirred for 2 hours. The aqueous layer was removed, and the organic layer was washed with distilled water, and the solid obtained by concentration was dissolved in chloroform, and purified through an alumina column and a ceria 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 of the polymer H in terms of polystyrene was 3.6 × 10 ⁴ . The polymer H is composed of a structural unit represented by the chemical formula (R).

[Experimental Example 11]

Synthesis of bismuth salt of polymer H

Polymer H (200 mg) was placed in a 100 mL flask and replaced with nitrogen. Tetrahydrofuran (14 mL) and methanol (7 mL) were added and mixed. An aqueous solution of cesium hydroxide (90 mg) 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 stirred at 65 ° C for 4 hours. After the mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (190 mg). The signal of the ethyl group derived from the ethyl ester moiety in the polymer H was completely disappeared by NMR spectroscopy. The obtained phosphonium salt of the polymer H is referred to as a conjugated polymer compound 11. The conjugated polymer compound 11 is composed of a structural unit represented by the chemical formula (S) ("a group including a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit). The ratio of one or more selected bases to the structural unit of one or more types represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula in the entire structural unit. (20) The ratio of the structural units indicated is 100% by mole.). The orbital energy system of HOMO of conjugated polymer compound 11 is -5.6 eV, and the orbital energy system of LUMO is -2.8 eV.

[Reference Example 15]

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

2,7-dibromo-9-one (34.1 g), 2,3-dihydroxybenzoic acid methyl ester (101.3 g) and thioglycolic acid (1.4 g) were placed in a 500 mL flask to carry out nitrogen substitution. Methanesulfonic acid (350 mL) was added here, 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 removed by filtration and washed by heating acetonitrile. The washed solid was dissolved in acetone, and the obtained acetone solution was subjected to recrystallization and filtration to remove. The solid (16.3 g), 2-[2-(2-methoxyethoxy)ethoxy]-p-tosylate (60.3 g), potassium carbonate (48.6 g) and 18-crown Ether-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 resulting mixture was allowed to cool to room temperature, added to ice water and stirred for 1 hour. By adding ethyl acetate (300 mL) to the reaction mixture, liquid separation extraction was carried out, and the solution was concentrated to dissolve the mixed solvent in chloroform/methanol (50/1 (volume ratio)) through a cerium oxide gel tube. The column is refined. By concentrating the solution of the solution in the column, 2,7-dibromo-9,9-bis[3,4-bis[2-[2-(2-methoxyethoxy)ethoxy) is obtained. Ethoxy]-5-methoxycarbonylphenyl]indole (Compound D) (20.5 g).

[Reference Example 16]

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

Compound D (0.70 g), 2-(4,4,5,5-tetramethyl-1,2,3-dioxaborolan-2-yl)-9 was mixed under an inert atmosphere. 9-Dioctyl thin (0.62 g), triphenylphosphine palladium (0.019 g), dioxane (40 mL), water (60 mL) and aqueous potassium carbonate (1.38 g), and heated to 80 °C. The reaction solution was allowed to react for 1 hour. After the reaction, 5 mL of saturated diethyldithiocarbamate sodium water was added, and after stirring for 30 minutes, the organic solvent was removed. The obtained solid was purified by an alumina column (developing solvent hexane: ethyl acetate = 1:1 (volume ratio)), and the solution was concentrated to obtain 2,7-bis[7-(4-A) Phenyl)-9,9-dioctylindol-2-yl]-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy) Ethoxy]ethoxy]phenyl]-thin (Polymer I) (660 mg).

The polystyrene-converted number average molecular weight of the polymer I was 2.0 × 10 ³ . Polymer I is represented by the chemical formula (T). Further, 2-(4,4,5,5-tetramethyl-1,2,3-dioxaborolan-2-yl)-9,9-dioctylfluorene can be, for example, The synthesis is carried out by the method described in The Journal of Physical Chemistry B 2000, 104, 9118-9125.

