JP2012224721A - Polymeric composite for conductive film, and production method and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite of a polystyrenesulfonic acid or its salt and a polythiophene derivative, capable of forming a highly conductive film at low cost; and to provide a coating composition including a water-dispersion of the composite.SOLUTION: The composite comprises: a polystyrenesulfonic acid or its salt obtained by polymerizing styrenesulfonic acid or its salt; and a polythiophene derivative obtained by polymerizing a thiophene derivative in the presence of the polystyrenesulfonic acid or its salt. Here, the composite is preferably the one made by polymerization of the polystyrenesulfonic acid or its salt in the presence of aminosulfonic acid, or the one obtained by mixing aminosulfonic acid after polymerization of the polystyrenesulfonic acid or its salt.

Description

  The present invention relates to a composite for a conductive film having high conductivity and low cost, an aqueous dispersion thereof, a method for producing the aqueous dispersion, and an application thereof. More specifically, the present invention relates to a polymer composite for conductive membranes synthesized in an aqueous solvent using polystyrene sulfonic acid or a salt thereof polymerized and / or mixed in the presence of aminosulfonic acid as a polyanion. Body, its aqueous dispersion, its production method, and its use.

  An aqueous dispersion containing a conductive polymer composite is used for an antistatic agent, an electrolytic capacitor, an electroluminescence display, a solar cell, a touch panel, and the like.

  Conventionally, a poly (3,4-dialkoxythiophene) / polyanion complex and an aqueous dispersion composed of an organic compound having a dihydroxy group, a polyhydroxy group, an amide group, and a lactam group are applied, dried, and annealed. Thus, it is known that a highly conductive coating can be obtained (for example, see Patent Document 1). It is also reported that the method can be obtained by drying a water-soluble crude product containing a polythiophene, a polyanion compound, and an aprotic compound having a dielectric constant of ε ≧ 15 to form a polymeric conductive layer without a high-temperature annealing step. (For example, refer to Patent Document 2).

  Furthermore, a coating composition containing a complex obtained by chemical oxidative polymerization at low pH from poly (3,4-dialkoxythiophene) and polyanion and an amide compound has been reported (for example, patents). Reference 3). Other examples of the effect of adding an imide compound as well as an amide compound have been reported (for example, see Patent Document 4). As an example of quantitative evaluation of the addition effect, a composition in which dimethyl sulfoxide (DMSO) is added to a complex dispersion of poly (3,4-dialkoxythiophene) and polystyrene sulfonic acid (hereinafter referred to as PEDOT / PSS) There is a report that the electrical conductivity increases by two orders of magnitude when an object is used (for example, see Non-Patent Document 1).

  By the way, in general, the effect of the additive for improving the conductivity of the conductive polymer has been explained by the deaggregation of the polymer molecule. In particular, in the case of polyaniline, the addition of cresol, phenol, and sulfonic acid compound to the polyaniline molecule. A deagglomeration effect has been reported (see, for example, Patent Document 5 and Non-Patent Document 2). In addition, with regard to PEDOT / PSS, detailed studies on structural changes in a system to which diethylene glycol was added were performed, and deagglomeration and rearrangement due to the addition of diethylene glycol were estimated. Excess PSS was removed and PEDOT was arranged in a large amount There has been a report on an increase in sites (see, for example, Non-Patent Document 3).

  On the other hand, when 3,4-ethylenedioxythiophene is chemically oxidatively polymerized, the viscosity of the oxidizing agent for polymerization can be obtained by using one selected from amine salts, quaternary ammonium salts, and aluminum salts of aromatic sulfonic acids. An example in which the above can be reduced has been reported (see, for example, Patent Document 6). In addition, a photopolymerization initiator and dimethyl sulfoxide are prepared by combining polythiophene, polystyrene sulfonic acid or a salt thereof and an amine compound having a polymerizable group such as an amine compound having a (meth) acryloyl group on a norbornene-based resin film. An example of obtaining a transparent conductive laminated film excellent in optical properties, environmental durability and conductivity by photopolymerization from the added film-forming composition has also been reported (see, for example, Patent Document 7).

  As described above, a dispersion using various additives for a polythiophene composite has been studied in search of a highly conductive polymer. However, in recent years, even with conductive polymers having other structures, high conductivity around 1000 S / cm has been demanded (see, for example, Patent Document 8 and Non-Patent Document 4), and further improvement is required for polythiophene composites. It is said that.

  As a result of various studies, it was suggested that the sequence of PEDOT is related to conductivity, but polystyrene sulfonic acid or its salt that affects the sequence of PEDOT during oxidative polymerization was improved, and high conductivity was achieved. An example of obtaining an aqueous dispersion giving a polymer has not been reported yet.

JP-A-8-048858 JP 2000-153229 A JP 2004-59666 A JP 2006-328276 A JP-A-8-231862 JP 2010-0530302 A JP 2010-103106 A JP 2010-212212 A

J. et al. Y. Kim et al., Synthetic Metals, 2002, 126, 311-316. A. G. MacDiarmid et al., Synthetic Metals, 1994, 65, 103-116. X. Crispin et al., Chemical Materials, 2006, 18: 4354-4360 L. Kwanghee et al., Nature, 2006, 44, 65-68.

  The present invention has been made in view of the background art described above, and the object thereof is to use a specific polystyrene sulfonic acid or a salt thereof as a polyanion at a low cost by using a simple technique as described above. Another object is to provide a composite containing a polythiophene derivative for forming a highly conductive film and an aqueous dispersion containing the composite.

