JP6146096B2 - Thiophene compound, water-soluble conductive polymer and aqueous solution thereof, and production method thereof - Google Patents

Description

  The present invention relates to a novel thiophene compound, polythiophenes, a water-soluble conductive polymer aqueous solution using the same, and a method for producing the same.

  Polymers having π-conjugated double bonds represented by polyacetylene, polythiophene, polyaniline, polypyrrole, etc. are known to become conductors (conductive polymers) by doping with acceptors and donors. Applications to solid electrolytes, conductive paints, electrochromic elements, transparent electrodes, transparent conductive films, chemical sensors, actuators, etc. are being studied. Conventionally, conductive polymers are insoluble and infusible and thus have a problem in molding processability, and it has been necessary to use a polar organic solvent (for example, an amide solvent) having a large environmental load in order to be dissolved. Therefore, there has been a demand for a water-soluble conductive polymer that can be easily molded and dissolved in water with a small environmental load. In recent years, polythiophene called poly (3,4-ethylenedioxythiophene (PEDOT)) has been actively studied as a conductive polymer (see, for example, Patent Document 1), but 3,4-ethylene which is a raw material monomer thereof. Since dioxythiophene (EDOT) has poor water solubility (2.1 g / L-water, 0.2% by weight), it is known that the resulting conductive polymer is also water-insoluble.

  For this reason, as a method for obtaining a water-soluble conductive polymer, a method of polymerizing EDOT in the presence of a water-soluble polymer dopant such as polystyrene sulfonic acid (PSS) has been proposed (for example, see Patent Document 2). Called PEDOT-PSS).

  According to Patent Document 2, it is said that the polyanion becomes water-soluble by being taken in as a dopant and water dispersant, and the molding processability is improved. However, since the conductive polymer described in Patent Document 2 contains a large amount of a low-conductivity polymer part that is not involved in doping, heat conductivity is reduced due to low conductivity and a large excess of sulfo groups. There are problems such as low water resistance and equipment corrosion due to strong acidity.

  By the way, since the conductive polymer described in Patent Document 2 has both good conductivity and molding processability, application to a polymer solid electrolyte of a capacitor and printable electronics is also directed.

  As an example of the former, there is a solid electrolyte of an aluminum solid electrolytic capacitor.

  In the latter case, for example, when a technique such as ink jet is applied, if the particle size of the conductive polymer in the aqueous solution is large, there is a concern that the nozzle is clogged.

  On the other hand, as an alternative method for obtaining a water-soluble conductive polymer, a substituent (for example, a sulfo group, a sulfonate group, etc.) having water solubility and a doping action is covalently bonded directly or via a spacer to a polymer molecular chain. It is proposed that a water-soluble self-doped conductive polymer excellent in molding processability is obtained by polymerizing the compound introduced in step 1 (see, for example, Patent Documents 3 to 4 and Non-Patent Documents 1 and 2). .

  As an application example of the water-soluble self-doped conductive polymer described in these documents, there is an application of a resist antistatic film forming material used when forming a semiconductor circuit pattern by electron beam lithography. This is because, since the conductive polymer is water-soluble, there is an advantage that it is difficult to damage the fat-soluble resist and can be washed with water after exposure (for example, see Non-Patent Document 3). However, with the recent high integration of semiconductors, there has been a demand for finer pattern formation, and therefore a polymer having higher conductivity (antistatic ability) has been demanded.

  Therefore, it is a self-doping type water-soluble conductive polymer that can provide processability without adding other components that do not contribute to improvement of conductivity due to water solubilization, in addition to good water solubility and conductivity When an aqueous solution is used, a polymer having a sufficiently small particle size has been demanded.

Japanese Patent No. 2721700 Japanese Patent No. 2636968 Japanese Patent Publication No.8-13873 Japanese Patent No. 3182239

Journal of American Chemical Society, 1987, pp. 1858-1859 Chemistry of Materials, 2009, 1815-1821 Electronic Materials, February 1990, 48-55

The present invention has been made in view of the above-described background art, and its purpose is as follows.
(1) providing a novel water-soluble thiophene compound used as a conductive material, and (2) providing a novel water-soluble polythiophene used as a conductive material,
It is.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention is the following novel thiophene compounds, polythiophenes, water-soluble conductive polymers, and methods for producing them.

  [1] A thiophene compound represented by the following formula (1).

［上記式中、Ｒ^１は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−Ｘ−ＳＯ_３Ｍを表す。Ｘは置換基を有していてもよい炭素数１〜６のアルキレン基又は炭素数６〜２０のアリーレン基を表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。ｍは０〜３の整数を表す。ｎは０〜１２の整数を表す。但し、ｎ＋ｍ≧１である。］
［２］下記式（２）乃至（４）のいずれかで表される上記［１］に記載のチオフェン化合物。

[In the above formula, R ¹ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —X—SO ₃ M. X represents an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 20 carbon atoms which may have a substituent. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 3. n represents an integer of 0 to 12. However, n + m ≧ 1. ]
[2] The thiophene compound according to the above [1], which is represented by any one of the following formulas (2) to (4).

［上記式（２）中、Ｒ^３は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−（ＣＨ_２）_ｌ−ＳＯ_３Ｍを表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。ｌは１〜６の整数を表す。ｎは０〜１２の整数を表す。］

[In the above formula (2), R ³ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ —. Represents SO ₃ M. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. l represents an integer of 1 to 6; n represents an integer of 0 to 12. ]

［上記式（３）中、Ｒ^４は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−Ａｒ−ＳＯ_３Ｍを表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。Ａｒは置換基を有していてもよい炭素数６〜２０のアリーレン基を表す。ｎは０〜１２の整数を表す。］

[In the above formula (3), R ⁴ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —Ar—SO ₃ M. Represent. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. Ar represents an arylene group having 6 to 20 carbon atoms which may have a substituent. n represents an integer of 0 to 12. ]

［上記式（４）中、Ｍは水素原子、Ｌｉ、Ｎａ、及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。ｎは０〜１２の整数を表す。］ ［３］下記式（５）で表されるチオフェン化合物と下記式（６）で表される化合物とを、非プロトン性の極性溶媒中、塩基存在下に反応させることを特徴とする上記［１］又は［２］に記載のチオフェン化合物の製造方法。

[In the above formula (4), M represents an alkali metal selected from the group consisting of a hydrogen atom, Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 12. [3] The thiophene compound represented by the following formula (5) and the compound represented by the following formula (6) are reacted in an aprotic polar solvent in the presence of a base: The manufacturing method of the thiophene compound as described in [1] or [2].

［上記式（５）中、Ｙはトシレート、メシレート、トリフラート、クロライド、ブロマイド、又はアイオダイドを表し、ｎは０〜１２の整数を表す。］

[In the above formula (5), Y represents tosylate, mesylate, triflate, chloride, bromide, or iodide, and n represents an integer of 0-12. ]

［上記式（６）中、Ｒ^１は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−Ｘ−ＳＯ_３Ｍを表す。Ｘは置換基を有していてもよい炭素数１〜６のアルキレン基又は炭素数６〜２０のアリーレン基を表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。］
［４］下記式（５）で表されるチオフェン化合物を、水溶媒中、亜硫酸塩と反応させ、上記［２］に記載の上記式（４）で表されるチオフェン化合物を得ることを特徴とするチオフェン化合物の製造方法。

[In the above formula (6), R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —X—SO ₃ M. Represent. X represents an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 20 carbon atoms which may have a substituent. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. ]
[4] A thiophene compound represented by the following formula (5) is reacted with a sulfite in an aqueous solvent to obtain the thiophene compound represented by the above formula (4) according to the above [2]. A method for producing a thiophene compound.

［上記式（５）中、Ｙはトシレート、メシレート、トリフラート、クロライド、ブロマイド、又はアイオダイドを表し、ｎは０〜１２の整数を表す。］
［５］下記式（５ａ）で表されるチオフェン化合物を、水とアルコールの混合溶媒中、ラジカル開始剤の存在下、亜硫酸水素塩と反応させ、上記［２］に記載の上記式（４）で表されるチオフェン化合物を得ることを特徴とするチオフェン化合物の製造方法。

[In the above formula (5), Y represents tosylate, mesylate, triflate, chloride, bromide, or iodide, and n represents an integer of 0-12. ]
[5] A thiophene compound represented by the following formula (5a) is reacted with bisulfite in a mixed solvent of water and alcohol in the presence of a radical initiator, and the formula (4) according to the above [2]. A method for producing a thiophene compound, characterized in that:

［上記式（５ａ）中、ｎは０〜１２の整数を表す。］
［６］下記式（１３）

[In said formula (5a), n represents the integer of 0-12. ]
[6] The following formula (13)

［上記式（１３）中、Ｒ^１は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−Ｘ−ＳＯ_３Ｍを表す。Ｘは置換基を有していてもよい炭素数１〜６のアルキレン基又は炭素数６〜２０のアリーレン基を表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。ｍは０〜３の整数を表す。ｎは０〜１２の整数を表す。但し、ｎ＋ｍ≧１である。］
で表される構造単位及び下記式（１４）

[In the above formula (13), R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —X—SO ₃ M. Represent. X represents an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 20 carbon atoms which may have a substituent. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 3. n represents an integer of 0 to 12. However, n + m ≧ 1. ]
And a structural unit represented by the following formula (14)

［上記式（１４）中、Ｒ^１、Ｘ、ｎ、ｍは上記式（１３）と同意義を示す。］
で表される構造単位からなる群より選ばれる少なくとも一種の構造単位を含むポリチオフェン類。

[In the above formula (14), R ¹ , X, n and m have the same meaning as in the above formula (13). ]
Polythiophenes containing at least one structural unit selected from the group consisting of structural units represented by:

  [7] Formula (15) below

［上記式（１５）中、Ｒ^３は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−（ＣＨ_２）_ｌ−ＳＯ_３Ｍを表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。ｌは１〜６の整数を表す。ｎは０〜１２の整数を表す。］
で表される構造単位、下記式（１６）

[In the above formula (15), R ³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ —. Represents SO ₃ M. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. l represents an integer of 1 to 6; n represents an integer of 0 to 12. ]
A structural unit represented by the following formula (16):

［上記式（１６）中、Ｒ^３、ｎ、ｌは上記式（１５）と同意義を示す。］
で表される構造単位、下記式（１７）

[In said formula (16), R < ³ >, n, l shows the same significance as said formula (15). ]
A structural unit represented by the following formula (17):

［上記式（１７）中、Ｒ^４は水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基、炭素数６〜２０のアリール基、若しくは−Ａｒ−ＳＯ_３Ｍを表す。Ｍは水素原子、Ｌｉ、Ｎａ及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。Ａｒは置換基を有していてもよい炭素数６〜２０のアリーレン基を表す。ｎは０〜１２の整数を表す。］
で表される構造単位、下記式（１８）

[In the above formula (17), R ⁴ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —Ar—SO ₃ M. Represent. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. Ar represents an arylene group having 6 to 20 carbon atoms which may have a substituent. n represents an integer of 0 to 12. ]
A structural unit represented by the following formula (18):

［上記式（１８）中、Ｒ^４、Ａｒ、ｎは上記式（１７）と同意義を示す。］
で表される構造単位、下記式（１９）

[In the above formula (18), R ⁴ , Ar, and n are as defined in the above formula (17). ]
A structural unit represented by the following formula (19):

［上記式（１９）中、Ｍは水素原子、Ｌｉ、Ｎａ、及びＫからなる群より選ばれるアルカリ金属、ＮＨ（Ｒ^２）_３又はＨＮＣ_５Ｈ_５を表す。Ｒ^２は各々独立して水素原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を表す。ｎは０〜１２の整数を表す。］
で表される構造単位、及び下記式（２０）

[In the above formula (19), M represents an alkali metal selected from the group consisting of a hydrogen atom, Li, Na, and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 to 12. ]
And a structural unit represented by the following formula (20)

［上記式（２０）中、ｎは上記式（１９）と同意義を示す。］
で表される構造単位からなる群より選ばれる少なくとも一種の構造単位を含む上記［５］に記載のポリチオフェン類。

[In the above formula (20), n is as defined in the above formula (19). ]
The polythiophene according to the above [5], comprising at least one structural unit selected from the group consisting of structural units represented by:

  [8] The polythiophene according to [6] or [7] above, wherein the polythiophene has a weight average molecular weight in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid.

  [9] The method according to any one of [6] to [8], wherein the thiophene compound according to [1] or [2] is polymerized in water or an alcohol solvent in the presence of an oxidizing agent. Of producing polythiophenes.

  [10] The method for producing a polythiophene according to the above [9], wherein the oxidizing agent is an iron salt (III) or a combined system of persulfate and iron salt (III).

  [11] A water-soluble conductive polymer aqueous solution comprising the aqueous solution of the polythiophenes according to any one of [6] to [8].

  [12] A method for producing a conductive coating, comprising applying the aqueous solution according to [11] above to a substrate and drying.

  [13] Use of the aqueous solution according to [11] above for a conductive film.