[Experimental Example 12]

Synthesis of bismuth salt of polymer I

Polymer I (236 mg) was placed in a 100 mL flask and replaced with argon. Here, tetrahydrofuran (20 mL) and methanol (10 mL) were added, and the mixture was warmed to 65 °C. Here, an aqueous solution of cesium hydroxide (240 mg) dissolved in water (2 mL) was added, and the mixture was stirred at 65 ° C for 7 hours. After the resulting mixture was cooled to room temperature, the reaction solvent was evaporated under reduced pressure. The resulting solid was washed with water and dried under reduced pressure to give a pale yellow solid (190 mg). The signal from the ethyl group at the ethyl ester site was completely disappeared by NMR spectroscopy. The obtained sulfonium salt of the polymer I is referred to as a conjugated polymer compound 12. The conjugated polymer compound 12 is selected from the group consisting of a group represented by the chemical formula (1) and a group represented by the chemical formula (2) in the entire structural unit represented by the chemical formula (U). The ratio of the above-mentioned base and the structural unit of one or more kinds of bases represented by the chemical formula (3) and the chemical formula (13), the chemical formula (15), the chemical formula (17), and the chemical formula (20) in the entire structural unit The ratio of the structural units indicated is rounded to the nearest third place of the decimal point to become 33.3 mol%.). The orbital energy system of HOMO of conjugated polymer compound 12 is -5.6 eV, and the orbital energy system of LUMO is -2.8 eV.

[Production and evaluation results of components for evaluation]

In order to evaluate the electron injecting property of the ionic polymer, an evaluation element having a diode structure of only flowing electrons was produced, and the current-voltage characteristics thereof were evaluated.

The evaluation element was produced as follows. First, an aluminum layer (lower electrode) having a thickness of 30 nm is formed on a glass substrate, and a polymer layer having a thickness of 80 nm formed by the repeating unit represented by the following chemical formula (I) is formed on the aluminum layer. An electron injecting layer of 5 nm was formed on the polymer layer, and an aluminum layer (upper electrode) having a thickness of 100 nm was formed on the electron injecting layer to fabricate an element for evaluation.

The evaluation element was produced using the materials of different electron injecting layers and the forming method thereof, and the following three types were produced.

(a) The evaluation element 1 of the ionic polymer synthesized in Example 1 was formed in the atmosphere by a coating method.

(b) An element 2 for evaluation of sodium fluoride is formed by a vapor deposition method.

(c) The evaluation element 3 of the crucible is formed by a vapor deposition method.

A positive voltage was applied to the lower electrode of each of the evaluation elements, a negative voltage was applied to the upper electrode, and the applied voltage was gradually increased, and the electron current flowing through the evaluation element was measured.

The result is shown in Figure 3. Figure 3 is a graph for explaining the electrical characteristics of an ionic polymer. The vertical axis represents the electron current (A: ampere), and the horizontal axis represents the applied voltage (V: volt). In the graph of Fig. 3, (a) indicates the evaluation result of the evaluation element 1, (b) indicates the evaluation result of the evaluation element 2, and (c) indicates the evaluation result of the evaluation element 3.

As is apparent from Fig. 3, the evaluation element 1 used for the electron injecting layer of the ionic polymer of the present invention is an evaluation element 2 for evaluation of sodium fluoride or ruthenium used for the electron injection layer, and an evaluation element. At 3 o'clock, a good electron injection characteristic is more exhibited in the entire region of 5 V or more of the applied voltage. It is understood that the electron current flowing in the evaluation element 1 for the ionic polymer used in the electron injection layer is relatively flowable in the sodium ion or the ruthenium used for the electron injection layer in terms of the electron current flowing when the applied voltage is 10 V. The electron currents of the evaluation elements 2 and 3 are extraordinarily large, and have excellent electron injection characteristics even in a region where the applied voltage is relatively low.

10. . . Organic thin film transistor

20. . . Substrate

20A. . . Gate electrode

30. . . Gate insulation

40. . . Organic semiconductor layer

50. . . Charge injection layer

50A. . . First charge injection layer

50B. . . Second charge injection layer

60A. . . First source/drain electrode

60B. . . Second source/drain electrode

70. . . Substrate

L1. . . The interval between the first charge injection layer 50A and the second charge injection layer 50B

L2. . . The width of the first charge injection layer 50A and the second charge injection layer 50B

X. . . The direction in which the first charge injection layer 50A and the second charge injection layer 50B are separated

Y. . . Vertical direction (perpendicular to the direction of the paper)

Z. . . Thickness direction

Fig. 1 is a cross-sectional view schematically showing an example of the structure of the organic thin film transistor of the first embodiment.

Fig. 2 is a cross-sectional view schematically showing an example of the structure of the organic thin film transistor of the second embodiment.