  The present inventors have studied a composite (conductive polymer) obtained using polystyrene sulfonic acid or a salt thereof, which is a polyanion having a different polymerization method and modification method. As a result, surprisingly, there is no need for special copolymerization, cross-linking polymerization, substituent introduction, or modification, and polystyrene sulfonic acid obtained by polymerizing styrene sulfonic acid or its salt in the presence of aminosulfonic acid. Highly conductive film can be formed easily and effectively by using acid or its salt and / or polystyrenesulfonic acid obtained by polymerization by conventional method or its salt mixed with aminosulfonic acid. It was found that an aqueous dispersion containing a composite for use and a composite was obtained, and the present invention was completed.

That is, as shown below, the present invention is a polystyrene sulfonic acid polymerized and / or mixed with aminosulfonic acid or a salt thereof, a complex comprising a polythiophene derivative, and an aqueous dispersion comprising the complex and its The present invention relates to a production method, a coating composition comprising an aqueous dispersion containing the composite, and a conductive coating obtained by applying and drying the coating composition.
[1] A composite comprising polystyrene sulfonic acid or a salt thereof obtained by polymerizing styrene sulfonic acid or a salt thereof, and a polythiophene derivative obtained by polymerizing a thiophene derivative in the presence of the polystyrene sulfonic acid or a salt thereof. [2] The complex according to [1], wherein the thiophene derivative is 3,4-ethylenedioxythiophene.
[3] The composite according to [1] or [2], wherein polystyrene sulfonic acid or a salt thereof is polymerized in the presence of aminosulfonic acid.
[4] The complex according to any one of [1] to [3], wherein the polystyrenesulfonic acid or a salt thereof is a mixture of aminosulfonic acid after polymerization.
[5] Aminosulfonic acid is represented by the following general formula (1)

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 3). The complex according to any one of [1] to [4].
[6] The complex according to [5], wherein the compound represented by the general formula (1) is taurine, methyltaurine, dimethyltaurine, aminomethanesulfonic acid, or aminopropanesulfonic acid.
[7] Aminosulfonic acid is represented by the following formula (2)

(Wherein R ₃ and R ₄ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), the sulfanilic acid derivative represented by any one of [1] to [4] Complex.
[8] The complex according to any one of [1] to [7], which is obtained by removing aminosulfonic acid.
[9] An aqueous dispersion obtained by dispersing the complex according to any one of [1] to [8] in water.
[10] The method for producing an aqueous dispersion according to [9], wherein polystyrene sulfonic acid or a salt thereof and a thiophene derivative are subjected to oxidative polymerization in the presence of dimethyl sulfoxide.
[11] The method for producing an aqueous dispersion according to [10], wherein the oxidative polymerization is chemical oxidative polymerization using ammonium peroxodisulfate and a ferric salt.
[12] In the presence of aminosulfonic acid, polystyrenesulfonic acid or a salt thereof obtained by polymerizing a monomer comprising styrenesulfonic acid or a salt thereof, and / or aminosulfonic acid and polystyrenesulfonic acid or a salt thereof are mixed. The method for producing an aqueous dispersion according to [10] or [11], which is obtained by removing aminosulfonic acid later.
[13] A coating composition comprising the aqueous dispersion described in [9].
[14] A conductive coating produced by applying and drying the coating composition according to [13] on a substrate surface.

  Polythiophene using polystyrene sulfonic acid or its salt obtained by polymerization in the presence of aminosulfonic acid according to the method of the present invention and / or polystyrene sulfonic acid or its salt mixed with aminosulfonic acid as a polyanion If a complex containing a derivative and an aqueous dispersion containing the complex are used, a coating composition for forming a highly conductive film can be provided at a low cost using a simple technique.

Hereinafter, the present invention will be described in detail.
<Method for producing polystyrene sulfonic acid or a salt thereof in the presence of aminosulfonic acid>
The composite of the present invention includes polystyrene sulfonic acid or a salt thereof obtained by polymerizing styrene sulfonic acid or a salt thereof, and a polythiophene derivative obtained by polymerizing a thiophene derivative in the presence of the polystyrene sulfonic acid or a salt thereof. It is a complex consisting of

  Examples of the polystyrene sulfonic acid or salt in the composite of the present invention include polystyrene sulfonic acid, polystyrene sulfonic acid sodium salt, polystyrene sulfonic acid potassium salt, polystyrene sulfonic acid lithium salt, polystyrene sulfonic acid ammonium salt, polystyrene sulfonic acid methylamine salt, Examples thereof include polystyrene sulfonic acid dimethylamine salt, polystyrene sulfonic acid trimethylamine salt, polystyrene sulfonic acid ethylamine salt, polystyrene sulfonic acid diethylamine salt, and polystyrene sulfonic acid triethylamine salt.

  Here, the polystyrene sulfonic acid or salt is obtained by polymerizing styrene sulfonic acid or a salt thereof. Examples of the styrene sulfonic acid or salt thereof used include styrene sulfonic acid, sodium styrene sulfonate, potassium styrene sulfonate, Styrenesulfonic acid lithium salt, styrenesulfonic acid ammonium salt, styrenesulfonic acid methylamine salt, styrenesulfonic acid dimethylamine salt, styrenesulfonic acid trimethylamine salt, styrenesulfonic acid ethylamine salt, styrenesulfonic acid diethylamine salt, styrenesulfonic acid triethylamine salt, etc. Is mentioned.

  The polymerization method is not particularly limited, and includes normal radical polymerization. Among them, polymerization is preferably performed in the presence of aminosulfonic acid. The temperature of the polymerization reaction is not particularly limited as long as it is a reaction temperature capable of producing ordinary polystyrene sulfonic acid, preferably 0 to 100 ° C, more preferably 10 to 90 ° C, particularly preferably. 40-90 ° C. The polymerization time is not particularly limited as long as it is a time necessary for polymerizing ordinary polystyrene sulfonic acid, preferably within 200 hours, and particularly preferably within 130 hours.