  ADVANTAGE OF THE INVENTION According to this invention, the novel thiophene compound useful as a raw material monomer of water-soluble conductive polymer can be provided with a simple manufacturing method.

  In addition, according to the present invention, novel polythiophenes having both good conductivity and sufficient water solubility for molding can be provided.

It is a UV-Vis-NIR analysis result of the polymer (23) obtained in Example 5. It is a UV-Vis-NIR analysis result of the polymer (26) obtained in Example 6. It is a UV-Vis-NIR analysis result of the polymer (23) obtained in Example 7. It is a UV-Vis-NIR analysis result of the polymer (26) obtained in Example 8. It is a UV-Vis-NIR analysis result of the polymer (29) obtained in Example 9. 4 is a result of UV-Vis-NIR analysis of the polymer (32) obtained in Example 10. 4 is a result of UV-Vis-NIR analysis of the polymer (35) obtained in Example 11. 4 is a result of UV-Vis-NIR analysis of the polymer (38) obtained in Example 12. It is a UV-Vis-NIR analysis result of the polymer (62) obtained in Example 13. It is a UV-Vis-NIR analysis result of the polymer (62) obtained in Example 14. It is a UV-Vis-NIR analysis result of the polymer (23) obtained in Example 15 and Example 16. It is IR analysis result of the polymer (23) obtained in Example 5. It is IR analysis result of the polymer (26) obtained in Example 6. 4 is an IR analysis result of the polymer (35) obtained in Example 11. It is an IR analysis result of the polymer (38) obtained in Example 12. It is IR analysis result of the polymer (62) obtained in Example 13. It is IR analysis result of the polymer (62) obtained in Example 14.

  Hereinafter, the present invention will be described in detail.

  First, the thiophene compound of the present invention will be described.

  The thiophene compound in the present invention is a compound represented by the above formula (1).

In the above formula (1), R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —X—SO ₃ M. . As the substituent of R ¹ is an alkyl group or an aryl group having a substituent, for example, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, hydroxy group, An amino group, a carboxyl group, etc. are mentioned.

The substituent R ¹ in the above formula (1) is not particularly limited as long as it falls within the above definition. For example, hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, 3,3-dimethyl group Alkyl group having 1 to 6 carbon atoms such as butyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, trifluoromethyl group; phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group , Aminophenyl group, trifluoromethylphenyl group, naphthyl group, biphenyl group, etc. It can be exemplified -X-SO ₃ M; aryl group.

Among these, R ¹ is more preferably a hydrogen atom, a methyl group, or —X—SO ₃ M.

  In the above formula (1), X represents an optionally substituted alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 20 carbon atoms. In addition, as said substituent in case X is an alkylene group or arylene group which has a substituent, a C1-C6 alkyl group or an alkoxy group, a C6-C20 aryl group, a hydroxy group, amino, for example Group, carboxyl group and the like.

  X in the formula (1) is not particularly limited as long as it falls within the above definition, and examples thereof include methylene, dimethylene, trimethylene, tetramethylene, hexamethylene, phenylene, biphenylene, naphthylene, anthrylene and the like. Can do.

  Among these, X is more preferably dimethylene, trimethylene, tetramethylene, or phenylene.

  N in the above formula (1) represents an integer of 0 to 12. n is preferably an integer of 0 to 6.

  M in the above formula (1) represents an integer of 0 to 3.

In the above formula (1), M represents an alkali metal selected from the group consisting of a hydrogen atom, Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ .

In that case, R < ² > represents a hydrogen atom or the C1-C6 alkyl group which may have a substituent each independently. Examples of the substituent R ² include the same as R ^1, and more preferably a hydrogen atom or a methyl group. As the substituent when R ² is an alkyl group having a substituent, for example, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, hydroxy group, an amino group, A carboxyl group etc. are mentioned.

As the compound represented by the above formula (1), specifically,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl ) Lithium 2-aminoethanesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] dioxin-2 Ylmethyl) -2-aminoethanesulfonic acid triethylammonium, N-(2,3-dihydro - thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (sodium 2-aminoethanesulfonate), N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (potassium 2-aminoethanesulfonate),
N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid, N-methyl-N- (2,3 -Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid sodium, N-methyl-N- (2,3-dihydro-thieno [3,4 b] [1,4] Dioxin-2-ylmethyl) -2-aminoethanesulfonic acid lithium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin- 2-ylmethyl) -2-aminoethanesulfonate potassium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethane Ammonium sulfonate, N-methyl -N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid triethylammonium, N-methyl-N- (2,3- Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonic acid pyridinium;
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonate sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl ) Lithium 3-aminopropanesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonic acid ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] Geo Cin-2-ylmethyl) -3-aminopropanesulfonic acid triethylammonium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminopropanesulfone Pyridinium acid, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonic acid pyridinium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (sodium 3-aminopropanesulfonate), N- (2,3-dihydro-thieno [3,4-b] [1, 4] dioxin-2-ylmethyl) -bis (potassium 3-aminopropanesulfonate),
N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonic acid, N-methyl-N- (2,3 -Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonic acid sodium, N-methyl-N- (2,3-dihydro-thieno [3,4 b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonic acid lithium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin- 2-ylmethyl) -3-aminopropanesulfonic acid potassium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropane Ammonium sulfonate N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonate triethylammonium, N-methyl-N- (2 , 3-Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminopropanesulfonate pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl ) Lithium 4-aminobutanesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] dioxin-2 Ylmethyl) -4-aminobutanesulfonate triethylammonium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate pyridinium, N -(2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (sodium 4-aminobutanesulfonate), N- (2,3-dihydro-thieno [ 3,4-b] [1,4] dioxin-2-ylmethyl) -bis (potassium 4-aminobutanesulfonate), N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonic acid,
N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate sodium, N-methyl-N- (2, 3-Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate, N-methyl-N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-ylmethyl) -4-aminobutanesulfonate, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin 2-ylmethyl) -4-aminobutanesulfonic acid ammonium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-amino Triethyl butane sulfonate Ammonium, N- methyl-N-(2,3-dihydro - thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-amino-butanoic acid pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonate sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl ) Lithium 4-aminobenzenesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonate ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] Geo Cin-2-ylmethyl) -4-aminobenzenesulfonic acid triethylammonium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfone Pyridinium acid, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (sodium 4-aminobenzenesulfonate), N- (2,3- Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (potassium 4-aminobenzenesulfonate), N-methyl-N- (2,3-dihydro-thieno [3, 4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonic acid, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxy 2-ylmethyl) -4-aminobenzenesulfonic acid sodium salt, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-amino Lithium benzenesulfonate, potassium N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonate, N-methyl- N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonate ammonium, N-methyl-N- (2,3-dihydro- Thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonate triethylammonium sulfonate, N-methyl-N- (2,3-dihydro-thieno [3,4] b] [1,4] dioxin-2-ylmethyl) -4-aminobenzenesulfonic acid pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonate sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl ) Lithium 3-aminobenzenesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonate ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] Geo Cin-2-ylmethyl) -3-aminobenzenesulfonic acid triethylammonium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfone Pyridinium acid, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (sodium 3-aminobenzenesulfonate), N- (2,3- Dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -bis (potassium 3-aminobenzenesulfonate), N-methyl-N- (2,3-dihydro-thieno [3, 4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonic acid, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxy 2-ylmethyl) -3-aminobenzenesulfonic acid sodium salt, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-amino Lithium benzenesulfonate, potassium N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonate, N-methyl- N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonate ammonium, N-methyl-N- (2,3-dihydro- Thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonate triethylammonium sulfonate, N-methyl-N- (2,3-dihydro-thieno [3,4] b] [1,4] dioxin-2-ylmethyl) -3-aminobenzenesulfonic acid pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl ) Lithium 2-aminoethanesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminoethanesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] dioxin-2-yl) -2-aminoethanesulfur Triethylammonium acid, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid pyridinium, N-methyl-N- (2 , 3-Dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid, N-methyl-N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid sodium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin 2-yl) -2-aminoethanesulfonic acid lithium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-amino Potassium ethanesulfonate, N-methyl-N- (2 3-Dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid ammonium, N-methyl-N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-yl) -2-aminoethanesulfonic acid triethylammonium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] Dioxin-2-yl) -2-aminoethanesulfonic acid pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid sodium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl ) Lithium 3-aminopropanesulfonate, potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonate, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] dioxin-2-yl) -3-amino Triethylammonium lopansulfonate, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -2-aminopropanesulfonate pyridinium, N- (2,3-dihydro -Thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid pyridinium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl ) Sodium 3-aminopropanesulfonate, lithium N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonate , N-Me Ru-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonate potassium, N-methyl-N- (2,3- Dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid ammonium, N-methyl-N- (2,3-dihydro-thieno [3,4-b ] [1,4] dioxin-2-yl) -3-aminopropanesulfonic acid triethylammonium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin- 2-yl) -3-aminopropanesulfonic acid pyridinium,
N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonic acid, N- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-yl) -3-aminobenzenesulfonic acid sodium salt, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl ) -3-aminobenzenesulfonate lithium, N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonate potassium, N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonate ammonium, N- (2,3-dihydro-thieno [3,4-b ] [1,4] dioxin-2-yl) -3-amino N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonate pyridinium, N-methyl-N- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonic acid, N-methyl-N- (2,3-dihydro-thieno [3, 4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonate sodium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] Dioxin-2-yl) -3-aminobenzenesulfonate lithium, N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3- Potassium aminobenzenesulfonate N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonate ammonium, N-methyl-N- (2, Triethylammonium 3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonate, N-methyl-N- (2,3-dihydro-thieno [3, 4-b] [1,4] dioxin-2-yl) -3-aminobenzenesulfonic acid pyridinium and the like.

  Of these, the raw material monomer for the water-soluble conductive polymer is preferably a compound represented by any one of the above formulas (2) to (4).

In the above formula (2), R ³ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, — (CH ₂ ) ₁ —SO _3. M is represented. l represents an integer of 1 to 6; n and M are as defined in the above formula (1).

In the above formula (3), R ⁴ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —Ar—SO ₃ M. Ar each independently represents an arylene group having 6 to 20 carbon atoms which may have a substituent. n and M are as defined in the above formula (1).

Examples of the substituent when the substituent R ³ or R ⁴ is an alkyl group having a substituent include an alkyl group having 1 to 6 carbon atoms or an alkoxy group, an aryl group having 6 to 20 carbon atoms, and a hydroxy group. , Amino group, carboxyl group and the like.

  In the above formula (4), n and M are as defined in the formula (1).

As the compound represented by the above formula (4), specifically,
2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethanesulfonic acid, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2 -Lithium ylmethanesulfonate, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethanesulfonate sodium, 2,3-dihydro-thieno [3,4-b] [1,4] potassium dioxin-2-ylmethanesulfonate, 2,3-dihydro-thieno [3,4-b] [1,4] ammonium dioxin-2-ylmethanesulfonate, 2,3-dihydro- Thieno [3,4-b] [1,4] dioxin-2-ylmethanesulfonate triethylammonium 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethanesulfone Acid pyridi 2- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) ethane-1-sulfonic acid, 2- (2,3-dihydro-thieno [3, 4-b] [1,4] dioxin-2-yl) ethane-1-sulfonate, 2- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl ) Lithium ethane-1-sulfonate, potassium 2- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) ethanesulfonate, 2- (2,3-dihydro) -Thieno [3,4-b] [1,4] dioxin-2-yl) ammonium ethanesulfonate, 2- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2 -Yl) ethane-1-triethylammonium sulfonate, 2- (2, - dihydro - thieno [3,4-b] [1,4] dioxin-2-yl) ethane-1-sulfonic acid pyridinium,
3- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) propane-1-sulfonic acid, 3- (2,3-dihydro-thieno [3,4- b] [1,4] dioxin-2-yl) propane-1-sulfonic acid sodium, 3- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) propane Lithium -1-sulfonate, potassium 3- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) propane-1-sulfonate, 3- (2,3- Dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) propane-1-sulfonic acid ammonium, 3- (2,3-dihydro-thieno [3,4-b] [1,4 Dioxin-2-yl) propane-1-sulfonic acid triethylammoni 3- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) propane-1-sulfonic acid pyridinium, 3- (2,3-dihydro-thieno [3] , 4-b] [1,4] dioxin-2-yl) propane-1-sulfonic acid pyridinium,
6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonic acid, 6- (2,3-dihydro-thieno [3,4- b] [1,4] dioxin-2-yl) hexane-1-sulfonic acid sodium, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane -1-lithium sulfonate, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate potassium, 6- (2,3- Dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) ammonium-1-sulfonate, 6- (2,3-dihydro-thieno [3,4-b] [1,4 ] Dioxin-2-yl) hexane-1-sulfonic acid triethylammoni 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonic acid pyridinium, 6- (2,3-dihydro-thieno [3 , 4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate, and the like.

  The thiophene compound represented by any one of the above formulas (1) to (3) of the present invention comprises a thiophene compound represented by the above formula (5) and a compound represented by the above formula (6) as a polar solvent. It can be conveniently obtained by reacting in the presence of a base.