Figure 3 is a graph illustrating the electrical characteristics of an ionic polymer.

10. . . Organic thin film transistor

20. . . Substrate

30. . . Gate insulation

40. . . Organic semiconductor layer

50. . . Charge injection layer

50A. . . First charge injection layer

50B. . . Second charge injection layer

60A. . . First source/drain electrode

60B. . . Second source/drain electrode

L1. . . The interval between the first charge injection layer 50A and the second charge injection layer 50B

L2. . . The width of the first charge injection layer 50A and the second charge injection layer 50B

X. . . The direction in which the first charge injection layer 50A and the second charge injection layer 50B are separated

Y. . . Vertical direction (perpendicular to the direction of the paper)

Z. . . Thickness direction

Claims (9)

An organic thin film transistor comprising: a gate electrode, a first source/drain electrode, a second source/drain electrode, and the first source/drain electrode and the second source/drain An organic semiconductor layer between the electrode and the gate electrode, and the first source/drain electrode between the first source/drain electrode and the second source/drain electrode and the organic semiconductor layer; An organic thin film transistor of a charge injection layer in which a second source/drain electrode is in contact with each other, wherein the charge injection layer contains an ionic polymer having charge injection characteristics, and the ionic polymer contains the following chemical formula ( 13) One selected from the group consisting of the structural unit represented by the following formula, the structural unit represented by the following chemical formula (15), the structural unit represented by the following chemical formula (17), and the structural unit represented by the following chemical formula (20) The polymer of the above structural unit, (In the chemical formula (13), R ¹ is a monovalent group of the group represented by the chemical formula (14), and Ar ¹ is a (2+n4)-valent aromatic group having or not having a substituent other than R ¹ N4 is an integer of 1 or more, and in a state where R ¹ has a plurality of plural, the plurality of R ¹ systems may be the same or different. (In the chemical formula (14), R ² represents an organic group having a (1+m1+m2) valence, m1 and m2 each independently represent an integer of 1 or more, and Q ¹ represents a divalent organic group, and Y ¹ is an Represents -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- or -PO ₃ ^2- , M ¹ represents a metal cation or an ammonium cation with or without a substituent, and Z ¹ represents F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^a SO ₃ ^- , R ^a COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , n1 represents an integer of 0 or more, a1 represents an integer of 1 or more, and b1 represents an integer of 0 or more. However, a1 and b1 are selected such that the charge of the group represented by -(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 becomes 0, and R ^a represents with or without a substituent. The alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms with or without a substituent, Q ³ represents an organic group having a divalent value, and Y ³ is represented by a -CN or a chemical formula ( 4) to the group represented by any one of the chemical formulas (12), n3 represents an integer of 0 or more, in Q ¹ , Q ³ Each of Y ¹ , M ¹ , Z ¹ , Y ³ , n1 , a1 , b1 , and n3 has a plurality of Q ¹ , Q ³ , Y ¹ , M ¹ , and Z ¹ in a plurality of states. Y ³ , n1 , a1 , b1 and n3 may be the same or different), -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 chemical formula (4) In the chemical formula (12), R' represents a divalent hydrocarbon group with or without a substituent, and R" represents a hydrogen atom, a monovalent hydrocarbon group with or without a substituent, -COOH, -SO ₃ H , -OH, -SH, -NR ^c ₂ , -CN or -C(=O)NR ^c ₂ , R''' represents a trivalent hydrocarbon group with or without a substituent, and a3 represents an integer of 1 or more A4 represents an integer of 0 or more, and R ^c represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or an aryl group having 6 to 50 carbon atoms with or without a substituent, in R When ', R' and R''' each have a plurality of states, a plurality of R', R", and R''' can be the same or different)), (In the chemical formula (15), R ³ represents a monovalent group of the group represented by the chemical formula (16), and Ar ² represents an (2+n5)-valent aromatic group having or not having a substituent other than R ³ N5 is an integer of 1 or more, and in a state where