  When polymerizing in the presence of aminosulfonic acid to obtain polystyrene sulfonic acid or a salt thereof, aminosulfonic acid and styrene sulfonic acid monomer or styrene sulfonate monomer are mixed in an aqueous solution, ammonium peroxodisulfate, and It is preferable to perform polymerization using an azo polymerization initiator (W-50 Pure Chemical, V-50).

  The polystyrene sulfonic acid or salt in the composite of the present invention is prepared by mixing aminosulfonic acid and a styrene sulfonic acid monomer or a styrene sulfonate monomer in an aqueous solution to produce ammonium peroxodisulfate and / or an azo polymerization initiator. It can also obtain by the method of polymerizing using (product made from Wako Purechemical, V-50), and then carrying out a mixing process with aminosulfonic acid.

  In the case of mixing treatment, polystyrene sulfonic acid obtained by polymerization of styrene sulfonic acid monomer or styrene sulfonate monomer, or polystyrene sulfonate and aminosulfonic acid are mixed in an aqueous solution to have a target molecular weight. It can be a polyanion.

  The treatment temperature in the above-described mixing treatment is not particularly limited as long as it is a reaction temperature at which an aqueous solution can be normally handled, and is preferably 0 to 100 ° C, more preferably 0 to 50 ° C, and particularly preferably 10 to 10 ° C. 40 ° C.

  The aminosulfonic acid used is preferably removed.

The weight average molecular weight of the polystyrene sulfonic acid or salt thereof obtained in the present invention is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 500,000, from the viewpoint of thin film formability, conductivity and viscosity. And particularly preferably 30,000 to 300,000.
<Aminosulfonic acid>
As the aminosulfonic acid used, compounds represented by the above general formulas (1) and (2) are preferable.

In the general formula (1), _wherein, R 1, _{R 2} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms each independently, n is an integer of 1-3.

Specifically, the substituents R ₁ and R ₂ in the general formula (1) are each independently a hydrogen atom; having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. An alkyl group can be mentioned, and among them, a hydrogen atom and a methyl group are particularly preferable.

  Moreover, n in General formula (1) is an integer of 1-3, and it is preferable that n is 2 especially.

In General formula (2), in formula, R < ₃ >, R < ₄ > respectively independently represents a hydrogen atom or a C1-C3 alkyl group.

Specifically, the substituents R ₃ and R ₄ in the general formula (2) are each independently a hydrogen atom; having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. An alkyl group can be mentioned, and among them, a hydrogen atom and a methyl group are particularly preferable.

  Examples of the aminosulfonic acid include compounds represented by the general formula (1) such as aminomethanesulfonic acid, N-methylaminomethanesulfonic acid, N, N-dimethylaminomethanesulfonic acid, N-ethylaminomethane. Sulfonic acid, N, N-diethylaminomethanesulfonic acid, N- (n-propylamino) methanesulfonic acid, N, N- (n-dipropylamino) methanesulfonic acid, N- (isopropylamino) methanesulfonic acid, N N- (diisopropylamino) methanesulfonic acid, taurine, N-methyltaurine, N, N-dimethyltaurine, N-ethyltaurine, N, N-diethyltaurine, N- (n-propyl) taurine, N, N- Di (n-propyl) taurine, N-isopropyltaurine, N, N-diisopropyltaurine, Minopropanesulfonic acid, N-methylaminopropanesulfonic acid, N, N-dimethylaminopropanesulfonic acid, N-ethylaminopropanesulfonic acid, N, N-diethylaminopropanesulfonic acid, N- (n-propylamino) propanesulfone Acid, N, N- (n-dipropylamino) propanesulfonic acid, N- (isopropylamino) propanesulfonic acid, N, N- (diisopropylamino) propanesulfonic acid, etc. Also good.

  Examples of the compound represented by the general formula (2) include sulfanilic acid, N-methylsulfanilic acid, N, N-dimethylsulfanilic acid, N-ethylsulfanilic acid, N, N-diethylsulfanilic acid, 4- (N -(N-propylamino)) phenylsulfonic acid, 4- (N, N- (n-dipropylamino)) phenylsulfonic acid, 4- (N- (isopropylamino)) phenylsulfonic acid, 4- (N, N- (diisopropylamino)) phenylsulfonic acid and the like may be mentioned, and these may be used alone or in a mixture.

  Of these, taurine, N-methyltaurine, N, N-dimethyltaurine, and sulfanilic acid are particularly preferred because of their solubility in water.

  The amount of aminosulfonic acid used is not particularly limited, and styrenesulfonic acid in the repeating unit contained in the raw material styrenesulfonic acid monomer or polymer (estimated from the weight average molecular weight Mw in terms of polystyrene). 0.2-5.0 times mole is preferable with respect to 1 mol, Most preferably, it is 1.0-2.0 times mole.

<Synthesis of complex>
The composite of the present invention uses polystyrene sulfonic acid or a salt thereof obtained by polymerizing the styrene sulfonic acid or a salt thereof as a polyanion, and polymerizes a thiophene derivative in the presence of the polystyrene sulfonic acid or a salt thereof. It is a composite comprising the resulting polythiophene derivative.

  Examples of the thiophene derivative in the present invention include 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, 3,4-dialkylthiophene 3,4-dialkoxythiophene. Among them, 3,4-ethylenedioxythiophene is particularly preferable.

  As the polyanion, polystyrene sulfonic acid was directly used for the polymerization reaction. Further, the salt of polystyrene sulfonic acid was used as the salt, or ion exchange was performed as necessary, and used as acid type polystyrene sulfonic acid.

  As the polymerization method for polymerizing the thiophene derivative in the presence of polystyrene sulfonic acid or a salt thereof in the composite of the present invention, oxidative polymerization is preferable.

  As the catalyst used for the oxidative polymerization reaction in the present invention, for example, general catalysts such as persulfate and ferric salt can be used. Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate. Examples of the ferric salt include ferric sulfate, ferric chloride, and ferric toluenesulfonate. Among them, ammonium persulfate and ferric sulfate are particularly preferable.