  In the compound represented by the above formula (5), Y is tosylate, mesylate, triflate, chloride, bromide, or iodide. n is as defined in the formula (1).

  Specific examples of the compound represented by the above formula (5) include 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl chloride, 2,3-dihydro. -Thieno [3,4-b] [1,4] dioxin-2-ylmethyl bromide, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl iodide, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl tosylate, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2 -Ylmethyl mesylate, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl triflate, 2,3-dihydro-thieno [3,4-b] [1, 4] Dioxin-2-ylmethyl chloride, 2,3-di Dro-thieno [3,4-b] [1,4] dioxin-2-ylethyl bromide, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylethyl iodide 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylethyl tosylate, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin- 2-ylethyl mesylate, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylethyl triflate, 2,3-dihydro-thieno [3,4-b] [1 , 4] dioxin-2-ylpropyl chloride, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylpropyl bromide, 2,3-dihydro-thieno [3,4] b] [1,4] dioxin-2-y Propyl iodide, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylpropyl tosylate, 2,3-dihydro-thieno [3,4-b] [1,4 Examples include dioxin-2-ylpropyl mesylate, 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylpropyl triflate, and the like.

In the compound represented by the above formula (6), R ¹ , X and M have the same meaning as in the above formula (1).

  Specific examples of the compound represented by the formula (6) include 2-aminoethanesulfonic acid, sodium 2-aminoethanesulfonate, potassium 2-aminoethanesulfonate, lithium 2-aminoethanesulfonate, 2 -Ammonium aminoethanesulfonate, N-methyl-2-aminoethanesulfonic acid, sodium N-methyl-2-aminoethanesulfonate, potassium N-methyl-2-aminoethanesulfonate, N-methyl-2-aminoethane Lithium sulfonate, ammonium N-methyl-2-aminoethanesulfonate, 3-aminopropanesulfonic acid, sodium 3-aminopropanesulfonate, potassium 3-aminopropanesulfonate, lithium 3-aminopropanesulfonate, 3-amino Ammonium propanesulfonate, N-methyl- -Aminopropanesulfonic acid, sodium N-methyl-3-aminopropanesulfonate, potassium N-methyl-3-aminopropanesulfonate, lithium N-methyl-3-aminopropanesulfonate, N-methyl-3-aminopropane Ammonium sulfonate, 4-aminobutanesulfonic acid, sodium 4-aminobutanesulfonate, potassium 4-aminobutanesulfonate, lithium 4-aminobutanesulfonate, ammonium 4-aminobutanesulfonate, N-methyl-4-amino Butanesulfonic acid, sodium N-methyl-4-aminobutanesulfonate, potassium N-methyl-4-aminobutanesulfonate, lithium N-methyl-4-aminobutanesulfonate, N-methyl-4-aminobutanesulfonic acid Ammonium and the like are exemplified.

  The polar solvent used in this reaction is not particularly limited as long as the reaction proceeds. For example, N, N-dimethylaminoformamide, N-methylformamide, N-methylpyrrolidone, N, N-dimethyl is used. Examples include acetamide, methanol, acetone, water and the like. Of these, N, N-dimethylformamide is more preferable. These may be used alone or in any desired mixture.

  The amount of the polar solvent used is not particularly limited as long as it is an amount that dissolves the compound represented by the above formula (5) and the compound represented by the above formula (6) as raw materials. The total charge of the compound represented by (5) and the compound represented by the above formula (6) is preferably 0.1 to 200 times by weight, more preferably 1 to 100 times by weight.

  The base used in this reaction is not particularly limited as long as the reaction proceeds. For example, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydride, lithium hydroxide, sodium hydroxide Potassium hydroxide, rubidium hydroxide, calcium hydroxide, aqueous ammonia, pyridine, trimethylamine, triethylamine, tributylamine and the like. Of these, sodium carbonate and potassium carbonate are more preferable.

  As a usage-amount of a base, 1-100 times mole is preferable with respect to the total mole number of a compound represented by the compound represented by the said Formula (5), and the said Formula (6), More preferably, it is 1-10 times. Mol, more preferably 2 to 5 times mol.

  Although the reaction temperature of this reaction is not particularly limited as long as the reaction proceeds, it is preferably -20 to 200 ° C, more preferably 30 to 180 ° C, still more preferably 50 to 120 ° C. .

  The reaction atmosphere of this reaction is preferably air or nitrogen or argon, more preferably nitrogen.

  The reaction pressure of this reaction may be an atmospheric pressure system or a pressurized system, and is preferably an atmospheric pressure system.

  The thiophene compound represented by the above formula (4) can be easily obtained by reacting the thiophene compound represented by the above formula (5) with a sulfite in an aqueous solvent.

  Examples of the sulfite used in this reaction include sodium sulfite, potassium sulfite, and ammonium sulfite.

  The amount of sulfite used in this reaction is preferably 0.5 to 50 times mol, more preferably 1 to 3 times mol, relative to the charged molar amount of the compound represented by the above formula (5). It is.

  The amount of the aqueous solvent used in this reaction is, for example, an amount in which the thiophene compound and sulfite are dissolved, and is not particularly limited, but is 0.1 to 0.1 of the amount of the compound represented by the above formula (5). It is preferably 200 times by weight, more preferably 1 to 100 times by weight.

  The temperature of this reaction is not particularly limited as long as the reaction proceeds, but is preferably 0 ° C. to reflux temperature (about 100 ° C.), more preferably 50 to reflux temperature (about 100 ° C.). is there.

  As another method for obtaining the thiophene compound represented by the above formula (4), for example, the thiophene compound represented by the above formula (5a) is a bisulfite salt in a mixed solvent of water and alcohol in the presence of a radical initiator. The method of making it react with is mentioned. In the above formula (5a), n is as defined in the formula (1).

  Specific examples of the compound represented by the above formula (5a) include 2- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-ethene. 3- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-propene, 4- (2,3-dihydro-thieno [3,4-b] ] [1,4] dioxin-2-yl) -1-butene, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-hexene, Examples include 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-octene and the like.

  Although it does not specifically limit by the preparation method and procedure in this reaction, For example, the aqueous solution containing the bisulfite separately prepared in the alcohol solution containing the thiophene compound represented by the said Formula (5a) and a radical initiator, and a small amount of sulfites. It is obtained by dropping and reacting at room temperature or under heating.

  Examples of the alcohol used in this reaction include methanol, ethanol, propanol, and butanol. Preferred is methanol or ethanol. The amount of alcohol used in this reaction is, for example, an amount in which the thiophene compound represented by the above formula (5a) is dissolved or suspended, and is not particularly limited, but in the above formula (5a) The amount of the compound to be represented is preferably 0.1 to 200 times by weight, more preferably 1 to 100 times by weight.

  The amount of water used in this reaction is, for example, an amount in which bisulfite and a small amount of sulfite are dissolved, and is not particularly limited, but is 0.1 to 200 times the amount of bisulfite charged. Is more preferable, and the range of 1 to 100 times by weight is more preferable.

  Examples of the bisulfite used in this reaction include sodium bisulfite, potassium bisulfite, and ammonium bisulfite. The amount of bisulfite used in this reaction is preferably 0.5 to 100 times mol, more preferably 1 to 10 times mol for the thiophene compound represented by the above formula (5a). It is.

  Examples of the sulfite used in this reaction include sodium sulfite, potassium sulfite, and ammonium sulfite. Further, the amount of sulfite used in this reaction is preferably 0.0001 to 10-fold mol, more preferably 0.001 to 1 mol, relative to the charged molar amount of the compound represented by the above formula (5a). The range is double moles.

  The temperature of this reaction is not particularly limited as long as the reaction proceeds, but is preferably 0 ° C to reflux temperature (about 100 ° C), more preferably 50 to reflux temperature (about 100 ° C).

  The reaction atmosphere of this reaction is preferably air or nitrogen or argon, more preferably nitrogen.

  The reaction pressure of this reaction may be an atmospheric pressure system or a pressurized system, and is preferably an atmospheric pressure system.

  As the thiophene compound of the present invention, a compound having a water solubility such that the compound is dissolved in water at a temperature of 0.5% by weight or more at room temperature or under heating is more preferable.

  Next, the polythiophenes of the present invention will be described.

  The polythiophenes in the present invention are polythiophenes containing at least one structural unit selected from the group consisting of the structural unit represented by the above formula (13) and the structural unit represented by the above formula (14).

In the above formula (13), R ¹ , M, X, n, and m are as defined in the above formula (1).

In the above formula (14), R ¹ , X, n, and m are as defined in the above formula (13). The structural unit represented by the above formula (14) represents the doping state of the structural unit represented by the above formula (13).

  The dopant causing the insulator-metal transition by doping is divided into an acceptor and a donor.

The former enters near the polymer chain of the conductive polymer by doping and takes π electrons from the conjugated system of the main chain. As a result, since positive charges (holes, holes) are injected onto the main chain, it is also called a p-type dopant. Specifically, halogens (Br ₂ , I ₂ , Cl ₂ ), Lewis acid (BF ₃ , PF ₅ , AsF ₅ ), protonic acid (H ₂ SO ₄ , HCl, CF ₃ SO ₃ H), transition metal Examples include halide (FeCl ₃ ), organic substance (TCNQ), and the like.

  The latter is also referred to as an n-type dopant because it gives electrons to the conjugated system of the main chain, which moves in the conjugated system of the main chain. Specific examples include alkali metals (Li, Na, K, Cs), alkylammonium ions, and the like.

  The dopant in the present invention is a sulfo group or a sulfonate group that is covalently bonded in the polymer molecule, and is a p-type dopant. Such a polymer that exhibits conductivity without externally adding a dopant is called a self-doped polymer.

  Specifically, the polythiophenes in the present invention include a structural unit represented by the above formula (15), a structural unit represented by the above formula (16), a structural unit represented by the above formula (17), and the above formula. It preferably contains at least one structural unit selected from the group consisting of the structural unit represented by (18), the structural unit represented by the above formula (19), and the structural unit represented by the above formula (20). .

In the above formula (15), R ³ , M, n, and l are as defined in the above formula (2).

Moreover, in said formula (16), R < ³ >, n, l shows the same meaning as said formula (15). The structural unit represented by the above formula (16) represents the doping state of the structural unit represented by the above formula (15).

In the above formula (17), R ⁴ , Ar, M, and n are as defined in the above formula (3).

Moreover, in said formula (18), R < ⁴ >, Ar, n shows the same meaning as said formula (17). The structural unit represented by the above formula (18) represents the doping state of the structural unit represented by the above formula (17).

  In the above formula (19), M and n are as defined in the above formula (4).

  Moreover, in said formula (20), n shows the same meaning as said formula (19). The structural unit represented by the above formula (20) represents the doping state of the structural unit represented by the above formula (19).

  The weight average molecular weight of the polythiophenes of the present invention is not particularly limited, but is usually in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid, and preferably 1,000 to 200,000 for water-soluble conductive polymer applications. It is a range. From the viewpoint of removing unreacted monomers, low-molecular impurities and inorganic salts from the polymer, the range of 3.5 to 100,000 is more preferable.

  By making the polythiophene of the present invention into an aqueous solution, it becomes easy to mold into various applications as a water-soluble conductive polymer aqueous solution. Although the preparation method of water-soluble conductive polymer aqueous solution is not specifically limited, It is achieved by mixing and dissolving with water at room temperature or under heating (preferably 100 ° C. or less). At that time, a general mixing and dissolving operation using a stirrer chip or a stirring blade can be used, and as other methods, ultrasonic irradiation, homogenization treatment (for example, use of a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, etc.) May be performed. In the case of homogenizing treatment, it is preferable to carry out the treatment while cooling in order to prevent thermal degradation of the polymer.

  The concentration of the polythiophene in the water-soluble conductive polymer aqueous solution is not particularly limited, but is usually 50% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less from the viewpoint of viscosity.

  In the present invention, “water solubility sufficient for molding for various uses” means that the particle diameter (D50) measured with a particle size distribution analyzer is 10% by weight or less in a polymer aqueous solution prepared at room temperature or under heating. The water solubility is such that it is 20 nm or less and passes through a 0.05 μm filter.

Moreover, in this invention, favorable electroconductivity means the electroconductivity whose electrical conductivity (electrical conductivity) in a film state is 10 ^<-1 > S / cm or more.

  Next, the manufacturing method of polythiophene of this invention is demonstrated.

  The method for producing the polythiophene of the present invention is characterized by polymerizing the above-described thiophene compound of the present invention in the presence of an oxidizing agent in water or an alcohol solvent. As a thiophene compound, it can use 1 type or in combination of 2 or more types.

  The solvent used in the polymerization reaction is water or an alcohol solvent. The water may be pure water, and may be distilled water or ion exchange water. Examples of the alcohol solvent include alcohols such as methanol, ethanol, propanol, and butanol. These alcohol solvents may be used alone or in combination with water. In the present invention, water or methanol is preferable, and water is more preferable. In addition, the solvent may be replaced with an inert gas such as degassed or nitrogen.

