JP2012056991A - Conductive thienopyrazine copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive thienopyrazine copolymer composition being useful as a material for a transparent conductive film exhibiting high solubility, being excellent in processability and having high conductivity and transparency.SOLUTION: The conductive thienopyrazine copolymer composition contains a thienopyrazine copolymer having repeating units represented by chemical formula (I) and a dopant. [In the formula (I), Rand Reach represents a hydrogen atom, an aryl group or a 1-20C alkyl group; W and Y each represents a divalent thiophene ring; n and m are 0-1, and R, R, Rand Reach represents a side chain group represented by chemical formula (II): R-[X-(CH)]-(X)- (in the formula (II), Rrepresents a hydrogen atom or a 1-20C alkyl group, Xand Xare same or different and each represents an oxygen atom or a sulfur atom, [X-(CH)] represents a repeating unit in which Xand -(CH)- are same or different in every repeating unit, a is 1-20, b is 0-20 and c is 0-1)].

Description

  The present invention relates to a conductive thienopyrazine copolymer composition useful as a material for a transparent conductive film.

  The transparent conductive film is used for coating of a transparent electrode such as a liquid crystal display, a plasma display, an electroluminescence display, an electrochromic display, a solar battery and a touch panel, or a substrate such as an electromagnetic shielding material.

  The most widely used transparent conductive film is a deposited film of indium-tin composite oxide (ITO). Since this ITO vapor deposition film is a rare metal indium, which is the main raw material for ITO, the raw material cost is high due to the rising prices and stable supply due to resource problems, and further high temperature treatment is required in the film formation process. The film formation cost is also high. Moreover, the transparent conductive film formed with inorganic oxides, such as ITO, is easy to crack by the distortion of a base material, Therefore, it is a thing which electroconductivity falls easily.

  In order to improve these problems, vigorous development of ITO substitute materials has been carried out. Especially when assuming next-generation electronic device applications such as flexible displays, the organic substance replacement technology using conductive polymers is that the conductive polymers are lightweight and easy to process, have high degree of freedom in shape, and exhibit flexibility. This is a promising means because of its various advantages.

  Many conductive polymers obtained by polymerizing thiophene, pyrrole, aniline, and derivatives thereof have been disclosed. For example, a conductive composition obtained by dispersing an ion pair of a polyanion doped with a π-conjugated conductive polymer and a basic organic compound in a solvent containing an organic solvent, and a transparent conductive film using the same (Patent Document 1). It is known that a metal-like property is expressed by injecting a dopant into such a π-conjugated polymer. Among them, in particular, a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (PEDOT / PSS) is one of conjugated polymers having high conductivity, and partly as an aqueous dispersion Although it has been put into practical use (Non-patent Document 1), its solubility in organic solvents is low and its processability is poor. In addition, PEDOT / PSS has been studied as a material for conductive thin films useful for solar cells and light emitting devices (Non-Patent Documents 2, 3, and 4), but PEDOT / PSS is mainly water-dispersed. There are problems in the process of use, such as aggregation of dispersed particles and the use of water, which causes a reduction in device performance in the electronics field.

  Since no material satisfying such a sufficient performance has been obtained, a material that is highly soluble in a solvent and excellent in workability, and that can form a transparent conductive film having high conductivity and transparency. Longed for.

JP 2007-254730 A

Synthetic Metals, 2003, 135-136, p.115-117 Solar Energy Materials & Solar Cells, 2006, Volume 90, pp. 3520-3530 Organic Electronics, 2002, Volume 3, pages 111-118 Journal of Electron Spectroscopy and Related Phenomena, 2001, Vol. 121, p. 1-17

  The present invention has been made in order to solve the above-described problems, and exhibits high solubility, excellent workability, and is useful as a material for a transparent conductive film having high conductivity and transparency. An object is to provide a conductive thienopyrazine copolymer composition.

［式（Ｉ）中、Ｒ^１及びＲ^２はそれぞれ水素原子、アリール基、又は置換基を有してもよい炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基、Ｗ及びＹはそれぞれ置換基を有してもよい２価のチオフェン環、ｎ及びｍは０〜１、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ下記化学式（II）
Ｒ^７−[Ｘ^１−(ＣＨ_２)_ａ]_ｂ−(Ｘ^２)_ｃ− ・・・（II）
（式（II）中、Ｒ^７は水素原子、又は炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基、Ｘ^１及びＸ^２は同一又は異なる酸素原子若しくは硫黄原子、[Ｘ^１−(ＣＨ_２)_ａ]は繰り返し単位毎にＸ^１と−(ＣＨ_２)_ａ−とが同一又は異なり、ａは１〜２０、ｂは０〜２０、ｃは０〜１）で示される側鎖基］で表される繰り返し単位を有するチエノピラジン共重合体と、ドーパントとを含有していることを特徴とする。 The conductive thienopyrazine copolymer composition according to claim 1, which has been made to achieve the above object, has the following chemical formula (I):

[In Formula (I), R ¹ and R ² are each a hydrogen atom, an aryl group, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, W and Y Are each a divalent thiophene ring optionally having a substituent, n and m are 0 to 1, and R ³ , R ⁴ , R ⁵ and R ⁶ are each represented by the following chemical formula (II)
^{R 7 - [X 1 - (} CH 2) a] b - (X 2) c - ··· (II)
(In formula (II), R ⁷ is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, X ¹ and X ² are the same or different oxygen atoms or sulfur atoms, [X ¹ - (CH _{2) a]} for each repeating unit ^{X 1} and - (CH _{2) a} - the same or different, side a is 1 to 20, b is 0 to 20, c is represented by 0 or 1) A thienopyrazine copolymer having a repeating unit represented by a chain group] and a dopant.