  The amount of the oxidative polymerization catalyst used is preferably 1.0 to 5.0 times mol, particularly preferably 1.0 to 1.5 times mol based on 1 mol of the thiophene derivative.

  The solvent used in the oxidative polymerization reaction described above is preferably an aqueous solvent, particularly preferably water. In addition, an auxiliary solvent can be used, and examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, diethylene glycol, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. One or a mixture may be used. Of these, dimethyl sulfoxide is particularly preferable.

  The amount of the auxiliary solvent used is not particularly limited, and styrene sulfonic acid in a repeating unit contained in the raw material styrene sulfonic acid monomer or polymer (estimated from the number average molecular weight Mn in terms of polystyrene) 1 0.2-100 times mole is preferable with respect to mole, Most preferably, it is 1.0-2.0 times mole.

  In this oxidative polymerization method, the reaction temperature is not particularly limited as long as it is a reaction temperature at which an aqueous solvent can be handled, and is preferably 0 to 100 ° C., more preferably because the reaction proceeds without changing the concentration. Is 0 to 50 ° C., particularly preferably 0 to 30 ° C.

  In addition, the amount of polystyrene sulfonic acid or a salt thereof used in the oxidative polymerization reaction in the present invention is preferably 50 to 2,000 parts by weight, more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the thiophene derivative. Particularly preferred is 150 to 300 parts by weight.

The content of polystyrene sulfonic acid or a salt thereof in the composite in the present invention is preferably 0.1 to 20% by weight, particularly preferably 0.4 to 5% by weight from the viewpoints of conductivity and dispersibility.
<Water dispersion>
The aqueous dispersion of the present invention is obtained by dispersing the above composite in water.

  An auxiliary solvent can be used for the aqueous dispersion, and examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, diethylene glycol, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. May be used alone or in combination. Of these, dimethyl sulfoxide is particularly preferable.

  The content of dimethylsulfoxy preferably used as an auxiliary solvent is preferably 0.5 to 50% by weight, particularly preferably 5 to 10% by weight, as a proportion of the total amount including the solvent, from the viewpoint of conductivity.

<Method for producing aqueous dispersion>
The method for producing an aqueous dispersion of the present invention can be produced by oxidative polymerization of polystyrene sulfonic acid or a salt thereof and a thiophene derivative in the presence of dimethyl sulfoxide.

  The polystyrene sulfonic acid used in the method for producing an aqueous dispersion, or a salt thereof, is a polystyrene sulfonic acid obtained by polymerizing a monomer comprising styrene sulfonic acid or a salt thereof in the presence of aminosulfonic acid, and / or a salt thereof, and / or The aminosulfonic acid is preferably obtained by mixing the aminosulfonic acid and polystyrene sulfonic acid or a salt thereof and then removing the aminosulfonic acid.

  As the catalyst used in the oxidative polymerization reaction, for example, general catalysts such as persulfate and ferric salt can be used. Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate. Examples of the ferric salt include ferric sulfate, ferric chloride, and ferric toluenesulfonate. Among them, ammonium persulfate and ferric sulfate are particularly preferable.

  The amount of the oxidative polymerization catalyst used is preferably 1.0 to 5.0 times mol, particularly preferably 1.0 to 1.5 times mol based on 1 mol of the thiophene derivative.

  The solvent used in the oxidative polymerization reaction described above is preferably an aqueous solvent, particularly preferably water. In addition, an auxiliary solvent can be used, and examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, diethylene glycol, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. One or a mixture may be used. Of these, dimethyl sulfoxide is particularly preferable.

  The amount of the auxiliary solvent used is not particularly limited, and is preferably styrene sulfonic acid in a repeating unit contained in the raw material styrene sulfonic acid monomer or polymer (estimated from the number average molecular weight Mn in terms of polystyrene). ) It is preferably 0.2 to 100 times mol, particularly preferably 0.5 to 2.0 times mol, per 1 mol.

In this oxidative polymerization method, the reaction temperature is not particularly limited as long as it is a reaction temperature at which an aqueous solvent can be handled, and is preferably 0 to 100 ° C., more preferably because the reaction proceeds without changing the concentration. Is 0 to 50 ° C., particularly preferably 0 to 30 ° C.
<Coating composition>
The coating composition comprising an aqueous dispersion containing a composite for forming the conductive coating of the present invention is a composition of an aqueous dispersion and dimethyl sulfoxide.
<Conductive coating>
If the coating composition of the present invention described above is used, a coating having excellent conductivity can be obtained by coating and drying the substrate surface.

  The substrate to be used is not particularly limited, and examples thereof include a plastic sheet, a plastic film, a nonwoven fabric, and a glass plate.

  Moreover, the application method is not particularly limited, and examples thereof include spin coating, wire coating, bar coating, roll coating, brate coating, curtain coating, and screen printing.

  The heating conditions for drying the applied coating composition are not particularly limited, and for example, 20 to 250 ° C is preferable, and 60 to 150 ° C is particularly preferable.

  The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto. In addition, the yield of the product in a present Example was confirmed with the isolated weight. The physical property values were measured using the following equipment.

Water-acetonitrile-based GPC: manufactured by Tosoh Corporation, HLC-8200 system Further, for measurement of ¹ H-NMR and ¹³ C-NMR of the compound, Gemini-200 manufactured by Varian was used.

  Moreover, the low resistivity meter (Mitsubishi Chemical Corporation Lorester GP, MCP-T600) was used for the measurement of electrical conductivity.