  The amount of the solvent used in the polymerization reaction is not particularly limited as long as the thiophene compound of the present invention is dissolved, but is preferably 0.1 to 100 times by weight with respect to the charged amount of the thiophene compound of the present invention.

  The oxidizing agent used in the main polymerization reaction is not particularly limited as long as it allows oxidative polymerization by oxidative dehydrogenation reaction to proceed. For example, persulfuric acid, iron salt (III), hydrogen peroxide Permanganate, dichromate, cerium (IV) sulfate, oxygen and the like, and may be used alone or in admixture of two or more.

  Specific examples of the persulfuric acid include persulfuric acid, ammonium persulfate, sodium persulfate, and potassium persulfate.

Specific examples of the iron salt (III) include FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , iron perchlorate, iron (III) para-toluenesulfonate, and the like. These may use anhydrides or hydrates.

  Specific examples of permanganate include sodium permanganate, potassium permanganate, and magnesium permanganate.

  Specific examples of the dichromate include ammonium dichromate and potassium dichromate.

Among these oxidizing agents, iron salt (III) or a combined system of persulfate and iron salt (III) is preferable. As the iron salt (III), FeCl ₃ and Fe ₂ (SO ₄ ) ₃ are preferable.

  The amount of the oxidizing agent used in the polymerization reaction is not particularly limited, but is preferably in the range of 1 to 50 times mol, more preferably 1 with respect to the charged mole number of the thiophene compound of the present invention. It is the range of -20 times mole.

  When the oxidizing agent used in the polymerization reaction is, for example, an iron salt (III), the iron salt (III) is equal to or more than the mole of the charged mole of the thiophene compound of the present invention, and the iron concentration relative to the solvent The polymerization is preferably carried out so that the amount is 10% by weight or more. From the viewpoint of doping necessary for developing better conductivity, the iron concentration relative to the solvent is more preferably 20% by weight or more. The “iron concentration” here is a value represented by iron salt / (iron salt + water) × 100 (% by weight), and the iron salt is calculated as an anhydride.

  The pressure of the polymerization reaction may be normal pressure, reduced pressure, or increased pressure.

  The reaction atmosphere of the polymerization reaction may be in the air or in an inert gas such as nitrogen or argon. More preferably, it is in an inert gas.

  Although the reaction temperature of this polymerization reaction will not be specifically limited if it is the temperature which can oxidatively polymerize the thiophene compound of this invention, -10-150 degreeC is preferable, More preferably, it is the range of 20-100 degreeC.

  The reaction time of the main polymerization reaction is not particularly limited as long as the oxidation polymerization of the thiophene compound of the present invention is sufficiently advanced, but is preferably 0.5 hours to 200 hours, more preferably 0.5 to 80 hours. .

  The reaction method of the present polymerization reaction is not particularly limited. For example, the thiophene compound of the present invention may be made into an aqueous solution, and a solid or aqueous solution of an oxidant may be dropped into the solution at once or slowly. The aqueous solution of the thiophene compound of the present invention may be dropped at once or slowly into a solid or an aqueous solution.

  The purification method of the polythiophene of the present invention obtained by the present polymerization reaction is not particularly limited, and examples thereof include solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, and ion exchange resin treatment. It is done. Each may be performed alone or in combination.

  For example, a typical isolation and purification method for the polythiophenes of the present invention is as follows.

  First, the polymer aqueous solution after the polymerization reaction is added to a poor solvent such as acetone to precipitate the polymer, and then the polymer obtained by filtration under reduced pressure is washed with the poor solvent until the filtrate becomes colorless and transparent. When this polymer contains an Fe salt that is insoluble in water, it is preferably added once to an aqueous sodium hydroxide solution and converted to a Na salt type polymer that dissolves in water.

  Next, this is added to a poor solvent such as alcohol to precipitate the polymer, the alkali is removed, and the solid obtained by filtration under reduced pressure is washed with a poor solvent such as alcohol. Next, it is washed with a poor solvent such as acetone to obtain a Na salt type polymer.

  When the obtained Na salt type polymer is subsequently converted to an H type polymer, it is treated with a cation exchange resin. Examples of the treatment method include a method in which an aqueous solution of the obtained Na salt type polymer is passed through a column filled with a cation exchange resin, a body feed method in which the cation exchange resin is added to the aqueous solution, and the like. In this case, it is preferable to remove the cation exchange resin with a filter paper after the treatment. The aqueous solution thus obtained is roughly concentrated, added to a poor solvent such as acetone for precipitation, and the solid obtained by filtration under reduced pressure is thoroughly washed with the poor solvent and dried under reduced pressure to obtain an H-type polymer. .

  Further, when salts with various amines are formed, for example, an amine salt type polymer can be easily prepared by adding a stock solution of various amines or an aqueous solution thereof or a solution diluted with an appropriate solvent to an aqueous solution of H salt type polymer. Can be converted to For example, when treated with aqueous ammonia, the reaction solution is roughly concentrated, the aqueous solution is added to a poor solvent such as acetone to cause polymer precipitation, and then the solid obtained by vacuum filtration is washed with the poor solvent, Ammonium salt type polymer is obtained by drying under reduced pressure.

  In each step of the post-polymerization treatment, centrifugal sedimentation and homogenization treatment may be performed as necessary. Thereby, improvement of filtration efficiency can be aimed at. Further, when persulfate is used as the polymerization oxidant, ultrafiltration, dialysis, and cation / anion exchange resin mixing treatment are performed to remove inorganic salts.

A conductive film can be produced using the polythiophenes of the present invention. For example, a conductive film can be easily obtained by applying the above water-soluble conductive polymer aqueous solution to a substrate and drying. Examples of the substrate include glass, plastic, polyester, polyacrylate, polycarbonate, resist substrate, and the like. Examples of the coating method include a casting method, a dipping method, a barcode method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, and an inkjet printing method. It not particularly limited as film ^thickness, but preferably in the range of 10 -2 ~10 ² μm. Although it does not specifically limit as surface resistance value of the coating film obtained, The thing of the range of 1-10 < ⁹ > ohm / square is preferable.

  First, examples relating to the thiophene compound of the present invention are shown below, but the present invention is not construed as being limited to these examples. The analytical instruments and measurement methods used in this example are listed below.

[GC measurement]
Apparatus: manufactured by Shimadzu, GC-2014.

[NMR measurement]
Apparatus: VARIAN, Gemini-200.

  The thiophene compound according to the present invention can be synthesized by the following scheme. The starting material (5) was synthesized from a commercially available compound (7) by a known method used in the synthesis of 3,4-ethylenedioxythiophene.

合成例１ ２，３−ジヒドロ−チエノ［３，４−ｂ］［１，４］ジオキシン−２−イルメチルブロマイドの合成［下記式（９）で表される化合物］．
冷却管、温度計挿入管、攪拌羽根、窒素導入管を備えた５００ｍＬセパラブルフラスコに、３，４−ジメトキシチオフェン［上記化合物（７）に相当］２０．０ｇ（１３４．５ｍｍｏｌ）、３−ブロモ−１，２−プロパンジオール［上記化合物（８）に相当］２５．０ｇ（１６１．５ｍｍｏｌ）、パラトルエンスルホン酸・一水和物（５．３３ｇ、３０．９ｍｍｏｌ）、トルエン３４０ｍｌを仕込んだ。その後、窒素雰囲気下、９０℃で２０時間反応させた。得られた黒色液を放冷し、塩化メチレンで希釈し水洗した。得られた緑褐色の有機層を硫酸マグネシウムで乾燥し、ろ液を濃縮して黄褐色の液体を得た。引き続きシリカゲルクロマトグラフィー（ヘキサン／トルエン＝４／１）で精製し、濃縮後に１８．９ｇの下記式（９）で表される化合物が得られた（白色固体、収率５８％）。

Synthesis Example 1 Synthesis of 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl bromide [compound represented by the following formula (9)].
In a 500 mL separable flask equipped with a cooling tube, a thermometer insertion tube, a stirring blade and a nitrogen introducing tube, 20.0 g (134.5 mmol) of 3,4-dimethoxythiophene [corresponding to the above compound (7)], 3-bromo -1,2-propanediol [corresponding to the above compound (8)] 25.0 g (161.5 mmol), para-toluenesulfonic acid monohydrate (5.33 g, 30.9 mmol), and toluene 340 ml were charged. Then, it was made to react at 90 degreeC under nitrogen atmosphere for 20 hours. The resulting black liquid was allowed to cool, diluted with methylene chloride and washed with water. The resulting green-brown organic layer was dried over magnesium sulfate and the filtrate was concentrated to give a tan liquid. Subsequently, it was purified by silica gel chromatography (hexane / toluene = 4/1), and after concentration, 18.9 g of a compound represented by the following formula (9) was obtained (white solid, yield 58%).

実施例１ Ｎ−（２，３−ジヒドロ−チエノ［３，４−ｂ］［１，４］ジオキシン−２−イルメチル）−２−アミノエタンスルホン酸カリウムの合成［下記式（１０）で表される化合物］．
窒素中２００ｍＬの三つ口フラスコに、合成例１で得た上記式（９）で表される化合物３．００ｇ（１２．６ｍｍｏｌ）、２−アミノエタンスルホン酸［上記化合物（６）に相当］１．５７ｇ（１２．６ｍｍｏｌ）、炭酸カリウム（塩基）５．２１ｇ（３７．７ｍｍｏｌ）、Ｎ、Ｎ−ジメチルホルムアミド（極性溶媒）１３１ｍＬを仕込み、窒素雰囲気下１００℃で１７時間反応させた。ＴＬＣ分析及びＧＣ分析から上記式（９）で表される化合物の消失を確認した。放冷後、析出物をろ過し、ジメチルホルムアミドで洗浄した。得られたろ液を粗濃縮し、塩化メチレン／ヘキサン混合溶媒で洗浄し、減圧濾過して目的の下記式（１０）で表される化合物を淡赤色固体として３．０１ｇ得た（収率７４％）。この化合物は室温で１重量％以上の水溶性を示した。また、大気中での保存・取扱いが可能だった。

Example 1 Synthesis of potassium N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonate [represented by the following formula (10) Compound].
In a 200 mL three-necked flask in nitrogen, 3.00 g (12.6 mmol) of the compound represented by the above formula (9) obtained in Synthesis Example 1 and 2-aminoethanesulfonic acid [corresponding to the above compound (6)] 1.57 g (12.6 mmol), 5.21 g (37.7 mmol) of potassium carbonate (base) and 131 mL of N, N-dimethylformamide (polar solvent) were charged and reacted at 100 ° C. for 17 hours in a nitrogen atmosphere. The disappearance of the compound represented by the formula (9) was confirmed from TLC analysis and GC analysis. After allowing to cool, the precipitate was filtered and washed with dimethylformamide. The obtained filtrate was roughly concentrated, washed with a mixed solvent of methylene chloride / hexane, and filtered under reduced pressure to obtain 3.01 g of the target compound represented by the following formula (10) as a pale red solid (yield 74%). ). This compound showed a water solubility of 1% by weight or more at room temperature. It could also be stored and handled in the atmosphere.

^１Ｈ−ＮＭＲ（２００ＭＨｚ，Ｄ_２Ｏ，２，２，３，３−ｄ（４）−３−（トリメチルシリル）プロピオン酸ナトリウム）δ（ｐｐｍ）６．６７−６．５３（２Ｈ，ｍ）、４．５５−４．１５（４Ｈ、ｍ）、３．３１−２．８８（６Ｈ、ｍ）。

¹ H-NMR (200 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium) δ (ppm) 6.67-6.53 (2H, m), 4.55-4.15 (4H, m), 3.31-2.88 (6H, m).

¹³ C-NMR (50 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionate sodium) δ (ppm) 46.66, 50.50, 52.65, 69 .29, 75.55, 102.89, 103.18, 143.12, 143.31.

Example 2 Synthesis of sodium N-methyl-N- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethyl) -2-aminoethanesulfonate [Formula (11 ) ".
In a 500 mL four-neck separable flask equipped with a cooling tube, a thermometer insertion tube, a stirring blade, and a nitrogen introduction tube, 3.00 g (12.6 mmol) of the compound represented by the above formula (9) obtained in Synthesis Example 1 was obtained. ), 65% aqueous solution of sodium N-methyltauratesulfonate [corresponding to the above compound (6)] 3.42 g (13.8 mmol), potassium carbonate (base) 5.21 g (37.7 mmol), N, N-dimethyl Formamide (polar solvent) (130 mL) was charged and reacted at 90 ° C. for 22 hours under a nitrogen atmosphere. The disappearance of the compound represented by the formula (9) was confirmed from TLC analysis and GC analysis. After allowing to cool, the precipitate was filtered and washed with dimethylformamide. The obtained filtrate was roughly concentrated, washed with a mixed solvent of methylene chloride / hexane, and filtered under reduced pressure to obtain 3.90 g of the desired compound represented by the following formula (11) as a white solid (yield 99%). . This compound showed a water solubility of 1% by weight or more at room temperature. It could also be stored and handled in the atmosphere.