The conductive thienopyrazine copolymer composition according to claim 2 is the composition according to claim 1, wherein R ³ and R ⁶ are each a hydrogen atom in the chemical formula (I), To do.

The conductive thienopyrazine copolymer composition according to claim 3 is the composition according to claim 1, wherein, in the chemical formula (I), R ³ and R ⁶ are a hydrogen atom, R ⁴ and R ⁵ , respectively. Is a side chain group in which at least one of b and c in the chemical formula (II) is a positive number, or b = c = 0 and R ⁷ is the alkyl group.

  The transparent conductive film according to claim 4 is characterized in that the conductive thienopyrazine copolymer composition according to claim 1 is cured on a substrate.

  The conductive thienopyrazine copolymer composition of the present invention can be used as a material for a transparent conductive film excellent in transparency and conductivity. Since this conductive thienopyrazine copolymer composition is highly stable and exhibits high solubility in a solvent, it is excellent in processability as a transparent conductive film and can easily form a transparent conductive film.

  The transparent conductive film of the present invention can be produced in large quantities using a conductive thienopyrazine copolymer composition having high solubility and workability, without requiring complicated steps and suppressing raw material costs and film formation costs. And can exhibit excellent transparency and conductivity.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The conductive thienopyrazine copolymer composition of the present invention contains a thienopyrazine copolymer having a repeating unit represented by the chemical formula (I), a dopant, and a solvent.

In the chemical formula (II) represented by R ³ , R ⁴ , R ⁵ and R ^{6 in the} chemical formula (I), the repeating unit of [X ^1- (CH ₂ ) _a ] is such that X ¹ is only an oxygen atom or Only a sulfur atom may be sufficient and both atoms may be contained regularly or irregularly.

In the chemical formulas (I) and (II), examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ⁷ include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, isopropyl group, isobutyl group, sec-butyl group , 2-methylhexyl group, 2-ethylhexyl group, cyclohexyl group, cyclopropyl group and the like.

In the chemical formula (I), examples of the aryl group represented by R ¹ and R ² include a phenyl group and a naphthyl group.

  Examples of the divalent thiophene ring represented by W and Y in the chemical formula (I) include thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3 -Hexylthiophene, 3-heptylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-hexadecylthiophene, 3- (2-ethylexyl) thiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-propoxythiophene, 3 -Butoxythiophene, 3-pentyloxythiophene, 3-hexyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-hexadecyloxythiophene, 3- [2- (2-methoxyethoxy) ethoxy] thiophene 3- {2- [2- (2-methoxyethoxy) ethoxy] ethoxy} thiophene, [2- (2-ethoxyethoxy) ethoxy] ethoxy} thiophene, 3- [2- (2-methoxyethoxy) ethoxy] methylthiophene 3,4-ethylenedioxythiophene and the like.

  These alkyl groups and divalent thiophene rings may have a substituent. Examples of the substituent include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group. Examples of the substituents listed above include groups.

  The listed alkyl group, aryl group, divalent thiophene ring and substituent are specific examples and are not limited thereto.

  Specific examples of the thienopyrazine copolymer represented by the chemical formula (I) are shown as chemical formulas (1) to (26) below, but the present invention is not limited thereto.

  The bond arrangement of the thienopyrazine copolymer structure represented by the chemical formula (I) and the chemical formulas (1) to (26) may be a head-tail repeating structure arranged in a positional order. The head repeating structure and / or the tail-tail repeating structure may be arranged. The number average molecular weight of these thienopyrazine copolymers is preferably in the range of 1,000 to 2,000,00, and more preferably in the range of 2,000 to 500,000.

  The conductive thienopyrazine copolymer composition of the present invention can be obtained by doping which is to impart conductivity by allowing a dopant to act on the thienopyrazine copolymer represented by the chemical formula (I).

  The dopant is not particularly limited as long as the conductivity can be improved by oxidizing and reducing the thienopyrazine copolymer, and various known electron donating substances and electron withdrawing substances can be appropriately selected and used. . Among these, it is preferable to use an electron-withdrawing substance as a dopant. The electron-withdrawing substance functions as a counter anion for the thienopyrazine copolymer represented by the chemical formula (I) that is oxidized and has a positive charge.