Synthesis Example 1 (Synthesis Example 1 of dimethyl taurine (aminosulfonic acid represented by the general formula (1))
A 150 ml stainless steel autoclave was charged with 25% sodium vinylsulfonate aqueous solution 100.1 g (0.19 mol) and 50% dimethylamine aqueous solution 19.0 g (0.21 mol) at 25 ° C. Thereafter, the temperature was raised to 115 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while stirring at 115 ° C. with heating. After completion of the reaction, the reaction mixture was cooled to 25 ° C., 249.4 g of methanol and 12.7 g (0.21 mol) of acetic acid were added, and the mixture was concentrated at 80 ° C. Further, recrystallization was performed from 200 ml of methanol and 100 ml of isopropanol. The solid was collected by filtration, washed with methanol and isopropanol, and then dried under reduced pressure to obtain 21.5 g of white powder (73%). When the obtained powder was measured by ¹ H-NMR and ¹³ C-NMR, it was confirmed to be dimethyltaurine.

¹ H-NMR (200 MHz, DMSO-d ₆ ) 2.81 (6H, s), 2.89 (2H, t), 3.29 (2H, t)
¹³ C-NMR (50 MHz, DMSO-d ₆ ) 42.47, 45.36, 53.91.
Synthesis example 2 (Production example 1 of post-taurine addition treatment of polystyrene sulfonic acid)
In a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade, 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) (0.042 mol) and water 40 at 25 ° C. 0.0 g was charged and dissolved, heated to 90 ° C., 0.05 g of ammonium persulfate was added, and polymerization was performed for 2 hours. 50.0 g of water was added to the obtained reaction liquid, and after passing through the column filled with 50 ml of a cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, 50 ml of washing water was added to the same column. The solution was passed through at 1 ml / min. Further, the entire treatment solution was passed through the column filled with 50 ml of an anion exchange resin (Amberlite IRA96SB manufactured by Organo) at 1 ml / min, and then 50 ml of washing water was passed through the column at 1 ml / min. Liquid-treated. Next, 5.3 g (0.042 mol) of taurine (manufactured by Wako Pure Chemicals, reagent grade 1), which is an aminosulfonic acid represented by the general formula (1), was added to and mixed with all the treatment liquids, followed by stirring at 25 ° C. for 24 hours. Processed.

  Thereafter, 150 ml of water was added to the treatment liquid, and about 150 ml of an aqueous solution was removed using an ultrafiltration apparatus (stirring ultrafilter manufactured by Advantech Toyo Co., Ltd., molecular weight cut off 50,000). This operation was repeated three times to obtain a polystyrene sulfonate aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and taurine were not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 340,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis example 3 (Production example 2 of post-taurine addition treatment of polystyrene sulfonic acid)
In a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade, 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) (0.042 mol) and water 40 at 25 ° C. 0.0 g was charged and dissolved, heated to 90 ° C., 0.05 g of ammonium persulfate was added, and polymerization was performed for 2 hours. The obtained reaction solution was added with 50.0 g of water, passed through the column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, and then washed with 50 ml of washing water. The solution was passed through at 1 ml / min. Further, the entire treated solution was passed through the column filled with 50 ml of an anion exchange resin (Amberlite IRA96SB manufactured by Organo) at 1 ml / min, and then 50 ml of washing water was passed through the column at 1 ml / min. Processed. Next, 5.3 g (0.042 mol) of taurine (manufactured by Wako Pure Chemicals, grade 1 reagent), which is an aminosulfonic acid represented by the general formula (1), was added to and mixed with the entire treatment liquid, and stirred at 25 ° C. for 120 hours. Processed. Thereafter, 150 ml of water was added to the treatment liquid, and about 150 ml of an aqueous solution was removed using an ultrafiltration apparatus (stirring ultrafilter manufactured by Advantech Toyo Co., Ltd., molecular weight cut off 50,000). This operation was repeated three times to obtain a polystyrene sulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and taurine were not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 320,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis example 4 (Production example 3 of post-taurine addition treatment of polystyrene sulfonic acid)
In a 200 ml four-necked flask equipped with a condenser, a thermometer and a stirring blade, at 25 ° C., 10.0 g (0.042 mol) of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and water 40 0.0 g was charged and dissolved, heated to 90 ° C., 0.05 g of ammonium persulfate was added, and polymerization was performed for 2 hours. The obtained reaction solution was added with 50.0 g of water, passed through the column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, and then washed with 50 ml of washing water at 1 ml / min. The solution was passed through. Further, the entire treated solution was passed through the column filled with 50 ml of an anion exchange resin (Amberlite IRA96SB manufactured by Organo) at 1 ml / min, and then 50 ml of washing water was passed through the column at 1 ml / min. Processed. Next, 5.3 g (0.042 mol) of taurine (manufactured by Wako Pure Chemicals, grade 1 reagent), which is an aminosulfonic acid represented by the general formula (1), was added to and mixed with the whole treatment liquid, and stirred at 50 ° C. for 24 hours. Processed. Thereafter, 150 ml of water was added to the treatment liquid, and about 150 ml of an aqueous solution was removed using an ultrafiltration apparatus (stirring ultrafilter manufactured by Advantech Toyo Co., Ltd., molecular weight cut off 50,000). This operation was repeated three times to obtain a polystyrene sulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonate and taurine were not detected. Moreover, the weight average molecular weight on the basis of standard sodium polystyrene sulfonate was 290,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis Example 5 (Production Example 1 of polystyrene sulfonic acid polymerized by addition of taurine)
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. After dissolving and passing through a column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, 50 ml of washing water was passed through the column at 1 ml / min. Next, 5.6 g of taurine (manufactured by Wako Pure Chemicals, reagent grade 1), which is an aminosulfonic acid represented by the general formula (1), is added to the total treatment liquid, heated to 90 ° C., and 0.03 g of ammonium persulfate is added. Polymerization was performed for a period of time, and 0.03 g of ammonium persulfate was further added, followed by polymerization for 20 hours. Thereafter, 30 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantec Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 50,000). This operation was repeated 4 times to obtain a polystyrenesulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and taurine were not detected. Moreover, the weight average molecular weight on the basis of standard sodium polystyrene sulfonate was 60,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis Example 6 (Production Example 2 of polystyrene sulfonic acid polymerized by addition of taurine)
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. After dissolving and passing through a column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, 50 ml of washing water was passed through the column at 1 ml / min. Next, 5.6 g of taurine (manufactured by Wako Pure Chemicals, reagent grade 1), which is an aminosulfonic acid represented by the general formula (1), is added to the entire treatment liquid, heated to 90 ° C., and 2,2-azobis (2-amidino Propane) dihydrochloride (trade name V-50, manufactured by Wako Pure Chemical Industries, Ltd.) 0.03 g was added in four portions and polymerized for 123 hours. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantech Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 50,000). This operation was repeated three times to obtain a polystyrene sulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and taurine were not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 40,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis Example 7 (Production Example 3 of polystyrene sulfonic acid polymerized by addition of taurine)
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. After dissolving and passing through a column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, 50 ml of washing water was passed through the column at 1 ml / min. Next, 1.1 g of taurine (manufactured by Wako Pure Chemicals, reagent grade 1), which is an aminosulfonic acid represented by the general formula (1), is added to the total treatment liquid, heated to 90 ° C., and 0.12 g of ammonium persulfate is added. Polymerization was conducted for a period of time, and 0.12 g of ammonium persulfate was further added, followed by polymerization for 1 hour. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantec Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 10,000). This operation was repeated three times to obtain a polystyrene sulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and taurine were not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 90,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis Example 8 (Production example of polystyrene sulfonic acid polymerized by addition of dimethyl taurine)
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. After dissolving and passing through a column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, 50 ml of washing water was passed through the column at 1 ml / min. Next, 6.5 g of dimethyltaurine, which is an aminosulfonic acid represented by the general formula (1) synthesized in Synthesis Example 1, was added to the entire treatment solution, heated to 90 ° C., and 0.12 g of ammonium persulfate was added in four portions. Polymerized for 22 hours. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantech Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 50,000). This operation was repeated three times to obtain a polystyrene sulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and dimethyl taurine were not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 40,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Synthesis Example 9 (Production example of polystyrene sulfonic acid polymerized by addition of sulfanilic acid)
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. The solution was dissolved and passed through a column filled with 50 ml of a cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, and then 50 ml of washing water was passed through the column at 1 ml / min. Next, 1.5 g of sulfanilic acid (manufactured by Kishida Chemical Co., Ltd., reagent special grade), which is an aminosulfonic acid represented by the general formula (2), is added to the entire treatment solution, heated to 90 ° C., and 0.12 g of ammonium persulfate is added. Polymerization was conducted for a period of time, and 0.12 g of ammonium persulfate was further added, followed by polymerization for 18 hours. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantech Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 50,000). This operation was repeated 5 times to obtain a polystyrenesulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid and sulfanilic acid were not detected. Moreover, the weight average molecular weight on the basis of standard sodium polystyrene sulfonate was 50,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