^１Ｈ−ＮＭＲ（２００ＭＨｚ，Ｄ_２Ｏ，２，２，３，３−ｄ（４）−３−（トリメチルシリル）プロピオン酸ナトリウム）δ（ｐｐｍ）６．５４−６．５２（２Ｈ，ｍ）、４．５０−４．４５（１Ｈ、ｍ）、３．１６−２．６２（８Ｈ、ｍ）、２．３７（３Ｈ、ｓ） ^１３Ｃ−ＮＭＲ（５０ＭＨｚ，Ｄ_２Ｏ，２，２，３，３−ｄ（４）−３−（トリメチルシリル）プロピオン酸ナトリウム）δ（ｐｐｍ）４４．２８、４９．９０、５４．４６、５８．１２、６９．５３、７４．０５、１０２．８６、１０３．３３、１４２．９４、１４３．２５。

¹ H-NMR (200 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium salt) δ (ppm) 6.54-6.52 (2H, m), 4.50-4.45 (1H, m), 3.16-2.62 (8H, m), 2.37 (3H, s) ¹³ C-NMR (50 MHz, D ₂ O, ₂ , ₂ , 3 , 3-d (4) -3- (trimethylsilyl) propionic acid sodium) δ (ppm) 44.28, 49.90, 54.46, 58.12, 69.53, 74.05, 102.86, 103 .33, 142.94, 143.25.

Example 3 Synthesis of sodium 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethanesulfonate [compound represented by the following formula (12)].
A 30 mL reaction tube was charged with 1.00 g (4.25 mmol) of the compound represented by the above formula (9) obtained in Synthesis Example 1, 1.07 g (8.51 mmol) of sodium sulfite, and 5 mL of water. The reaction was carried out at 90 ° C. for 36 hours. The disappearance of the compound represented by the formula (9) was confirmed from TLC analysis and GC analysis. After standing to cool, it was concentrated to dryness and washed with methylene chloride. Further, extraction and filtration with dimethylformamide was carried out, and the obtained filtrate was roughly concentrated. Subsequently, the obtained solid was washed with acetone and filtered under reduced pressure to obtain 1.02 g of the target compound represented by the following formula (12) as a white solid (yield 93%). This compound showed a water solubility of 1% by weight or more at room temperature. It could also be stored and handled in the atmosphere.

^１Ｈ−ＮＭＲ（２００ＭＨｚ，Ｄ_２Ｏ，２，２，３，３−ｄ（４）−３−（トリメチルシリル）プロピオン酸ナトリウム）δ（ｐｐｍ）６．５５（２Ｈ，ｓ）、４．３３−４．１０（３Ｈ，ｍ）、３．３１−３．２８（２Ｈ、ｍ）。

¹ H-NMR (200 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium salt) δ (ppm) 6.55 (2H, s), 4.33- 4.10 (3H, m), 3.31-3.28 (2H, m).

¹³ C-NMR (50 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium) δ (ppm) 53.78, 69.82, 72.84, 103 .07, 103.61, 142.59, 143.05.

Example 4 Synthesis of 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-hexanesulfonate sodium (59) [In the above formula (4) Corresponding compound].
(4-1) Synthesis of 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-hexene (58) [represented by the above formula (57) Compound].
In a 500 mL separable flask equipped with a cooling tube, a thermometer insertion tube, a stirring blade, and a nitrogen introduction tube, 20.0 g (97.0 GC) of a commercially available 3,4-dimethoxythiophene [compound represented by the above formula (7)]. %, 134.5 mmol) and 7-octene-1,2-diol [compound corresponding to the above formula (56)] 23.3 g (161.5 mmol), sodium para-toluenesulfonate monohydrate (5. 3 g, 30.9 mmol) and 400 mL of toluene were charged and reacted at 90 ° C. for 42 hours. After allowing to cool, it was transferred to a separatory funnel, washed with water and a saturated aqueous sodium hydrogen carbonate solution, and further extracted with dichloromethane. The obtained organic layer was dried over magnesium sulfate, and the filtrate was concentrated to obtain a pale yellow liquid. Subsequently, the product was purified by silica gel chromatography (eluent: hexane / toluene = 4/1) to obtain the target compound (58) as a pale yellow oil in 14.9 g (yield 49%).

^１Ｈ−ＮＭＲ（２００ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ）δ（ｐｐｍ）６．２９（２Ｈ，ｓ）、５．９１−５．７０（１Ｈ，ｍ）、５．０７−４．９２（２Ｈ，ｍ）、４．１５−４．０３（２Ｈ，ｍ）、３．８４（１Ｈ，ｄｄ， Ｊ＝１０．６Ｈｚ，８．４Ｈｚ）、２．１３−２．０３（２Ｈ，ｍ）、１．７０−１．４３（６Ｈ，ｍ）
^１３Ｃ−ＮＭＲ（５０ＭＨｚ，ＣＤＣｌ_３，ＴＭＳ）δ（ｐｐｍ）２４．４５、２８．６８、３０．４９、３３．４９、６８．３４、７３．６３、９９．１２、９９．１８、１１４．５４、１４１．５３、１４１．９９。

¹ H-NMR (200 MHz, CDCl ₃ , TMS) δ (ppm) 6.29 (2H, s), 5.91-5.70 (1H, m), 5.07-4.92 (2H, m) 4.15-4.03 (2H, m), 3.84 (1H, dd, J = 10.6 Hz, 8.4 Hz), 2.13 to 2.03 (2H, m), 1.70- 1.43 (6H, m)
¹³ C-NMR (50 MHz, CDCl ₃ , TMS) δ (ppm) 24.45, 28.68, 30.49, 33.49, 68.34, 73.63, 99.12, 99.18, 114. 54, 141.53, 141.99.

(4-2) Synthesis of 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) -1-hexanesulfonate sodium (59) [formula (4 The compound corresponding to
In a 500 mL separable flask equipped with a cooling tube, a thermometer insertion tube, a stirring blade, and a nitrogen introduction tube, 14.9 g (98.0 GC%, 65.1 mmol) of the compound represented by the above formula (58), azobisiso 140.8 mg of butyronitrile (0.98 mmol) and 150 mL of methanol were charged, dissolved at room temperature, and 10.2 g (97.6 mmol) of sodium bisulfite and 2.1 g (16.3 mmol) of sodium sulfite separately prepared there. An aqueous solution dissolved in 130 mL of water was added dropwise at room temperature. The cloudy reaction solution was reacted for 44 hours under reflux conditions. As the reaction progressed, an insoluble material once precipitated from the cloudy solution, and then redissolved to obtain a uniform solution. After allowing to cool, ethanol was added to the white solid obtained by concentration, and the mixture was stirred and extracted overnight at room temperature. Subsequently, insoluble matters were removed by filtration under reduced pressure, and the resulting colorless filtrate was concentrated to obtain 11.9 g (yield 56%) of the desired compound (59) as a white solid. This compound showed a water solubility of 1% by weight or more at room temperature. It could also be stored and handled in the atmosphere.

^１Ｈ−ＮＭＲ（２００ＭＨｚ，Ｄ_２Ｏ，２，２，３，３−ｄ（４）−３−（トリメチルシリル）プロピオン酸ナトリウム）δ（ｐｐｍ）６．３４（２Ｈ，ｓ）、４．２０−４．１４（２Ｈ，ｍ）、３．９０−３．８４（１Ｈ、ｍ）、２．８８（２Ｈ、ｔ、Ｊ＝８．２Ｈｚ）、１．７３−１．３７（１０Ｈ、ｍ）。

¹ H-NMR (200 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium) δ (ppm) 6.34 (2H, s), 4.20- 4.14 (2H, m), 3.90-3.84 (1H, m), 2.88 (2H, t, J = 8.2 Hz), 1.73-1.37 (10H, m).

¹³ C-NMR (50 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium salt) δ (ppm) 26.85, 27.07, 30.56, 53 .84, 70.92, 76.91, 102.51, 102.58, 143.66, 143.95.

  Next, examples relating to the polythiophenes of the present invention are shown below, but the present invention is not construed as being limited to these examples. The analytical instruments and measurement methods used in this example are listed below.

[UV-Vis-NIR analysis]
Apparatus: manufactured by SHIMADZU, UV-3100.

[GPC measurement]
Equipment: manufactured by Tosoh Corporation
Column: α-6000 + α-3000,
Detector: UV-8020.

[IR analysis]
Apparatus: System 2000 FT-IR, manufactured by PerkinElmer.
[Surface resistivity measurement]
Apparatus: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.
[Film thickness measurement]
Apparatus: DEKTAK XT manufactured by BRUKER.
[Particle size measurement]
Apparatus: Microtrac Nanotrac UPA-UT151 manufactured by Nikkiso Co., Ltd.

[Filter flow test]
Filter: Nippon Integris Optimizer V-47 disposable filter (hydrophilic), particle removal diameter 0.05 μm.

Example 5 Synthesis of polymer (23) [polymer containing a structural unit represented by the following formula (21) or the following formula (22)].
0.50 g (1.60 mmol) of the compound represented by the above formula (11) obtained in Example 2 was dissolved in 4 mL of water to obtain an aqueous monomer solution. Next, an aqueous monomer solution was slowly added to 2.06 g (12.7 mmol) of FeCl ₃ charged in advance in a 30 mL reaction tube equipped with a nitrogen line. Then, it stirred at 80 degreeC under nitrogen for 60 hours. The obtained black liquid was slowly added to 500 mL of acetone with stirring, and the resulting precipitate was collected by filtration under reduced pressure (0.39 g, black solid). When this solid was suspended in 5 mL of water and vigorously stirred, 24 g of 0.1N NaOH aqueous solution was added to obtain a dark blue liquid. Subsequently, this solution was slowly added to 150 mL of ethanol with stirring, and the resulting precipitate was collected by vacuum filtration. Subsequently, the aqueous polymer solution obtained by redissolving in 50 g of water was filtered under reduced pressure to remove iron hydroxide. The filtrate was concentrated and dried to obtain 354 mg (black solid) of the intended Na salt type polymer (23). As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 1). FIG. 12 shows the result of the IR analysis, and characteristic band absorption was observed around 3600-1800 cm ⁻¹ due to doping. Furthermore, the electrical conductivity of a film obtained by casting a 0.5% by weight aqueous solution of this polymer on an alkali-free glass plate was 3.7 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

実施例６ ポリマー（２６）の合成［下記式（２４）又は下記式（２５）で表される構造単位を含む重合体］．
実施例５で得られたＮａ塩型ポリマー（２３）１５０ｍｇを水で１５ｇに希釈溶解させた。この水溶液に、陽イオン交換樹脂アンバーライト（ＩＲ１２０Ｈ型）を添加して一晩攪拌した。減圧ろ過でアンバーライトを除去して濃青色Ｈ型ポリマー水溶液を得た。粗濃縮した水溶液に、モノマーの繰返し単位当りのモル数に対して過剰量の２．８重量％のアンモニア水を加え、窒素下に室温で一晩攪拌した。減圧ろ過で得たろ液を粗濃縮し、その水溶液をアセトン中に添加して得られた沈殿物を減圧ろ過で回収した。乾燥後、目的のＮＨ_４塩型の黒色ポリマー（２６）を９９ｍｇ（収率６６％）得た。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図２参照）。図１３にはそのＩＲ分析の結果を示したが、ドーピングに起因する３６００〜１８００ｃｍ^−１辺りに特徴的なバンド吸収を観測した。さらに、本ポリマーの０．５重量％水溶液を無アルカリガラス板にキャストして得た膜の導電率は４．９Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。ＧＰＣによる重量平均分子量（ポリスチレンスルホン酸換算、以下同じ）は１５，０００だった。

Example 6 Synthesis of polymer (26) [polymer containing a structural unit represented by the following formula (24) or the following formula (25)].
150 mg of the Na salt type polymer (23) obtained in Example 5 was diluted and dissolved in 15 g of water. To this aqueous solution, cation exchange resin amberlite (IR120H type) was added and stirred overnight. Amberlite was removed by vacuum filtration to obtain a dark blue H-type polymer aqueous solution. To the roughly concentrated aqueous solution, an excess amount of 2.8% by weight of ammonia water relative to the number of moles per repeating unit of the monomer was added, and the mixture was stirred overnight at room temperature under nitrogen. The filtrate obtained by vacuum filtration was roughly concentrated, the aqueous solution was added into acetone, and the resulting precipitate was collected by vacuum filtration. After drying, 99 mg (yield 66%) of the target NH ₄ salt type black polymer (26) was obtained. As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 2). FIG. 13 shows the results of the IR analysis, and characteristic band absorption was observed around 3600-1800 cm ⁻¹ due to doping. Furthermore, the conductivity of a film obtained by casting a 0.5 wt% aqueous solution of this polymer on an alkali-free glass plate was 4.9 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed. The weight average molecular weight (in terms of polystyrene sulfonic acid, hereinafter the same) by GPC was 15,000.