Electron withdrawing materials used as dopants are specifically Cl ₂ , Br ₂ , I ₂ , ICl, IBr, and IF as halogens, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , IF as Lewis acids, BBr _3, and SO _{3, HF} as a proton _{acid, HCl, HNO 3, H 2} SO 4, HClO 4, FSO 3 H, CISO 3 H, CF 3 SO 3 H, p- toluenesulfonic acid, naphthalenesulfonic acid, camphor As transition metal compounds such as sulfonic acid, dodecylbenzene sulfonic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, other various organic acids, and amino acids, FeCl ₃ , Fe (ClO ₄ ) ₃ , TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF _{5 , NbCl 5, TaCl 5, MoF} 5, MoCl 5, UF ^Cl, and LnCl ₃ as (Ln = La, Ce, Pr , Nd, lanthanoid Sm, etc.), electrolyte anions ^{_{-, Br -, I -,}} ClO 4 -, AlCl 4 -, FeCl 4 -, SnC l5 -, PF ^{_{6 -, AsF 6 -, SbF}} 6 -, BF 4 -, NO 3 -, SO 4 2-, p- toluenesulfonate anion, a naphthalenesulfonic acid anion, camphorsulfonic acid anion, dodecylbenzenesulfonic acid anion, and various other Examples include organic acid anions such as FSO ₂ OOSO ₂ F, AgClO ₄ , H ₂ IrCl ₆ , La (NO ₃ ) ₃ .6H ₂ O, and the like. The electron withdrawing substance is not limited to these.

  The dopant contained in this invention may be used individually by 1 type, or may be used in combination of 2 or more type. The addition method of this dopant is not specifically limited, For example, a desired dopant can be added suitably after superposition | polymerization.

  There is no restriction | limiting in particular in the content rate of the dopant in the electroconductive thienopyrazine copolymer composition of this invention, Although it can select arbitrarily, It is preferable in it being the range of 1-50 mass%. The content can be appropriately adjusted by an ion exchange resin, various filtration methods, or the like in the step of preparing the conductive thienopyrazine copolymer composition.

  The conductive thienopyrazine copolymer composition of the present invention may contain a solvent in addition to the essential components of the thienopyrazine copolymer and the dopant. The solvent is not particularly limited as long as it can disperse and dissolve the thienopyrazine copolymer composition. For example, water, alcohols such as methanol, ethanol, butanol and octanol, and ketones such as acetone and methyl ethyl ketone. , Ethers such as diisopropyl ether and tetrahydrofuran, cellosorob such as 1,2-ethanediol, aliphatic hydrocarbons such as hexane, heptane and octane, aromatic hydrocarbons such as toluene and xylene, chlorobenzene, dichlorobenzene, And halogenated compounds such as chloroform. The thienopyrazine copolymer shows high solubility in these solvents.

  Furthermore, the conductive thienopyrazine copolymer composition may contain any additive as necessary in addition to the thienopyrazine copolymer, dopant, and solvent components, and the timing of addition thereof is also arbitrary. You can choose. The additive can be appropriately selected from known additives, for example, ultraviolet absorbers, antioxidants, deterioration inhibitors, polymerization inhibitors, surface modifiers, defoamers, plasticizers, Examples include antibacterial agents. These additives may be used individually by 1 type, or may be used in combination of 2 or more types.

  The method for producing the thienopyrazine copolymer containing the repeating unit represented by the chemical formula (I) is not particularly limited, and may be any synthetic method such as a cross-coupling polymerization method, a chemical oxidation polymerization method, or an electrolytic polymerization method. For example, Journal of Polymer Science Part A: Polymer Chemistry, 2002, Vol. 40, pp. 2360-2372, Macromolecules, 2006, Vol. 39 , P.8712-8719, Macromolecules, 2008, Vol. 41, p.6952-6959, as shown in the following chemical reaction formula (A), a metal complex exists. Below, a copolymer can be obtained by the method of cross coupling.

In the chemical reaction formula (A), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , W, and Y are the same as those in the chemical formulas (I) and (II), and L And L ′ are leaving groups that are the same or different halogen atoms, Q and Q ′ are the same or different, and —MgCl, —MgBr, —MgI, —ZnCl, —ZnBr, —ZnI, and —Sn (Aky) ₃ is a group selected from ₃ ; In the formula, m to n may be integers. Here, Aky represents an alkyl group.

  The thienopyrazine copolymer obtained by the above cross-coupling polymerization method is in a neutral state, and becomes a conductive thienopyrazine copolymer composition having conductivity through a doping step.

  The conductive thienopyrazine copolymer composition of the present invention thus obtained is useful as a material for a transparent conductive film having excellent transparency and electrical conductivity. After applying this neutral state thienopyrazine copolymer to a transparent substrate, the above-mentioned doping operation may be performed to form a transparent conductive film as a conductive thienopyrazine copolymer composition, or a thienopyrazine copolymer and A transparent conductive film may be formed by applying a conductive thienopyrazine copolymer composition containing a dopant to a transparent substrate and forming a film.

  There is no restriction | limiting in particular as a transparent base material, About the material, a shape, thickness, etc., it can select arbitrarily from well-known things, For example, glass and a resin material are mentioned.