Example 1 (Production example of PEDOT-PSS)
In a 200 ml four-necked flask equipped with a condenser, a thermometer, and a stirring blade, 18.6 g of a 5% by weight aqueous solution of polystyrene sulfonic acid obtained in Synthesis Example 2 at 25 ° C. (pure content 0.93 g,. 005 mol, 200 parts by weight with respect to 100 parts by weight of 3,4-ethylenedioxythiophene), 0.26 g (0.003 mol) of dimethyl sulfoxide as an auxiliary solvent, 0.77 g (0.003 mol) of ammonium persulfate as an oxidation polymerization catalyst, sulfuric acid Ferric iron (0.02 g, 0.123 mmol) was charged, water was added to make a total amount of 100 g, and dissolved by stirring. Subsequently, under strong stirring, 0.47 g (0.003 mol) of 3,4-ethylenedioxythiophene was added as a thiophene derivative and polymerized at 25 ° C. for 24 hours.

  The obtained polymerization solution was dispersed with an ultrasonic homogenizer (UT-300T manufactured by Nippon Seiki Co., Ltd.) for 20 minutes to form an aqueous dispersion, and then 10 g of a cation exchange resin (Amberlite IR120B manufactured by Organo Co., Ltd.) and an anion exchange resin. 10 g (Amberlite IRA96SB manufactured by Organo Corporation) was added and stirred for 1 hour. Thereafter, the dispersion was filtered with a filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) to remove the ion exchange resin together with cations and anions. Next, 400 ml of water was added to the filtrate, and about 400 ml of an aqueous solution was removed using an ultrafiltration device (stirring ultrafilter manufactured by Advantech Toyo Co., Ltd., molecular weight cut off 10,000). This operation was repeated three times to remove free low molecular components. Further, this treatment liquid was passed through a membrane filter (pore diameter 0.45 μm) to finally obtain a conductive polymer dispersion. To the dispersion obtained by the above operation, 5% by weight of dimethyl sulfoxide was added to obtain a coating composition. The coating composition thus obtained was cast on a glass plate, dried at 25 ° C. for 5 hours, and further dried at 130 ° C. for 30 minutes to form a conductive film. When the electrical conductivity of this film was measured with a low resistivity meter (Loresstar GP, MCP-T600, manufactured by Mitsubishi Chemical Corporation), it showed a high electrical conductivity of 704 S / cm. The results are summarized in Table 1.

Example 2 (Production Example of PEDOT-PSS)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that the polystyrene sulfonic acid obtained in Synthesis Example 3 was used. Using this dispersion, a conductive film was prepared in the same manner as in Example 1. As a result of measuring the conductivity of this film by the same method as in Example 1, it showed a high conductivity of 637 S / cm. The results are summarized in Table 1.