実施例７ ポリマー（２３）の合成［上記式（２１）又は上記式（２２）で表される構造単位を含む重合体］．
実施例５で重合温度を室温に変更した以外は、実施例５に準拠して行い、目的のＮａ塩型ポリマー（２３）を３７０ｍｇ（黒色固体）得た。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図３参照）。さらに、本ポリマーの０．５重量％水溶液を無アルカリガラス板にキャストして得た膜の導電率は２．９Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。

Example 7 Synthesis of Polymer (23) [Polymer Containing Structural Unit Represented by Formula (21) or Formula (22) above].
Except having changed the polymerization temperature into room temperature in Example 5, it carried out based on Example 5, and obtained 370 mg (black solid) of the target Na salt type polymer (23). As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 3). Furthermore, the conductivity of a film obtained by casting a 0.5 wt% aqueous solution of this polymer on an alkali-free glass plate was 2.9 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

Example 8 Synthesis of polymer (26) [polymer containing structural unit represented by (24) or (25) above].
157 mg of the Na salt polymer (23) obtained in Example 7 was diluted with water to 15 g and dissolved. To this aqueous solution, cation exchange resin amberlite (IR120H type) was added and stirred overnight. Amberlite was removed by filtration under reduced pressure to obtain a dark blue H-type polymer aqueous solution (particle size was below the detection limit by Microtrac. Further, a 20 nm filter was passed through). To the roughly concentrated aqueous solution, an excess amount of 2.8% by weight of ammonia water relative to the number of moles per repeating unit of the monomer was added, and the mixture was stirred overnight at room temperature under nitrogen. A precipitate obtained by adding a crude concentrated aqueous solution of the filtrate obtained by filtration under reduced pressure to acetone was collected by filtration under reduced pressure. After drying, 90 mg of the target NH ₄ salt type black polymer (26) was obtained. As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 4). Furthermore, the electrical conductivity of a film obtained by casting a 0.5% by weight aqueous solution of this polymer onto an alkali-free glass plate was 2.4 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed. The weight average molecular weight by GPC was 12,000.

Example 9 Synthesis of polymer (29) [polymer containing a structural unit represented by the following formula (27) or the following formula (28)].
1.01 g (3.18 mmol) of the compound represented by the above formula (10) obtained in Example 1 was dissolved in 14 mL of water to obtain an aqueous monomer solution. Next, an aqueous monomer solution was slowly added to 4.12 g (25.4 mmol) of FeCl ₃ previously charged in a 30 mL reaction tube equipped with a nitrogen line. Then, it stirred at 80 degreeC under nitrogen for 60 hours. The obtained black liquid was slowly added to 200 mL of acetone with stirring, and the resulting precipitate was collected by filtration under reduced pressure (0.96 g, black solid). When this solid was suspended in 10 mL of water and vigorously stirred, 48 g of 0.1N NaOH aqueous solution was added to obtain a dark blue liquid. Subsequently, this solution was slowly added to 700 mL of ethanol with stirring, and the resulting black precipitate was collected by vacuum filtration. Subsequently, the aqueous polymer solution obtained by redissolving in 100 g of water was filtered under reduced pressure to remove iron hydroxide. The filtrate was concentrated and dried to obtain 860 mg (black solid) of the desired Na salt type polymer (29). As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 5). Furthermore, the electrical conductivity of a film obtained by casting a 0.5 wt% aqueous solution of this polymer on an alkali-free glass plate was 2.1 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed. The weight average molecular weight by GPC was 23,000.

実施例１０ ポリマー（３２）の合成［下記式（３０）又は下記式（３１）で表される構造単位を含む重合体］．
実施例９で得られたＮａ塩型ポリマー（２９）１５０ｍｇを水で１５ｇに希釈溶解させた。この水溶液に、陽イオン交換樹脂アンバーライト（ＩＲ１２０Ｈ型）を添加して一晩攪拌した。減圧ろ過でアンバーライトを除去して濃青色Ｈ型ポリマー水溶液を得た。粗濃縮した水溶液に、モノマーの繰返し単位当りのモル数に対して過剰量の２．８重量％のアンモニア水を加え、窒素下に室温で一晩攪拌した。減圧ろ過で得たろ液を粗濃縮し、その水溶液をアセトン中に添加して得られた沈殿物を減圧ろ過で回収した。乾燥後、目的のＮＨ_４塩型の黒色ポリマー（３２）を１８ｍｇ得た。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図６参照）。さらに、本ポリマーの０．５重量％水溶液を無アルカリガラス板にキャストして得た膜の導電率は２．７Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。

Example 10 Synthesis of polymer (32) [polymer containing a structural unit represented by the following formula (30) or the following formula (31)].
150 mg of the Na salt type polymer (29) obtained in Example 9 was diluted and dissolved in 15 g of water. To this aqueous solution, cation exchange resin amberlite (IR120H type) was added and stirred overnight. Amberlite was removed by vacuum filtration to obtain a dark blue H-type polymer aqueous solution. To the roughly concentrated aqueous solution, an excess amount of 2.8% by weight of ammonia water relative to the number of moles per repeating unit of the monomer was added, and the mixture was stirred overnight at room temperature under nitrogen. The filtrate obtained by vacuum filtration was roughly concentrated, the aqueous solution was added into acetone, and the resulting precipitate was collected by vacuum filtration. After drying, 18 mg of the target NH ₄ salt type black polymer (32) was obtained. As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 6). Furthermore, the electrical conductivity of a film obtained by casting a 0.5% by weight aqueous solution of this polymer on an alkali-free glass plate was 2.7 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

実施例１１ ポリマー（３５）の合成［下記式（３３）又は下記式（３４）で表される構造単位を含む重合体）．
実施例４で得られた上記式（１２）で表される化合物１１００ｍｇ（２．２６ｍｍｏｌ、純度５３．１重量％：無機塩含有）を水１２ｍＬに溶解させてモノマーの水溶液を得た。次に、窒素ラインを備えた３０ｍＬ反応管中に予め仕込んでおいたＦｅＣｌ_３ ２．９３ｇ（１８．０ｍｍｏｌ）に対して、モノマーの水溶液をゆっくり添加した。その後、窒素下に８０℃で６０時間攪拌した。得られた黒色液を攪拌下にアセトン２００ｍＬにゆっくり添加し、得られた沈殿物を減圧ろ過により回収した（１．０６ｇ、黒色固体）。この固体を水５ｍＬに懸濁させて激しく攪拌しながら、０．１ＮのＮａＯＨ水溶液４８ｇ加えると、濃青色液が得られた。引き続き、攪拌下にエタノール７００ｍＬにこの液をゆっくり添加した。さらに、遠心沈降（３０００ｒｐｍ）させて上澄みを除去し、黒色沈殿物を減圧ろ過で回収した。引き続き、水１００ｇに再溶解して得たポリマー水溶液を減圧ろ過して水酸化鉄を除去した。ろ液を濃縮、乾燥して目的のＮａ塩型ポリマー（３５）を９６０ｍｇ（黒色固体）得た。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図７参照）。図１４にはＩＲ分析の結果を示したが、ドーピングに起因する３６００〜１８００ｃｍ^−１辺りに特徴的なバンド吸収を観測した。さらに、本ポリマーの０．５重量％水溶液を無アルカリガラス板にキャストして得た膜の導電率は０．４Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。ＧＰＣによる重量平均分子量は３６，０００だった。

Example 11 Synthesis of polymer (35) [polymer containing a structural unit represented by the following formula (33) or the following formula (34)].
1100 mg (2.26 mmol, purity 53.1 wt%: containing inorganic salt) of the compound represented by the above formula (12) obtained in Example 4 was dissolved in 12 mL of water to obtain an aqueous monomer solution. Next, an aqueous monomer solution was slowly added to 2.93 g (18.0 mmol) of FeCl ₃ previously charged in a 30 mL reaction tube equipped with a nitrogen line. Then, it stirred at 80 degreeC under nitrogen for 60 hours. The obtained black liquid was slowly added to 200 mL of acetone with stirring, and the resulting precipitate was collected by vacuum filtration (1.06 g, black solid). When this solid was suspended in 5 mL of water and vigorously stirred, 48 g of 0.1N NaOH aqueous solution was added to obtain a dark blue liquid. Subsequently, this solution was slowly added to 700 mL of ethanol with stirring. Further, the supernatant was removed by centrifugal sedimentation (3000 rpm), and the black precipitate was collected by vacuum filtration. Subsequently, the aqueous polymer solution obtained by redissolving in 100 g of water was filtered under reduced pressure to remove iron hydroxide. The filtrate was concentrated and dried to obtain 960 mg (black solid) of a desired Na salt type polymer (35). As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 7). FIG. 14 shows the result of IR analysis, and characteristic band absorption around 3600-1800 cm ⁻¹ due to doping was observed. Furthermore, the conductivity of a film obtained by casting a 0.5 wt% aqueous solution of this polymer on an alkali-free glass plate was 0.4 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed. The weight average molecular weight by GPC was 36,000.

実施例１２ ポリマー（３８）の合成［下記式（３６）又は下記式（３７）で表される構造単位を含む重合体）．
実施例１０で得られたＮａ塩型ポリマー（３５）１５０ｍｇを水で１５ｇに希釈溶解させた。この水溶液に、陽イオン交換樹脂アンバーライト（ＩＲ１２０Ｈ型）を添加して一晩攪拌した。減圧ろ過でアンバーライトを除去して濃青色Ｈ型ポリマー水溶液を得た（粒径はマイクロトラックで検出限界以下だった。また２０ｎｍフィルターを通液した。）。粗濃縮液をアセトン中に添加して得られた沈殿物を減圧ろ過で回収した。乾燥後、目的のＨ型の黒色ポリマー（３８）を３８ｍｇ得た。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図８参照）。図１５にそのＩＲ分析の結果を示したが、ドーピングに起因する３６００〜１８００ｃｍ^−１辺りに特徴的なバンド吸収を観測した。さらに、本ポリマーの０．５重量％水溶液を無アルカリガラス板にキャストして得た膜の導電率は２．１Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。

Example 12 Synthesis of polymer (38) [polymer containing a structural unit represented by the following formula (36) or the following formula (37)].
150 mg of the Na salt polymer (35) obtained in Example 10 was diluted and dissolved in 15 g with water. To this aqueous solution, cation exchange resin amberlite (IR120H type) was added and stirred overnight. Amberlite was removed by filtration under reduced pressure to obtain a dark blue H-type polymer aqueous solution (particle size was below the detection limit by Microtrac. Further, a 20 nm filter was passed through). The precipitate obtained by adding the crude concentrate to acetone was collected by vacuum filtration. After drying, 38 mg of the desired H-type black polymer (38) was obtained. As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 8). FIG. 15 shows the results of the IR analysis, and characteristic band absorption was observed around 3600-1800 cm ⁻¹ due to doping. Furthermore, the electrical conductivity of a film obtained by casting a 0.5 wt% aqueous solution of this polymer on an alkali-free glass plate was 2.1 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

実施例１３ ポリマー（６２）の合成［下記式（６０）又は下記式（６１）で表される構造単位を含む重合体）．
実施例４で得られた上記式（５９）で表される化合物０．５０ｇ（１．５２ｍｍｏｌ）を水５．９ｍＬに溶解させてモノマーの水溶液を得た。次に、窒素ラインを備えた３０ｍＬ反応管中に予め仕込んでおいたＦｅＣｌ_３ １．９８ｇ（１２．２ｍｍｏｌ）に対して、モノマーの水溶液をゆっくり添加した。その後、窒素下に８０℃で４８時間攪拌した。得られた黒色液を攪拌下にアセトン１５０ｍＬにゆっくり添加し、得られた沈殿物を減圧ろ過により回収した（０．４５ｇ、黒色固体）。この固体を水５ｍＬに懸濁させて激しく攪拌しながら、０．１ＮのＮａＯＨ水溶液６０ｇ加えると、濃青色液が得られた。ろ過により不溶物を除去した後、攪拌下にエタノール３５０ｍＬにこの液をゆっくり添加した。さらに、遠心沈降（３０００ｒｐｍ）させて上澄みを除去し、黒色沈殿物を減圧ろ過で回収した。引き続き、水１００ｇに再溶解して得たポリマー水溶液を減圧ろ過して水酸化鉄を除去した。ろ液を濃縮、乾燥して目的のＮａ塩型ポリマーを０．２７ｇ（黒色固体）得た。このポリマーの重量平均分子量は１１，０００だった。このポリマーを水５０ｇに希釈溶解させ、陽イオン交換樹脂アンバーライト（ＩＲ１２０Ｈ型）を添加して一晩攪拌した。減圧ろ過でアンバーライトを除去して濃青色Ｈ型ポリマー水溶液を得た。粗濃縮液をアセトン中に添加して得られた沈殿物を減圧ろ過で回収した。乾燥後、目的のＨ型の黒色ポリマー（６２）を０．１９ｇ得た。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図９参照）。図１６にそのＩＲ分析の結果を示したが、ドーピングに起因する３６００〜１８００ｃｍ^−１辺りに特徴的なバンド吸収を観測した。さらに、本ポリマーの０．５重量％水溶液を無アルカリガラス板にキャストして得た膜の導電率は３１Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。