  The resin material can be arbitrarily selected from known materials, such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, polyethersulfone resin, polycarbonate resin, polystyrene resin. , Polyimide resin, polyetherimide resin, polyvinyl acetate resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polyacrylonitrile resin, polyolefin resin, polyamide resin, polybutadiene resin, acetic acid Examples thereof include cellulose, cellulose nitrate, and acrylonitrile-butadiene-styrene copolymer resin. These may be used alone or in combination of two or more.

  The thickness of the transparent conductive film obtained by using the conductive thienopyrazine copolymer composition of the present invention is not particularly limited and can be arbitrarily selected. Considering adhesiveness and the like, it is preferably 0.01 to 10 μm, for example.

  The electrical resistance value of the transparent conductive film is preferably 10,000 Ω / □ or less, more preferably 1000 Ω / □ or less, as the surface resistivity. The surface resistivity can be measured based on, for example, JIS-K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

  The visible light transmittance of the transparent conductive film is preferably 70% or more, more preferably 80% or more, and most preferably 90% or more.

  The method for forming the transparent conductive film obtained using the conductive thienopyrazine copolymer composition of the present invention is not particularly limited and can be appropriately selected from known methods. For example, a coating method or a printing method. Etc. are preferable. These may be a single method, or a method using two or more in combination.

  There is no restriction | limiting in particular as a coating method, It can select suitably from well-known methods, for example, a spin coat method, a roll coat method, a bar coat method, a dip coating method, a gravure coat method, a curtain coat method, a die coat method , Spray coating method, doctor coating method and the like. The printing method is not particularly limited and can be appropriately selected from known methods. Examples include screen printing methods, spray printing methods, ink jet printing methods, letterpress printing methods, intaglio printing methods, lithographic printing methods, and the like. be able to.

  The transparent conductive film may be formed on the entire surface of the transparent substrate, or may be partially formed such as forming an electrode or a wiring pattern.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  Synthesis of thienopyrazine copolymer used in the conductive thienopyrazine copolymer composition of the present invention is shown in Synthesis Examples 1 to 5, and the conductive thienopyrazine copolymer composition containing the obtained thienopyrazine copolymer, and the same Examples 1 to 15 show examples in which a thin film was prepared using a transparent conductive film.

  The number average molecular weight (Mn) of the obtained thienopyrazine copolymer and the dispersity (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), are measured using a differential refractometer as a detector. It was determined by gel permeation chromatography (GPC) measurement using tetrahydrofuran as an eluent and calculated as a conversion value using a calibration curve prepared with standard polystyrene.

  GPC measurement: A column in which two TSK-gel SuperMultipore HZ-M (trade name: manufactured by Tosoh Corporation) are connected in series is used, the column temperature is 40 ° C., and the eluent flow rate is 0.35 mL / min. Measured under conditions.

温度計、ジムロート、三方コック、滴下漏斗を付した内容量５０ｍｌの３つ口フラスコに窒素雰囲気下、５，７−ビス〔５’−ブロモジチエン−２−イル−チエノ〔３，４−ｂ〕ピラジン〕１４３ｍｇ、２，５−ジデシルオキシ−１，４−ビス(４，４，５，５−テトラメチル−１，３，２−ジ−オキサボロレート)２００ｍｇ、テトラキス(トリフェニルホスフィン)パラジウム０価３．６ｍｇ、及びトリオクチルメチルアンモニウムクロリド（Ａｌｉｑｕａｔ ３３６）（２滴）を入れ、脱水トルエン１５ｍｌに溶解させた。そこへ、２Ｍの炭酸ナトリウム溶液１３ｍｌを投入し、反応液をオイルバスで加熱して内温９０℃で７２時間攪拌した。その後、ブロモベンゼン４９ｍｇを投入し、内温９０℃で１時間攪拌した。フェニルボロン酸６３ｍｇを添加し、反応終了後、室温まで冷やし、多量のメタノールに注ぎ込んだ。ろ過し、水、メタノール、アセトンで洗浄した。得られたものを５０℃で減圧乾燥し、ポリ〔２，５−ジデシロキシ−１，４−フェニレン−５，７−ジチエン−２−イル−チエノ〔３，４−ｂ〕ピラジン〕を８９ｍｇ取得した。得られたチエノピラジン共重合体１のＭｎは２５００、分散度は２．５であった。 <Synthesis Example 1>
Of poly [2,5-dideroxy-1,4-phenylene-5,7-dithien-2-yl-thieno [3,4-b] pyrazine] (thienopyrazine copolymer 1) represented by the following chemical formula (III) Composition

5,7-bis [5'-bromodithien-2-yl-thieno [3,4-b] pyrazine in a nitrogen atmosphere in a 50 ml three-necked flask equipped with a thermometer, Dimroth, three-way cock, and dropping funnel 143 mg, 2,5-didecyloxy-1,4-bis (4,4,5,5-tetramethyl-1,3,2-di-oxaborolate) 200 mg, tetrakis (triphenylphosphine) palladium 0 valent 3 .6 mg and trioctylmethylammonium chloride (Aliquat 336) (2 drops) were added and dissolved in 15 ml of dehydrated toluene. Thereto, 13 ml of 2M sodium carbonate solution was added, and the reaction solution was heated in an oil bath and stirred at an internal temperature of 90 ° C. for 72 hours. Thereafter, 49 mg of bromobenzene was added and stirred at an internal temperature of 90 ° C. for 1 hour. After adding 63 mg of phenylboronic acid, the reaction mixture was cooled to room temperature and poured into a large amount of methanol. Filtered and washed with water, methanol, acetone. The obtained product was dried at 50 ° C. under reduced pressure to obtain 89 mg of poly [2,5-didecyloxy-1,4-phenylene-5,7-dithien-2-yl-thieno [3,4-b] pyrazine]. . The obtained thienopyrazine copolymer 1 had an Mn of 2500 and a dispersity of 2.5.