Example 3 to Example 8
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that the polystyrene sulfonic acid obtained in each of Synthesis Examples 4 to 9 was used. Using this dispersion, a conductive film was prepared in the same manner as in Example 1. The conductivity of this film was measured by the same method as in Example 1, and the results are summarized in Table 1.

Comparative Example 1
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. The solution was dissolved, heated to 90 ° C., 0.05 g of ammonium persulfate was added, and polymerization was performed for 2 hours. The obtained reaction solution was added with 50.0 g of water, passed through the column filled with 50 ml of cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, and then washed with 50 ml of washing water. The solution was passed at 1 ml / min. Further, the entire treatment solution was passed through the column filled with 50 ml of anion exchange resin (Amberlite IRA96SB manufactured by Organo) at 1 ml / min, and the column was passed through with washing water at 50 ml / min. A sulfonic acid aqueous solution was obtained. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid was not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 340,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

  A polymer dispersion was obtained in the same manner as in Example 1 except that the obtained polystyrene sulfonic acid was used. Using this dispersion, a film was prepared in the same manner as in Example 1. The conductivity of this film was measured by the same method as in Example 1. As a result, the thiophene derivative was not used, and thus the conductivity was as low as 493 S / cm as compared with Example 2 having the same molecular weight. The results are summarized in Table 1.

Comparative Example 2
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. The solution was dissolved and passed through a column filled with 50 ml of a cation exchange resin (Amberlite IR120B manufactured by Organo) at 1 ml / min, and then 50 ml of washing water was passed through the column at 1 ml / min. Next, the whole treatment liquid was heated to 90 ° C., 0.05 g of ammonium persulfate was added and polymerized for 2 hours, and 0.05 g of ammonium persulfate was further added for polymerization for 2 hours. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantec Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 10,000). This operation was repeated 5 times to obtain a polystyrenesulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid was not detected. Moreover, the weight average molecular weight on the basis of standard sodium polystyrene sulfonate was 70,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

  A polymer dispersion was obtained in the same manner as in Example 1 except that the obtained polystyrene sulfonic acid was used. Using this dispersion, a film was prepared in the same manner as in Example 1. As a result of measuring the conductivity of this film by the same method as in Example 1, it showed a low conductivity of 127 S / cm because no thiophene derivative was used. The results are summarized in Table 1.

Comparative Example 3
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. Dissolved. This solution was passed through a column filled with 50 ml of a cation exchange resin (Amberlite IR120B manufactured by Organo Corporation) at 1 ml / min. Further, 50 ml of washing water was passed through the column at 1 ml / min. Next, the whole treatment liquid was heated to 90 ° C., 0.05 g of ammonium persulfate was added and polymerized for 2 hours, and 0.05 g of ammonium persulfate was further added for polymerization for 2 hours. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantec Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 10,000). This operation was repeated 5 times to obtain a polystyrenesulfonic acid aqueous solution. As a result of analyzing the obtained polystyrene sulfonic acid aqueous solution by GPC, low molecular weight styrene sulfonic acid was not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 40,000. Further, the chlorine, bromine and sodium contents were all 50 ppm or less based on polystyrene sulfonic acid, as determined by ion chromatography and inductively coupled plasma emission spectrometry.

  A polymer dispersion was obtained in the same manner as in Example 1 except that the obtained polystyrene sulfonic acid was used. Using this dispersion, a film was prepared in the same manner as in Example 1. The conductivity of this film was measured by the same method as in Example 1. As a result, no thiophene derivative was used, so that the conductivity was as low as 74 S / cm as compared with Examples 5 and 7 having the same molecular weight. . The results are summarized in Table 1.

Comparative Example 4
Polymerization was obtained in the same manner as in Example 1 except that dimethyl sulfoxide was not added in the method of Example 1. Using this dispersion, a film was prepared in the same manner as in Example 1. As a result of measuring the electrical conductivity of this film by the same method as in Example 1, dimethyl sulfoxide was not added, so that the coating composition had a conductivity as low as 395 S / cm as compared with Example 1 having the same molecular weight. Showed the rate. The results are summarized in Table 1.

Comparative Example 5
Polymerization was obtained in the same manner as in Example 2 without adding dimethyl sulfoxide in the method of Example 2. Using this dispersion, a film was prepared by the same method as in Example 2. As a result of measuring the conductivity of this film by the same method as in Example 2, dimethyl sulfoxide was not added, so that the coating composition had a conductivity as low as 300 S / cm as compared with Example 2 having the same molecular weight. Showed the rate. The results are summarized in Table 1.

Synthesis Example 10 (Production Example 4 of Sodium Polystyrenesulfonate Polymerized by Adding Taurine)
Into a 200 ml four-necked flask equipped with a condenser, thermometer, and stirring blade was charged 10.0 g of sodium styrenesulfonate (Spinomer NaSS manufactured by Tosoh Corporation, purity 87%) and 40.0 g of water at 25 ° C. Next, 5.6 g of taurine (manufactured by Wako Pure Chemicals, reagent grade 1), which is an aminosulfonic acid represented by the general formula (1), is added to the solution, heated to 90 ° C., and 0.04 g of ammonium persulfate is added. Polymerized for 2 hours. Thereafter, 50 ml of water was added to the treatment liquid, and about 50 ml of an aqueous solution was removed using an ultrafiltration device (advantech Toyo Co., Ltd. stirring type ultrafilter, molecular weight cut off 50,000). This operation was repeated 3 times to obtain an aqueous sodium polystyrenesulfonate solution. As a result of analyzing the obtained sodium polystyrenesulfonate aqueous solution by GPC, low molecular sodium styrenesulfonate and taurine were not detected. The weight average molecular weight based on standard sodium polystyrene sulfonate was 310,000. Furthermore, the chlorine and bromine contents were all 50 ppm or less based on polystyrene sulfonic acid, as measured by ion chromatography and inductively coupled plasma emission spectrometry.