R ³ has a plurality of plural, the plurality of R ³ systems may be the same or different. (In the chemical formula (16), R ⁴ represents an organic group having a (1+m3+m4) valence, Q ² represents a divalent organic group, and Y ² represents a cation, an ammonium cation, a phosphine cation or a phosphonium cation or Iodine cation, M ² represents F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^b SO ₃ ^- , R ^b COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , Z ² represents a metal cation or The ammonium cation with or without a substituent, n2 represents an integer of 0 or more, a2 represents an integer of 1 or more, and b2 represents an integer of 0 or more, but a2 and b2 are such that -(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) The choice of the base represented by _b2 is 0, and R ^b represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or with or without The aryl group having 6 to 50 carbon atoms in the substituent, Q ³ , Y ² , and n ^{3 are the} same as defined above, and m 3 and m 4 each independently represent an integer of 1 or more, in Q ² , Q ³ , ^{Y 2, M 2, Z 2} , Y 3, n2, a2, b2 , and n3 Each line having a plurality of state, having a plurality of ^{Q 2, Q 3, Y 2} , M 2, Z 2, Y 3, n2, a2, b2 , and n3 may be the same or different)), (In the chemical formula (17), R ⁵ is a monovalent group of the group represented by the chemical formula (18), R ⁶ is a monovalent group of the group represented by the chemical formula (19), and Ar ³ means having or not having The (2+n6+n7)-valent aromatic group of the substituent other than R ⁵ and R ⁶ , n6 and n7 each independently represent an integer of 1 or more, and each of R ⁵ and R ⁶ has a plurality of states. Next, having a plurality of R ⁵ and R ⁶ , respectively, may be the same or different, -R ⁷ -{(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 } _m5 (18) (in In the chemical formula (18), R ⁷ represents a direct bond or an organic group having a (1+m5) valence, and Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1 are the same as those described above. M5 represents an integer of 1 or more, and each of Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1, and b1 has a plurality of Q ¹ , Y ¹ , M ¹ , and Z in a plurality of states. ¹ , n1 , a1 and b1 , respectively, may be the same or different), -R ⁸ -{(Q ³ ) _n3 -Y ³ } _m6 (19) (In the chemical formula (19), R ⁸ represents a single bond or (1+m6) the organic group of the valence, Q ³ , Y ³ and n3 are the same meanings as described above, and m6 is an integer of 1 or more. However, when R ⁸ is a single bond of, based M6 represents 1, Q ^3, Y ³ and n3 each line having a plurality of one of the state, having a plurality of Q ^3, Y ³ and n3, respectively, may be the same , can also be different)), (In the chemical formula (20), R ⁹ is a monovalent group of the group represented by the chemical formula (21), R ¹⁰ is a monovalent group of the group represented by the chemical formula (22), and Ar ⁴ means having or not having An aromatic group of (2+n8+n9) valence of a substituent other than R ⁹ and R ¹⁰ , n ⁸ and n ⁹ each independently represent an integer of 1 or more, and each of R ⁹ and R ¹⁰ has a plurality of states Next, having a plurality of R ⁹ and R ¹⁰ , respectively, may be the same or different, -R ¹¹ -{(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) _b2 } _m7 (21) (in In the chemical formula (21), R ¹¹ represents a single bond or an organic group of (1+m7) valence, and Q ² , Y ² , M ² , Z ² , n2, a2 and b2 represent the same meaning as described above, m7 It means an integer of 1 or more, but when R ¹¹ is a single bond, m7 represents 1, and each of Q ² , Y ² , M ² , Z ² , n2, a2, and b2 has a plurality of states. , having a plurality of Q ² , Y ² , M ² , Z ² , n2, a2, and b2, respectively, may be the same or different), -R ¹² -{(Q ³ ) _n3 -Y ³ } _m8 (22) (In the chemical formula (22), R ¹² represents a single bond or an organic group of (1+m8) valence, and Q ³ , Y ³ and n3 are the same as In the above-mentioned sense, m8 represents an integer of 1 or more, but when R ¹² is a single bond, m8 represents 1, and each of Q ³ , Y ³ and n3 has a plurality of states, and has a plurality of Q ³ , Y ³ and n3 may be the same or different)). The organic thin film transistor according to claim 1, wherein the conductive type of the conductive charge injection layer is n-type, and the conductive type of the organic semiconductor layer is n-type. The organic thin film transistor according to claim 2, wherein a gate insulating layer disposed adjacent to the gate electrode is provided between the organic semiconductor layer and the gate