温度計、ジムロート、三方コック、滴下漏斗を付した内容量５０ｍｌの３つ口フラスコに窒素雰囲気下、５，７−ビス（５’−ブロモ−３−ヘキシルチオフェン−２−イル）チエノ〔３，４−ｂ〕ピラジン１９５ｍｇ、２，５−ジデシルオキシ−１，４−ビス(４，４，５，５−テトラメチル−１，３，２−ジ−オキサボロレート)２００ｍｇ、テトラキス(トリフェニルホスフィン)パラジウム３．６ｍｇ、及びＡｌｉｑｕａｔ３３６（２滴）を入れ、脱水トルエン１５ｍｌに溶解させた。そこへ、２Ｍの炭酸ナトリウム溶液１３ｍｌを投入し、反応液をオイルバスで加熱して内温９０℃で７２時間攪拌した。その後、ブロモベンゼン４９ｍｇを投入し内温９０℃で１時間攪拌した。フェニルボロン酸６３ｍｇを添加し、反応終了後、室温まで冷やし、多量のメタノールに注ぎ込んだ。ろ過し、水、メタノール、アセトンで洗浄した。得られたものを５０℃で減圧乾燥し、ポリ〔２，５−ジデシロキシ−１，４−フェニレン−ａｌｔ−５，７−ビス（３−ヘキシルチオフェン−２−イル）−チエノ〔３，４−ｂ〕ピラジン〕を９２ｍｇ取得した。得られたチエノピラジン共重合体２のＭｎは８２００、分散度は１．８であった。 <Synthesis Example 2>
Poly [2,5-dideroxy-1,4-phenylene-alt-5,7-bis (3-hexylthiophen-2-yl) -thieno [3,4-b] pyrazine] represented by the following chemical formula (IV) Synthesis of (thienopyrazine copolymer 2)

5,7-bis (5′-bromo-3-hexylthiophen-2-yl) thieno [3, under a nitrogen atmosphere, in a three-necked flask with an internal volume of 50 ml equipped with a thermometer, Dimroth, three-way cock, and dropping funnel 4-b] pyrazine 195 mg, 2,5-didecyloxy-1,4-bis (4,4,5,5-tetramethyl-1,3,2-di-oxaborolate) 200 mg, tetrakis (triphenylphosphine) Palladium 3.6 mg and Aliquat 336 (2 drops) were added and dissolved in 15 ml of dehydrated toluene. Thereto, 13 ml of 2M sodium carbonate solution was added, and the reaction solution was heated in an oil bath and stirred at an internal temperature of 90 ° C. for 72 hours. Thereafter, 49 mg of bromobenzene was added and stirred at an internal temperature of 90 ° C. for 1 hour. After adding 63 mg of phenylboronic acid, the reaction mixture was cooled to room temperature and poured into a large amount of methanol. Filtered and washed with water, methanol, acetone. The obtained product was dried at 50 ° C. under reduced pressure to obtain poly [2,5-didecyloxy-1,4-phenylene-alt-5,7-bis (3-hexylthiophen-2-yl) -thieno [3,4 b] Pyrazine] was obtained in an amount of 92 mg. Mn of the obtained thienopyrazine copolymer 2 was 8200, and dispersion degree was 1.8.

温度計、ジムロート、三方コック、滴下漏斗を付した内容量５０ｍｌの３つ口フラスコに窒素雰囲気下、２，３−ジデシルオキシ−５，７−ビス〔５’−ブロモジチエン−２−イル−チエノ〔３，４−ｂ〕ピラジン〕２４７ｍｇ、２，５−ジデシロキシ−１，４−ビス(４，４，５，５−テトラメチル−１，３，２−ジ−オキサボロレート)２００ｍｇ、テトラキス(トリフェニルホスフィン)パラジウム０価３．６ｍｇ、及びＡｌｉｑｕａｔ３３６（２滴）を入れ、脱水トルエン１５ｍｌに溶解させた。そこへ、２Ｍの炭酸ナトリウム溶液１３ｍｌを投入し、反応液をオイルバスで加熱して内温９０℃で７２時間攪拌した。その後、ブロモベンゼン４９ｍｇを投入し内温９０℃で１時間攪拌した。フェニルボロン酸６３ｍｇを添加し、反応終了後、室温まで冷やし、多量のメタノールに注ぎ込んだ。ろ過し、水、メタノール、アセトンで洗浄した。得られたものを５０℃で減圧乾燥し、ポリ〔２，５−ジドデシル−１，４−フェニレン−ａｌｔ−２，３−ジドデシル−５，７−ジチエン−２−イル〕チエノ〔３，４−ｂ〕ピラジン〕を９０ｍｇ取得した。得られたチエノピラジン共重合体３のＭｎは１５０００、分散度は３．７であった。 <Synthesis Example 3>
Poly [2,5-didecyloxy-1,4-phenylene-alt-2,3-didodecyl-5,7-dithien-2-yl] thieno [3,4-b] pyrazine represented by the following chemical formula (V) Synthesis of thienopyrazine copolymer 3)