Example 13 Synthesis of polymer (62) [polymer containing structural unit represented by formula (60) or formula (61) below].
The compound represented by the above formula (59) obtained in Example 4 (0.50 g, 1.52 mmol) was dissolved in 5.9 mL of water to obtain an aqueous monomer solution. Next, an aqueous monomer solution was slowly added to 1.98 g (12.2 mmol) of FeCl ₃ previously charged in a 30 mL reaction tube equipped with a nitrogen line. Then, it stirred at 80 degreeC under nitrogen for 48 hours. The obtained black liquid was slowly added to 150 mL of acetone with stirring, and the resulting precipitate was collected by filtration under reduced pressure (0.45 g, black solid). When this solid was suspended in 5 mL of water and vigorously stirred, 60 g of a 0.1N NaOH aqueous solution was added to obtain a dark blue liquid. After removing insoluble materials by filtration, this solution was slowly added to 350 mL of ethanol with stirring. Further, the supernatant was removed by centrifugal sedimentation (3000 rpm), and the black precipitate was collected by vacuum filtration. Subsequently, the aqueous polymer solution obtained by redissolving in 100 g of water was filtered under reduced pressure to remove iron hydroxide. The filtrate was concentrated and dried to obtain 0.27 g (black solid) of the target Na salt type polymer. The weight average molecular weight of this polymer was 11,000. This polymer was diluted and dissolved in 50 g of water, cation exchange resin amberlite (IR120H type) was added, and the mixture was stirred overnight. Amberlite was removed by vacuum filtration to obtain a dark blue H-type polymer aqueous solution. The precipitate obtained by adding the crude concentrate to acetone was collected by vacuum filtration. After drying, 0.19 g of the target H-type black polymer (62) was obtained. As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 9). FIG. 16 shows the result of the IR analysis, and characteristic band absorption was observed around 3600-1800 cm ⁻¹ due to doping. Furthermore, the conductivity of a film obtained by casting a 0.5% by weight aqueous solution of this polymer on an alkali-free glass plate was 31 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

実施例１４ ポリマー（６２）の合成［上記式（６０）又は上記式（６１）で表される構造単位を含む重合体）．
３０ｍＬ反応管に、実施例４で得た化合物（５９）を１０００ｍｇ（２．８５ｍｍｏｌ）、水１４．８ｇを仕込んでモノマーの水溶液を得た。次にＦｅＣｌ_３ ２３１ｍｇ（１．４３ｍｍｏｌ）を添加し、３０分間室温で攪拌した。得られた褐色水溶液に別途調製したＮａ_２Ｓ_２Ｏ_８ １３５９ｍｇ（５．７１ｍｍｏｌ）を水８ｍＬに溶かして調製した酸化剤水溶液をゆっくり添加した。添加とともに濃青色液に変化し、系が固化した。室温で２４時間重合させた後、アセトン７００ｍＬに重合液を注ぎ、ポリマーを析出させた。得られたポリマーをろ過して１．４３ｇの淡緑色固体を得た。引き続き、水で全量２００ｇの水溶液を調製し、陽イオン交換樹脂アンバーライト（ＩＲ１２０Ｈ型）を添加して一晩攪拌した。減圧ろ過でアンバーライトを除去して濃青色Ｈ型ポリマー水溶液を得た。さらに透析（透析膜：Ｓｐｅｃｔｒａ／Ｐｏｒ ＭＷＣＯ＝３５００）により無機塩を除去した。精製した水溶液を濃縮乾燥して目的のＨ型ポリマー（６２）を黒色固体として４６０ｍｇ得た（収率４６％）。このポリマーを１００ｐｐｍ含む水溶液のＵＶ−Ｖｉｓ−ＮＩＲ分析を行った結果、ドーピングに起因する長波長吸収が観測された（図１０参照）。図１７にそのＩＲ分析の結果を示したが、ドーピングに起因する３６００〜１８００ｃｍ^−１辺りに特徴的なバンド吸収を観測した。本ポリマーの０．５重量％水溶液を調製し、無アルカリガラス板にキャストして得た膜の導電率は１０Ｓ／ｃｍだった。０．５重量％水溶液におけるポリマーの粒径（Ｄ５０）は検出限界（０．８ｎｍ）以下であり、また０．０５μｍフィルターを通液した。

Example 14 Synthesis of polymer (62) [polymer containing structural unit represented by formula (60) or formula (61) above].
A 30 mL reaction tube was charged with 1000 mg (2.85 mmol) of the compound (59) obtained in Example 4 and 14.8 g of water to obtain an aqueous monomer solution. Next, 231 mg (1.43 mmol) of FeCl ₃ was added and stirred at room temperature for 30 minutes. An aqueous oxidizing agent solution prepared by dissolving 1359 mg (5.71 mmol) of Na ₂ S ₂ O ₈ separately prepared in 8 mL of water was slowly added to the obtained brown aqueous solution. With the addition, it changed to a dark blue liquid and the system solidified. After polymerization at room temperature for 24 hours, the polymerization solution was poured into 700 mL of acetone to precipitate a polymer. The obtained polymer was filtered to obtain 1.43 g of a light green solid. Subsequently, an aqueous solution having a total amount of 200 g was prepared with water, cation exchange resin amberlite (IR120H type) was added, and the mixture was stirred overnight. Amberlite was removed by vacuum filtration to obtain a dark blue H-type polymer aqueous solution. Further, inorganic salts were removed by dialysis (dialysis membrane: Spectra / Por MWCO = 3500). The purified aqueous solution was concentrated and dried to obtain 460 mg of the intended H-type polymer (62) as a black solid (yield 46%). As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 10). FIG. 17 shows the result of the IR analysis, and characteristic band absorption around 3600-1800 cm ⁻¹ due to doping was observed. The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 10 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

Example 15 Synthesis of polymer (23) [polymer containing structural unit represented by formula (21) or formula (22) above].
0.50 g (1.60 mmol) of the compound represented by the above formula (11) obtained in Example 2 was charged into a 30 mL reaction tube equipped with a nitrogen line, and 0.8 mL of water was added and dissolved. An aqueous monomer solution was obtained. Next, an aqueous monomer solution was slowly added to 5.2 g (12.7 mmol) of a commercially available 40 wt% FeCl ₃ aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). The iron concentration relative to the solvent (water) in the charged solution was 35% by weight. The aqueous solution was then stirred at 80 ° C. for 24 hours under nitrogen. The obtained black liquid was slowly added to 500 mL of acetone with stirring, and the resulting precipitate was collected by filtration under reduced pressure (black solid 0.26 g). The solid was suspended in 5 mL of water and 100 g of 0.1 N aqueous NaOH was added with vigorous stirring to obtain a dark blue liquid. Subsequently, this solution was slowly added to 600 mL of ethanol with stirring, and the resulting precipitate was collected by vacuum filtration. Subsequently, the aqueous polymer solution obtained by redissolving in 50 g of water was filtered under reduced pressure to remove iron hydroxide. The filtrate was concentrated and dried to obtain 0.24 g (black solid) of a desired Na salt type polymer (23).

  As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 11, solid line). The conductivity of a film obtained by casting a 0.5% by weight aqueous solution of this polymer onto an alkali-free glass plate was 14.0 S / cm. Furthermore, the particle size (D50) of the polymer in the 0.5 wt% aqueous solution was not more than the detection limit (0.8 nm), and a 0.05 μm filter was passed through.

Example 16 Synthesis of polymer (23) [polymer containing structural unit represented by formula (21) or formula (22) above].
In the method of Example 15, the 40 wt% FeCl ₃ aqueous solution was changed from 5.2 g (12.7 mmol) to 3.9 g (9.5 mmol), and the monomer aqueous solution was adjusted to match the monomer concentration with respect to Example 15 with that of Example 15. The procedure described in Example 15 was followed except that the amount of water in preparing the was increased from 0.8 g to 2.3 g. Here, the iron concentration with respect to the solvent (water) in the charged solution was 25% by weight. As a result, Na salt type polymer (23) was obtained as 0.22 g of a black solid.

  As a result of UV-Vis-NIR analysis of an aqueous solution containing 100 ppm of this polymer, long wavelength absorption due to doping was observed (see FIG. 11, broken line). The conductivity of a film obtained by casting a 0.5% by weight aqueous solution of this polymer onto an alkali-free glass plate was 8.0 S / cm. Furthermore, the particle size (D50) of the polymer in the 0.5 wt% aqueous solution was not more than the detection limit (0.8 nm), and a 0.05 μm filter was passed through.

Comparative Example 1 Synthesis of polymer (45) [polymer containing a structural unit represented by the following formula (43) or the following formula (44)].
The compound was synthesized according to the following scheme with reference to Macromolecules, 1995, pages 975-984.

（１Ａ）３−アリルチオフェン（４０）の合成．
３００ｍＬの４つ口フラスコに、３−ブロモチオフェン（３９）２０．１ｇ（１２３．４ｍｍｏｌ）、ジエチルエーテル（脱水）８０ｍＬを仕込み、−７８℃に冷却した。その後、１．６Ｍのノルマル−ブチルリチウム９２ｍＬ（１４７．２ｍｍｏｌ）を滴下ロートで１時間かけてゆっくりと滴下した。同温度で２時間熟成させた後、アリルブロミド１５．０ｇ（１２３．６ｍｍｏｌ）をシリンジでゆっくり添加し、同温度で５時間熟成させた。０℃まで昇温した後、飽和塩化アンモウム水溶液１００ｍＬでクエンチして、有機層を抽出した。さらに、水と飽和食塩水で洗浄し、分液して得られた有機層を硫酸マグネシウムで乾燥した。ろ過して得た有機層を５０℃、＜２０Ｔｏｒｒで濃縮すると、褐色油状物が３．２ｇ得られた。これをＫｕｇｅｌｒｏｈｒ蒸留（７０−１２５℃、２５Ｔｏｒｒ）で精製し、無色透明油状物として目的の化合物（４０）を２．５ｇ（収率１６％）
（１Ｂ）３−（３−チエニル）プロパン−１−スルホン酸ナトリウム（４１）の合成． １００ｍＬのナスフラスコに、上記（１Ａ）で合成した３−アリルチオフェン（４０）３ｇ（２４．２ｍｍｏｌ）をメタノール３７ｍＬに溶解させた後、アゾビスイソブチロニトリル０．０５ｇ（０．３０ｍｍｏｌ）を添加した。さらに、ＮａＨＳＯ_３ ２．９ｇ（２７．９ｍｍｏｌ）とＮａ_２Ｓ_２Ｏ_３ ０．５９ｇ（４．６０ｍｍｏｌ）を水２４ｍＬに溶かした液を室温下で加えた後、８０℃で一晩攪拌した。その間に反応液は懸濁液から均一溶液に変化した。冷却後、濃縮すると白色固体が７．３０ｇ得られた。引き続き、ジエチルエーテル３５ｍＬで洗浄し、ろ過して得られた白色固体を乾燥して５．１４ｇの粗体を得た。さらに、エタノール１００ｍＬでその固体を抽出洗浄し、減圧ろ過で得たろ液を濃縮乾燥すると、目的の化合物（４１）が２．２１ｇの白色結晶として得られた（収率５２％）。

(1A) Synthesis of 3-allylthiophene (40).
A 300 mL four-necked flask was charged with 20.1 g (123.4 mmol) of 3-bromothiophene (39) and 80 mL of diethyl ether (dehydrated), and cooled to -78 ° C. Thereafter, 92 mL (147.2 mmol) of 1.6 M normal-butyllithium was slowly added dropwise over 1 hour with a dropping funnel. After aging for 2 hours at the same temperature, 15.0 g (123.6 mmol) of allyl bromide was slowly added with a syringe and aged for 5 hours at the same temperature. After heating up to 0 degreeC, it quenched with 100 mL of saturated ammonium chloride aqueous solution, and the organic layer was extracted. Furthermore, it wash | cleaned with water and a saturated salt solution, and the organic layer obtained by liquid-separating was dried with magnesium sulfate. The organic layer obtained by filtration was concentrated at 50 ° C. and <20 Torr, yielding 3.2 g of a brown oil. This was purified by Kugelrohr distillation (70-125 ° C., 25 Torr) to obtain 2.5 g of the desired compound (40) as a colorless transparent oil (yield 16%).
(1B) Synthesis of sodium 3- (3-thienyl) propane-1-sulfonate (41). In a 100 mL eggplant flask, 3 g (24.2 mmol) of 3-allylthiophene (40) synthesized in (1A) above was dissolved in 37 mL of methanol, and 0.05 g (0.30 mmol) of azobisisobutyronitrile was then added. Added. Furthermore, a solution prepared by dissolving 2.9 g (27.9 mmol) of NaHSO ₃ and 0.59 g (4.60 mmol) of Na ₂ S ₂ O _{3 in} 24 mL of water was added at room temperature, followed by stirring at 80 ° C. overnight. Meanwhile, the reaction solution changed from a suspension to a homogeneous solution. After cooling, it was concentrated to obtain 7.30 g of a white solid. Subsequently, the white solid obtained by washing with 35 mL of diethyl ether and filtering was dried to obtain 5.14 g of a crude product. Furthermore, the solid was extracted and washed with 100 mL of ethanol, and the filtrate obtained by filtration under reduced pressure was concentrated and dried to obtain the target compound (41) as 2.21 g of white crystals (yield 52%).