electrode, and the gate electrode It is composed of an n-type semiconductor substrate. An organic thin film transistor substrate having the organic thin film transistor according to claim 1 of the patent application. A display device comprising the organic thin film transistor substrate according to claim 4 of the patent application as a drive substrate. A method for producing an organic thin film transistor, comprising: forming a gate electrode, a first source/drain electrode, a second source/drain electrode, and the first source/drain electrode and the second source; An organic semiconductor layer between the gate electrode and the gate electrode, and the first source/german between the first source/drain electrode and the second source/drain electrode and the organic semiconductor layer A method for producing an organic thin film transistor of a charge injection layer in which a pole electrode and a second source/drain electrode are in contact with each other, comprising: forming a charge injection layer containing an ionic polymer having charge injection characteristics; In the step, the ionic polymer contains a structural unit represented by the following chemical formula (13), a structural unit represented by the following chemical formula (15), a structural unit represented by the following chemical formula (17), and the following chemical formula (20). a polymer of one or more structural units selected from the group consisting of structural units, (In the chemical formula (13), R ¹ is a monovalent group of the group represented by the chemical formula (14), and Ar ¹ is a (2+n4)-valent aromatic group having or not having a substituent other than R ¹ N4 is an integer of 1 or more, and in the state in which R ¹ has a plurality of plural, the plurality of R ¹ systems may be the same or different. (In the chemical formula (14), R ² represents an organic group having a (1+m1+m2) valence, m1 and m2 each independently represent an integer of 1 or more, and Q ¹ represents a divalent organic group, and Y ¹ is an Represents -CO ₂ ^- , -SO ₃ ^- , -SO ₂ ^- or -PO ₃ ^2- , M ¹ represents a metal cation or an ammonium cation with or without a substituent, and Z ¹ represents F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^a SO ₃ ^- , R ^a COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , n1 represents an integer of 0 or more, a1 represents an integer of 1 or more, and b1 represents an integer of 0 or more. However, a1 and b1 are selected such that the charge of the group represented by -(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 becomes 0, and R ^a represents with or without a substituent. The alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms with or without a substituent, Q ³ represents an organic group having a divalent value, and Y ³ is represented by a -CN or a chemical formula ( 4) to the group represented by any one of the chemical formulas (12), n3 represents an integer of 0 or more, in Q ¹ , Q ³ Each of Y ¹ , M ¹ , Z ¹ , Y ³ , n1 , a1 , b1 , and n3 has a plurality of Q ¹ , Q ³ , Y ¹ , M ¹ , and Z ¹ in a plurality of states. Y ³ , n1 , a1 , b1 and n3 may be the same or different), -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 chemical formula (4) In the chemical formula (12), R' represents a divalent hydrocarbon group with or without a substituent, and R" represents a hydrogen atom, a monovalent hydrocarbon group with or without a substituent, -COOH, -SO ₃ H , -OH, -SH, -NR ^c ₂ , -CN or -C(=O)NR ^c ₂ , R''' represents a trivalent hydrocarbon group with or without a substituent, and a3 represents an integer of 1 or more A4 represents an integer of 0 or more, and R ^c represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or an aryl group having 6 to 50 carbon atoms with or without a substituent, in R When ', R' and R''' each have a plurality of states, a plurality of R', R", and R''' can be the same or different)), (In the chemical formula (15), R ³ represents a monovalent group of the group represented by the chemical formula (16), and Ar ² represents an (2+n5)-valent aromatic group having or not having a substituent other than R ³ N5 is an integer of 1 or more, and in a state where R ³ has a plurality of plural, the plurality of R ³ systems may be the same or different. (In the chemical formula (16), R ⁴ represents an organic group having a (1+m3+m4) valence, Q ² represents a divalent organic group, and Y ² represents a cation, an ammonium cation, a phosphine cation or a phosphonium cation or Iodine cation, M ² represents F ^- , Cl ^- , Br ^- , I ^- , OH ^- , R ^b SO ₃ ^- , R ^b COO ^- , ClO ^- , ClO ₂ ^- , ClO ₃ ^- , ClO ₄ ^- , SCN ^- , CN ^- , NO ₃ ^- , SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , BF ₄ ^- or PF ₆ ^- , Z ² represents a metal cation or The ammonium cation with or without a substituent, n2 represents an integer of 0 or more, a2 represents an integer of 1 or more, and b2 represents an integer of 0 or more, but a2 and b2 are such that -(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) The choice of the base represented by _b2 is 0, and R ^b represents an alkyl group having 1 to 30 carbon atoms with or without a substituent or with or without The aryl group having 6 to 50 carbon atoms in the substituent, Q ³ , Y ² , and n ^{3 are the} same as defined above, and m 3 and m 4 each independently represent an integer of 1 or more, in Q ² , Q ³ , ^{Y 2, M 2, Z 2} , Y 3, n2, a2, b2 , and n3 Each line having a plurality of state, having a plurality of ^{Q 2, Q 3, Y 2} , M 2, Z 2, Y 3, n2, a2, b2 , and n3, respectively, may be the same or different)), (In the chemical formula (17), R ⁵ is a monovalent group of the group represented by the chemical formula (18), R ⁶ is a monovalent group of the group represented by the chemical formula (19), and Ar ³ means having or not having The (2+n6+n7)-valent aromatic group of the substituent other than R ⁵ and R ⁶ , n6 and n7 each independently represent an integer of 1 or more, and each of R ⁵ and R ⁶ has a plurality of states. Next, having a plurality of R ⁵ and R ⁶ , respectively, may be the same or different, -R ⁷ -{(Q ¹ ) _n1 -Y ¹ (M ¹ ) _a1 (Z ¹ ) _b1 } _m5 (18) (in In the chemical formula (18), R ⁷ represents a direct bond or an organic group having a (1+m5) valence, and Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1 and b1 are the same as those described above. M5 represents an integer of 1 or more, and each of Q ¹ , Y ¹ , M ¹ , Z ¹ , n1, a1, and b1 has a plurality of Q ¹ , Y ¹ , M ¹ , and Z in a plurality of states. ¹ , n1 , a1 and b1 , respectively, may be the same or different), -R ⁸ -{(Q ³ ) _n3 -Y ³ } _m6 (19) (In the chemical formula (19), R ⁸ represents a single bond or (1+m6) the organic group of the valence, Q ³ , Y ³ and n3 are the same meanings as described above, and m6 is an integer of 1 or more. However, when R ⁸ is a single bond of, based M6 represents 1, Q ^3, Y ³ and n3 each line having a plurality of one of the state, having a plurality of Q ^3, Y ³ and n3, respectively, may be the same , can also be different)), (In the chemical formula (20), R ⁹ is a monovalent group of the group represented by the chemical formula (21), R ¹⁰ is a monovalent group of the group represented by the chemical formula (22), and Ar ⁴ means having or not having An aromatic group of (2+n8+n9) valence of a substituent other than R ⁹ and R ¹⁰ , n ⁸ and n ⁹ each independently represent an integer of 1 or more, and each of R ⁹ and R ¹⁰ has a plurality of states Next, having a plurality of R ⁹ and R ¹⁰ , respectively, may be the same or different, -R ¹¹ -{(Q ² ) _n2 -Y ² (M ² ) _a2 (Z ² ) _b2 } _m7 (21) (in In the chemical formula (21), R ¹¹ represents a single bond or an organic group of (1+m7) valence, and Q ² , Y ² , M ² , Z ² , n2, a2 and b2 represent the same meaning as described above, m7 It means an integer of 1 or more, but when R ¹¹ is a single bond, m7 represents 1, and each of Q ² , Y ² , M ² , Z ² , n2, a2, and b2 has a plurality of states. , having a plurality of Q ² , Y ² , M ² , Z ² , n2, a2, and b2, respectively, may be the same or different), -R ¹² -{(Q ³ ) _n3 -Y ³ } _m8 (22) (In the chemical formula (22), R ¹² represents a single bond or an organic group of (1+m8) valence, and Q ³ , Y ³ and n3 are the same as In the above-mentioned meaning, m8 represents an integer of 1 or more, but when R ¹² is a single bond, m8 represents 1, and each of Q ³ , Y ³ and n3 has a plurality of states, and has a plurality of Q ³ , Y ³ and n3 may be the same or different)). The method for producing an organic thin film transistor according to claim 6, wherein in the step of forming the charge injection layer, the coating liquid containing the ionic polymer is coated under a normal pressure environment. Film formation is performed to form the aforementioned charge injection layer. The method for producing an organic thin film transistor according to claim 6, wherein the first source/drain electrode and the second source/drain electrode are coated in a normal pressure environment. The cloth liquid is formed by coating and forming a film. The method for producing an organic thin film transistor according to the sixth aspect of the invention, wherein the organic semiconductor layer is formed by coating a coating liquid into a film under a normal pressure environment.