2,3-didecyloxy-5,7-bis [5′-bromodithien-2-yl-thieno [3] under a nitrogen atmosphere in a 50 ml three-necked flask equipped with a thermometer, Dimroth, three-way cock, and dropping funnel , 4-b] pyrazine] 247 mg, 2,5-didecyloxy-1,4-bis (4,4,5,5-tetramethyl-1,3,2-di-oxaborolate) 200 mg, tetrakis (triphenyl) Phosphine) palladium 0-valent 3.6 mg and Aliquat 336 (2 drops) were added and dissolved in 15 ml of dehydrated toluene. Thereto, 13 ml of 2M sodium carbonate solution was added, and the reaction solution was heated in an oil bath and stirred at an internal temperature of 90 ° C. for 72 hours. Thereafter, 49 mg of bromobenzene was added and stirred at an internal temperature of 90 ° C. for 1 hour. After adding 63 mg of phenylboronic acid, the reaction mixture was cooled to room temperature and poured into a large amount of methanol. Filtered and washed with water, methanol, acetone. The obtained product was dried at 50 ° C. under reduced pressure, and poly [2,5-didodecyl-1,4-phenylene-alt-2,3-didodecyl-5,7-dithien-2-yl] thieno [3,4- 90 mg of [b] pyrazine] was obtained. The obtained thienopyrazine copolymer 3 had an Mn of 15000 and a dispersity of 3.7.

温度計、ジムロート、三方コック、滴下漏斗を付した内容量５０ｍｌの３つ口フラスコに窒素雰囲気下、５，７−ビス〔５’−ブロモジチエン−２−イル−チエノ〔３，４−ｂ〕ピラジン〕１４３ｍｇ、２，５−ヘキシルデシルオキシ−１，４−ビス(４，４，５，５−テトラメチル−１，３，２−ジ−オキサボロレート)２２６ｍｇ、テトラキス(トリフェニルホスフィン)パラジウム０価３．６ｍｇ、及びＡｌｉｑｕａｔ３３６（２滴）を入れ、脱水トルエン１５ｍｌに溶解させた。そこへ、２Ｍの炭酸ナトリウム溶液１３ｍｌを投入し、反応液をオイルバスで加熱して内温９０℃で７２時間攪拌した。その後、ブロモベンゼン４９ｍｇを投入し内温９０℃で１時間攪拌した。フェニルボロン酸６３ｍｇを添加し、反応終了後、室温まで冷やし、多量のメタノールに注ぎ込んだ。ろ過し、水、メタノール、アセトンで洗浄した。得られたものを５０℃で減圧乾燥し、ポリ〔２，５−ジヘキシルデシルオキシ−１，４−フェニレン−５，７−ジチエン−２−イル−チエノ〔３，４−ｂ〕ピラジン〕を９６ｍｇ取得した。得られたチエノピラジン共重合体４のＭｎは２５００、分散度は２．５であった。 <Synthesis Example 4>
Poly [2,5-dihexyldecyloxy-1,4-phenylene-5,7-dithien-2-yl-thieno [3,4-b] pyrazine] (thienopyrazine copolymer 4) represented by the following chemical formula (VI) ) Synthesis

5,7-bis [5'-bromodithien-2-yl-thieno [3,4-b] pyrazine in a nitrogen atmosphere in a 50 ml three-necked flask equipped with a thermometer, Dimroth, three-way cock, and dropping funnel 143 mg, 2,5-hexyldecyloxy-1,4-bis (4,4,5,5-tetramethyl-1,3,2-di-oxaborolate) 226 mg, tetrakis (triphenylphosphine) palladium 0 A value of 3.6 mg and Aliquat 336 (2 drops) were added and dissolved in 15 ml of dehydrated toluene. Thereto, 13 ml of 2M sodium carbonate solution was added, and the reaction solution was heated in an oil bath and stirred at an internal temperature of 90 ° C. for 72 hours. Thereafter, 49 mg of bromobenzene was added and stirred at an internal temperature of 90 ° C. for 1 hour. After adding 63 mg of phenylboronic acid, the reaction mixture was cooled to room temperature and poured into a large amount of methanol. Filtered and washed with water, methanol, acetone. The resulting product was dried under reduced pressure at 50 ° C., and 96 mg of poly [2,5-dihexyldecyloxy-1,4-phenylene-5,7-dithien-2-yl-thieno [3,4-b] pyrazine] was obtained. I got it. Mn of the obtained thienopyrazine copolymer 4 was 2500, and the dispersity was 2.5.