(1C) Synthesis of polymer (42).
FeCl ₃ 2.40 g (14 .8 mmol) was added slowly. Thereafter, polymerization was carried out at room temperature for 22 hours. Meanwhile, the reaction solution became a black solution with a greenish color. After the polymerization, the polymer was precipitated by slowly pouring into 150 mL of acetone with stirring. After thoroughly washing with acetone, 0.17 g of black polymer was obtained. The polymer was suspended in 2 g of water and 1.5 mL of 1N NaOH aqueous solution was added with vigorous stirring. The suspension changed from a suspension to a reddish brown homogeneous solution by adding NaOH aqueous solution. Subsequently, the polymer was precipitated by pouring into 20 mL of methanol. After filtration and drying, 0.12 g of the target Na salt type polymer (42) was obtained as a black solid (yield 14%).

(1D) Synthesis of polymer (45).
In a 30 mL reaction tube, 122 mg of the polymer (42) obtained in (1C) above was suspended in 15 mL of water and stirred for 2 hours. Thereafter, filtration under reduced pressure gave a dark red solution. 2 g of cation exchange resin (Lewatit S100 H type) was added to the solution and stirred overnight. The filtrate obtained by filtration was concentrated and dried to obtain the desired acid type polymer (45) as a black solid in 76 mg (yield 63%). The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 0.06 S / cm. The particle size (D50) of the polymer in a 0.5 wt% aqueous solution was 10 nm.

Comparative Example 2 Synthesis of polymer (51) [polymer containing a structural unit represented by the following formula (49) or the following formula (50)].
The compound was synthesized according to the following scheme with reference to Japanese Patent No. 3182239.

（２Ａ）１、３−ジヒドロイソチアナフテン（４７）の合成．
２Ｌのセパラブルフラスコに、化合物（４６）を１０．０ｇ（３８．０ｍｍｏｌ）、テトラ−ノルマル−ブチルアンモニウム硫化水素を２５．７ｇ（７５．８ｍｍｏｌ）、クロロホルム９５０ｍＬを仕込んだ。窒素バブリング後、別途調製した硫化ナトリウム９水和物１３．９ｇ（５７．８ｍｍｏｌ）、炭酸水素ナトリウム６．４ｇ（７５．６ｍｍｏｌ）を水７００ｍＬに溶解した水溶液を室温で１．５時間かけて滴下し、さらに１時間熟成させた。反応後、有機層を分液し、さらに水２５０ｍＬで２回洗浄した。硫酸マグネシウムで乾燥した有機層を濃縮すると白色固体と油状物の混合物が得られた。引き続き、シリカゲルカラムクロマトグラフィ精製（溶離液：ヘキサン／クロロホルム＝４／１）により、目的の化合物（４７）を２．８ｇの無色透明油状物として得た（収率５５％）。

(2A) Synthesis of 1,3-dihydroisothianaphthene (47).
In a 2 L separable flask, 10.0 g (38.0 mmol) of the compound (46), 25.7 g (75.8 mmol) of tetra-normal-butylammonium hydrogen sulfide, and 950 mL of chloroform were charged. After nitrogen bubbling, an aqueous solution prepared by dissolving 13.9 g (57.8 mmol) of sodium sulfide nonahydrate and 6.4 g (75.6 mmol) of sodium hydrogen carbonate in 700 mL of water was added dropwise at room temperature over 1.5 hours. And further aged for 1 hour. After the reaction, the organic layer was separated and further washed twice with 250 mL of water. The organic layer dried over magnesium sulfate was concentrated to give a mixture of white solid and oil. Subsequently, silica gel column chromatography purification (eluent: hexane / chloroform = 4/1) gave 2.8 g of the objective compound (47) as a colorless transparent oil (yield 55%).

(2B) Synthesis of polymer (48).
A 30-mL reaction tube was charged with 3.0 g of 30% fuming sulfuric acid and cooled in an ice bath. Further, the compound (47) obtained in (2A) above was dropped into the fuming sulfuric acid with a syringe under a nitrogen stream. After stirring at room temperature for 1 hour, the mixture was reacted at 70 ° C. for 1 hour. The reaction solution changed from brown to dark blue immediately after dropping. After the reaction, it was added dropwise to 200 mL of a 0.1N NaOH-methanol solution to precipitate the polymer. The polymer was precipitated by centrifugation (3000 rpm), and after drying, 1.4 g of black powder was obtained. Subsequently, it was dissolved in 100 g of water, and inorganic salts were removed by dialysis (dialysis membrane: Spectra / Por MWCO = 0.1-0.5K). The purified aqueous solution was concentrated and dried to obtain 1.1 g of the objective Na salt type polymer (48) as a black solid (yield 64%).

(2C) Synthesis of polymer (51).
A 30 mL reaction tube was charged with 160 mg of the Na salt polymer (48) obtained in (2B) and 23 g of water to prepare an aqueous solution. Thereto was added 2.5 g of a cation exchange resin (Lewatit S100) that had been acidified in advance, and the mixture was stirred overnight. The ion exchange resin was removed by filtration, and the obtained filtrate was concentrated and dried to obtain 140 mg of the desired acid type polymer (51) as a black solid (yield 89%). The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 0.1 S / cm. The particle size (D50) of the polymer in a 0.5 wt% aqueous solution was 6 nm.

Comparative Example 3 Synthesis of polymer (56) [polymer containing a structure represented by the following formula (54) or the following formula (55)].
The compounds were synthesized according to the following scheme with reference to Journal of Electroanalytical Chemistry, 1998, pages 217-226 and Chemistry of Materials, 2009, pages 1815-1821.

（３Ａ）化合物（５３）の合成．
１００ｍＬナスフラスコに、市販の化合物（５２）１．８３ｇ、トルエン４５ｍＬ、６０％ＮａＨを０．３２ｇ（１３．２ｍｍｏｌ）を仕込み、還流条件下で１時間反応させた。トルエン１２ｍＬに溶解した１，４−ブタンスルトン１．４６ｇ（１０．７ｍｍｏｌ）を還流下に滴下した。さらに２時間熟成させた後、室温まで冷却し、アセトン２００ｍＬに添加して、ゼリー状固体を沈殿させた。ろ紙でろ過後、減圧乾燥して目的の化合物（５３）を淡褐色固体として２．０ｇ得た（収率５６％）。

(3A) Synthesis of compound (53).
A 100 mL eggplant flask was charged with 1.83 g of a commercially available compound (52), 45 mL of toluene, and 0.32 g (13.2 mmol) of 60% NaH, and reacted under reflux conditions for 1 hour. 1.46 g (10.7 mmol) of 1,4-butane sultone dissolved in 12 mL of toluene was added dropwise under reflux. After further aging for 2 hours, the mixture was cooled to room temperature and added to 200 mL of acetone to precipitate a jelly-like solid. After filtration through filter paper, drying under reduced pressure gave 2.0 g of the target compound (53) as a light brown solid (yield 56%).

(3B) Synthesis of polymer (56).
A 50 mL Schlenk tube was charged with 0.81 g (2.44 mmol) of the compound (53) obtained in (3A) above and 12 mL of water to obtain an aqueous monomer solution. An aqueous oxidizing agent solution prepared by dissolving 1.16 g (4.86 mmol) of Na ₂ S ₂ O ₈ and 0.02 g (0.10 mmol) of FeCl ₃ separately in 12 mL of water was slowly added to the aqueous monomer solution. After polymerization at room temperature for 16 hours, the polymerization solution was poured into 160 mL of acetone to precipitate a polymer. The obtained slurry was completely precipitated by centrifugal sedimentation (3000 rpm), and 1.4 g of a black solid was obtained. Subsequently, an aqueous solution having a total amount of 80 g was prepared with water, and inorganic salts were removed by dialysis (dialysis membrane: Spectra / Por MWCO = 0.1-0.5K). The purified aqueous solution was concentrated and dried to obtain 553 mg of the objective Na salt type polymer (56) as a black solid (yield 69%). The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 0.3 S / cm. The particle size (D50) of the polymer in the 0.5 wt% aqueous solution was below the detection limit (0.8 nm).

  According to the production method of the present invention, the novel thiophene compound of the present invention can be easily provided.

  The thiophene compound of the present invention is an antistatic agent, a solid electrolyte of a solid electrolytic capacitor, a conductive paint, a conductive film, an electrochromic element, a solar cell, an organic EL, a capacitor, a monomer of a conductive polymer polythiophene used for a chemical sensor. Available as In particular, since the thiophene compound of the present invention has a sulfo group having water solubility and a role as an intramolecular dopant, the resulting polymer is expected to be a water-soluble self-doping conductive polymer. .

  Further, according to the present invention, novel polythiophenes having both good conductivity and sufficient water solubility for molding are provided. The novel polythiophenes can be applied to antistatic agents, capacitor solid electrolytes, conductive paints, electrochromic elements, transparent electrodes, transparent conductive films, chemical sensors, actuators, and the like. In particular, since it is water-soluble, damage to the fat-soluble resist is small, and peeling cleaning is easy. Therefore, it is expected to be used as an antistatic film forming material for suppressing resist charging during electron beam lithography. . In addition, since the polymer particle diameter is very small when an aqueous solution is used, for example, the permeability to the etched aluminum foil subjected to the chemical conversion treatment of the aluminum solid electrolytic capacitor is improved, and the covering area by the conductive polymer is improved. Improvements in capacitor performance such as increased capacitance and lower ESR are expected.

Claims (11)

The thiophene compound of Claim 1 represented by following formula (2) or (4 ) .

[In the above formula (2), R ³ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ —. Represents SO ₃ M. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. l represents an integer of 1 to 6; n represents an integer of 0 to 12. ]

[In the above formula (4), M represents an alkali metal selected from the group consisting of a hydrogen atom, Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. n represents 6 . ] And the following formula (5) represented by a thiophene compound and a compound represented by the following formula (6), in an aprotic polar solvent, according to claim 1 which comprises reacting in the presence of a base A method for producing a thiophene compound.

[In the above formula (5), Y represents tosylate, mesylate, triflate, chloride, bromide, or iodide, and n represents an integer of 0-12. ]

[In the above formula (6), R ¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —X—SO ₃ M. Represent. X represents a C1-C6 alkylene group which may have a substituent. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. ] A thiophene compound represented by the following formula (5) is reacted with a sulfite in an aqueous solvent to obtain a thiophene compound represented by the formula (4) according to claim 1. Method.

[In the above formula (5), Y represents tosylate, mesylate, triflate, chloride, bromide, or iodide, and n represents 6 . ] The thiophene compound represented by the following formula (5a) is reacted with bisulfite in the presence of a radical initiator in a mixed solvent of water and alcohol, and the thiophene represented by the formula (4) according to claim 1. The manufacturing method of the thiophene compound characterized by obtaining a compound.

[In the above formula (5a), n represents 4 . ] Following formula (15)

[In the above formula (15), R ³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ —. Represents SO ₃ M. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. l represents an integer of 1 to 6; n represents an integer of 0 to 12. ]
A structural unit represented by the following formula (16):

[In said formula (16), R < ³ >, n, l shows the same significance as said formula (15). ]
In a structural unit represented by the lower following formula (19)

[In the above formula (19), M represents an alkali metal selected from the group consisting of a hydrogen atom, Li, Na, and K, NH (R ² ) ₃ or HNC ₅ H ₅ . R ² each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. n represents 6 .
]
And a structural unit represented by the following formula (20)

[In the above formula (20), n is as defined in the above formula (19). ]
Containing Mupo Li thiophenes at least one structural unit selected from the group consisting of a structural unit represented in. The polythiophene according to claim 5 , wherein the weight average molecular weight of the polythiophene is in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid. Water or alcohol solvent, in the presence of an oxidizing agent, method for producing the polythiophenes according to claim 5, characterized in that the polymerization of a thiophene compound of claim 1. The method for producing a polythiophene according to claim 7 , wherein the oxidizing agent is iron salt (III) or a combined system of persulfate and iron salt (III). A water-soluble conductive polymer aqueous solution comprising an aqueous solution of the polythiophenes according to claim 5 . A method for producing a conductive film, wherein the aqueous solution according to claim 9 is applied to a substrate and dried. Use of the aqueous solution according to claim 9 for a conductive film.

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