温度計、ジムロート、三方コック、滴下漏斗を付した内容量５０ｍｌの３つ口フラスコに窒素雰囲気下、５，７−ジブロモチエノ〔３，４−ｂ〕ピラジン９１ｍｇ、２，５−ジデシロキシ−１，４−ビス(４，４，５，５−テトラメチル−１，３，２−ジ−オキサボロレート)２００ｍｇ、テトラキス(トリフェニルホスフィン)パラジウム０価３．６ｍｇ、及びＡｌｉｑｕａｔ３３６（２滴）を入れ、脱水トルエン１５ｍｌに溶解させた。そこへ、２Ｍの炭酸ナトリウム溶液１３ｍｌを投入し、反応液をオイルバスで加熱して内温９０℃で７２時間攪拌した。その後、ブロモベンゼン４９ｍｇを投入し内温９０℃で１時間攪拌した。フェニルボロン酸６３ｍｇを添加し、反応終了後、室温まで冷やし、多量のメタノールに注ぎ込んだ。ろ過し、水、メタノール、アセトンで洗浄した。得られたものを５０℃で減圧乾燥し、ポリ〔２，５−ジデシロキシ−１，４−フェニレン−ａｌｔ−５，７−（チエノ〔３，４−ｂ〕ピラジン）を９７ｍｇ取得した。得られたチエノピラジン共重合体５のＭｎは３８００、分散度は１．２であった。 <Synthesis Example 5>
Synthesis of poly [2,5-didecyloxy-1,4-phenylene-alt-5,7- (thieno [3,4-b] pyrazine) (thienopyrazine copolymer 5) represented by the following chemical formula (VII)

Under a nitrogen atmosphere, a 5-ml three-necked flask equipped with a thermometer, Dimroth, three-way cock, and dropping funnel was charged with 91 mg of 5,7-dibromothieno [3,4-b] pyrazine, 2,5-didecyloxy-1,4. -Put 200 mg of bis (4,4,5,5-tetramethyl-1,3,2-di-oxaborolate), 3.6 mg of tetrakis (triphenylphosphine) palladium, and Aliquat 336 (2 drops), Dissolved in 15 ml of dehydrated toluene. Thereto, 13 ml of 2M sodium carbonate solution was added, and the reaction solution was heated in an oil bath and stirred at an internal temperature of 90 ° C. for 72 hours. Thereafter, 49 mg of bromobenzene was added and stirred at an internal temperature of 90 ° C. for 1 hour. After adding 63 mg of phenylboronic acid, the reaction mixture was cooled to room temperature and poured into a large amount of methanol. Filtered and washed with water, methanol, acetone. The obtained product was dried under reduced pressure at 50 ° C. to obtain 97 mg of poly [2,5-didecyloxy-1,4-phenylene-alt-5,7- (thieno [3,4-b] pyrazine). Mn of the obtained thienopyrazine copolymer 5 was 3800, and the degree of dispersion was 1.2.

<Preparation example>
(Preparation of PEDOT / PSS dispersion)
19 g of an aqueous solution containing 1% by weight of polystyrene sulfonic acid (PSS), 490 mg of 1% iron (III) sulfate aqueous solution, 300 mg of concentrated nitric acid, 90 mg of 3,4-ethylenedioxythiophene, and 11% by weight of peroxodisulfuric acid 1.2 g of aqueous solution was added. The reaction was stirred at 18 ° C. for 20 hours. Subsequently, after adding an ion exchange resin to this reaction mixture and stirring for 2 hours, the ion exchange resin is filtered and desalted to disperse a composite of poly (3,4-tylenedithiothiophene) and polystyrenesulfonic acid. The product (solid content 1.42%) was obtained.

<Example 1>
(Thin film production by composition 1-1)
5 mg of thienopyrazine copolymer 1 was dissolved in 1 ml of chlorobenzene. This liquid was dropped on a glass plate (2.5 cm × 2.5 cm × 0.1 cm) and rotated at 1000 rpm for 30 seconds with a spin coater to produce a thin film of about 50 nm. Thereafter, the obtained thin film was exposed to an iodine atmosphere for 1 hour.

<Example 2>
(Thin film production by composition 1-2)
A thin film of thienopyrazine copolymer 1 was produced in the same manner as in Example 1. Thereafter, the obtained thin film was immersed in a 0.3 M tetrabutylammonium perchlorate-acetonitrile solution and a voltage was applied. Then, it wash | cleaned with water and acetone, and air-dried.

<Example 3>
(Thin film preparation with composition 1-3)
A thin film of thienopyrazine copolymer 1 was produced in the same manner as in Example 1. Thereafter, the obtained thin film was immersed in a 0.3 M solution of tetrabutylammonium p-toluenesulfonate-acetonitrile and a voltage was applied. Then, it wash | cleaned with water and acetone, and air-dried.

<Example 4>
(Thin film production by composition 2-1)
The same operation was performed except that the thienopyrazine copolymer 2 was used instead of the thienopyrazine copolymer 1 of Example 1.

<Example 5>
(Thin film production by composition 2-2)
The same operation was performed except that thienopyrazine copolymer 2 was used instead of thienopyrazine copolymer 1 of Example 2.

<Example 6>
(Thin film production by composition 2-3)
The same operation was performed except that the thienopyrazine copolymer 2 was used in place of the thienopyrazine copolymer 1 of Example 3.

<Example 7>
(Thin film production by composition 3-1)
The same operation was performed except that the thienopyrazine copolymer 3 was used in place of the thienopyrazine copolymer 1 of Example 1.

<Example 8>
(Thin film production by composition 3-2)
The same operation was performed except that thienopyrazine copolymer 3 was used instead of thienopyrazine copolymer 1 of Example 2.

<Example 9>
(Thin film production by composition 3-3)
The same operation was performed except that thienopyrazine copolymer 3 was used instead of thienopyrazine copolymer 1 of Example 3.

<Example 10>
(Thin film production by composition 4-1)
The same operation was performed except that thienopyrazine copolymer 4 was used instead of thienopyrazine copolymer 1 of Example 1.

<Example 11>
(Thin film production by composition 4-2)
The same operation was performed except that thienopyrazine copolymer 4 was used instead of thienopyrazine copolymer 1 of Example 2.

<Example 12>
(Thin film production by composition 4-3)
The same operation was performed except that thienopyrazine copolymer 4 was used instead of thienopyrazine copolymer 1 of Example 3.

<Example 13>
(Thin film production by composition 5-1)
The same operation was performed except that thienopyrazine copolymer 5 was used instead of thienopyrazine copolymer 1 of Example 1.

<Example 14>
(Preparation of thin film by composition 5-2)
The same operation was performed except that thienopyrazine copolymer 5 was used instead of thienopyrazine copolymer 1 of Example 2.

<Example 15>
(Preparation of thin film by composition 5-3)
The same operation was performed except that thienopyrazine copolymer 5 was used instead of thienopyrazine copolymer 1 of Example 3.

<Comparative example>
The PEDOT / PSS dispersion produced in the preparation example was dropped on a glass plate (2.5 cm × 2.5 cm × 0.1 cm) and rotated at 1000 rpm for 30 seconds with a spin coater to produce a thin film of about 400 nm.

<Measurement of electrical conductivity>
The electrical conductivities of the thin films obtained in Examples 1 to 15 and the comparative example were measured with a 4-probe type measuring instrument (MCP-T610 manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1.

<Measurement of transmittance>
The transmittance | permeability of the thin film obtained in Examples 1-15 and the comparative example was measured with the ultraviolet visible spectrophotometer (UV-VIS-NIR) (Shimadzu Corporation Solidspec-3700). The results are shown in Table 1.

  As is clear from Table 1, the thin film using the conductive thienopyrazine copolymer composition of Examples 1 to 15 according to the present invention is compared with the thin film using the PEDOT / PSS dispersion as a comparative example. It showed high electrical conductivity and higher transmittance. From the above results, it was confirmed that the conductive thienopyrazine copolymer composition of the present invention was useful as a material for the transparent conductive film.

  The conductive thienopyrazine copolymer composition of the present invention is highly transparent and can be used as a material for a transparent conductive film exhibiting excellent conductivity. Moreover, the transparent conductive film formed from the conductive thienopyrazine copolymer composition is used for transparent electrodes such as liquid crystal displays, plasma displays, electroluminescence displays, electrochromic displays, solar cells, touch panels, capacitors, secondary batteries, and connections. It can be used for members, polymer semiconductor elements, antistatic materials such as antistatic coatings, antistatic packaging materials, electromagnetic shielding materials, and electrophotographic equipment parts such as transfer belts, developing rolls, charging rolls, transfer rolls, etc. .

Claims (4)

The following chemical formula (I)

[In Formula (I), R ¹ and R ² are each a hydrogen atom, an aryl group, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, W and Y Are each a divalent thiophene ring optionally having a substituent, n and m are 0 to 1, and R ³ , R ⁴ , R ⁵ and R ⁶ are each represented by the following chemical formula (II)
^{R 7 - [X 1 - (} CH 2) a] b - (X 2) c - ··· (II)
(In formula (II), R ⁷ is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, X ¹ and X ² are the same or different oxygen atoms or sulfur atoms, [X ¹ - (CH _{2) a]} for each repeating unit ^{X 1} and - (CH _{2) a} - the same or different, side a is 1 to 20, b is 0 to 20, c is represented by 0 or 1) Chain group]
A conductive thienopyrazine copolymer composition comprising a thienopyrazine copolymer having a repeating unit represented by formula (I) and a dopant. 2. The conductive thienopyrazine copolymer composition according to claim 1, wherein in the chemical formula (I), R ³ and R ⁶ are each a hydrogen atom. In the chemical formula (I), R ³ and R ⁶ are each a hydrogen atom, R ⁴ and R ⁵ are positive numbers in at least one of b and c in the chemical formula (II), or R ^{7 when} b = c = 0. 2. The conductive thienopyrazine copolymer composition according to claim 1, wherein the side chain group is an alkyl group.   A transparent conductive film, wherein the conductive thienopyrazine copolymer composition according to claim 1 is cured on a substrate.