Example 9 (Production Example of PEDOT-PSS)
In a 200 ml four-necked flask equipped with a condenser, a thermometer, and a stirring blade, 18.6 g of a 5% by weight aqueous solution of sodium polystyrenesulfonate obtained in Synthesis Example 10 at 25 ° C., 0.26 g of dimethyl sulfoxide, 0.77 g of ammonium sulfate and 0.02 g of ferric sulfate were charged, and water was added to make the total amount 100 g and dissolved by stirring. Subsequently, 0.47 g of 3,4-ethylenedioxythiophene was added under strong stirring, and polymerization was performed at 25 ° C. for 24 hours. The obtained polymerization solution was dispersed with an ultrasonic homogenizer (UT-300T manufactured by Nippon Seiki Co., Ltd.) for 20 minutes, and then 10 g of a cation exchange resin (Amberlite IR120B manufactured by Organo) and an anion exchange resin (Amber manufactured by Organo). 10 g of LIGHT IRA96SB) was added and stirred for 1 hour. Thereafter, the dispersion was filtered with a filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) to remove the ion exchange resin together with cations and anions. Add 5% by weight of dimethyl sulfoxide to the dispersion obtained by the above operation (coating composition), cast and apply on a glass plate, dry at 25 ° C for 5 hours, and further dry at 130 ° C for 30 minutes. Thus, a conductive film was prepared. When the conductivity of this film was measured with a low resistivity meter (Loresstar GP, MCP-T600 manufactured by Mitsubishi Chemical Corporation), a conductivity of 313 S / cm was shown. The results are summarized in Table 2.

Comparative Example 6
In a 200 ml four-necked flask equipped with a condenser, a thermometer, and a stirring blade, 5.2 g of a 20 wt% sodium polystyrene sulfonate aqueous solution (PS-50, Tosoh Corporation) and 0.26 g of dimethyl sulfoxide at 25 ° C. Then, 0.77 g of ammonium persulfate and 0.04 g of ferric sulfate were charged, water was added to make the total amount 100 g, and dissolved by stirring. Subsequently, 0.47 g of 3,4-ethylenedioxythiophene was added under strong stirring, and polymerization was performed at 25 ° C. for 24 hours. The obtained polymerization solution was dispersed with an ultrasonic homogenizer (UT-300T manufactured by Nippon Seiki Co., Ltd.) for 20 minutes, and then 10 g of a cation exchange resin (Amberlite IR120B manufactured by Organo) and an anion exchange resin (Amber manufactured by Organo). 10 g of LIGHT IRA96SB) was added and stirred for 1 hour. Thereafter, the dispersion was filtered with a filter paper (No. 2 manufactured by Toyo Roshi Kaisha, Ltd.) to remove the ion exchange resin together with cations and anions. Next, 400 ml of water was added to the filtrate, and about 400 ml of an aqueous solution was removed using an ultrafiltration device (stirring ultrafilter manufactured by Advantech Toyo Co., Ltd., molecular weight cut off 10,000). This operation was repeated three times to remove free low molecular components. Further, this treatment liquid was passed through a membrane filter (pore diameter 0.45 μm) to obtain a conductive polymer dispersion. 5% by weight of dimethyl sulfoxide is added to the dispersion obtained by the above operation, cast on a glass plate, dried at 25 ° C. for 5 hours, and further dried at 130 ° C. for 30 minutes to form a conductive film. It was created. When the electrical conductivity of this film was measured with a low resistivity meter (Mitsubishi Chemical Corporation Lorester GP, MCP-T600), it showed a low electrical conductivity of 41 S / cm. The results are summarized in Table 2.

  From the above results, if polystyrene sulfonic acid obtained by polymerization in the presence of aminosulfonic acid or a salt thereof, and / or polystyrene sulfonic acid mixed with aminosulfonic acid or a salt thereof is used as a polyanion, Compared to the case where untreated polystyrene sulfonic acid or a salt thereof having an equivalent molecular weight is used as a polyanion, a conductive film having a clearly higher conductivity can be obtained.

  According to the method of the present invention, polystyrene sulfonic acid obtained by polymerization in the presence of aminosulfonic acid or a salt thereof, and / or polystyrene sulfonic acid mixed with aminosulfonic acid or a salt thereof is used as a polyanion. A composition for forming a highly conductive film can be provided at low cost from a complex of poly (3,4-dialkoxythiophene) using a simple method.

  By using this novel coating composition, a coating with excellent conductivity can be obtained by applying and drying on the surface of the substrate, and to antistatic agents, electrolytic capacitors, electroluminescent displays, solar cells, touch panels, etc. Is expected to be used.

Claims (14)

It comprises a polystyrene sulfonic acid or a salt thereof obtained by polymerizing styrene sulfonic acid or a salt thereof, and a polythiophene derivative obtained by polymerizing a thiophene derivative in the presence of the polystyrene sulfonic acid or a salt thereof. Complex. The composite according to claim 1, wherein the thiophene derivative is 3,4-ethylenedioxythiophene. The composite according to claim 1 or 2, wherein the polystyrene sulfonic acid or a salt thereof is polymerized in the presence of aminosulfonic acid. The composite according to any one of claims 1 to 3, wherein the polystyrenesulfonic acid or a salt thereof is a mixture of aminosulfonic acid after polymerization. Aminosulfonic acid is represented by the following general formula (1)

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 3). The composite according to any one of claims 1 to 4, wherein: 6. The complex according to claim 5, wherein the compound represented by the general formula (1) is taurine, methyltaurine, dimethyltaurine, aminomethanesulfonic acid or aminopropanesulfonic acid. Aminosulfonic acid is represented by the following formula (2)

(Wherein R ₃ and R ₄ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), a sulfanilic acid derivative represented by any one of claims 1 to 4 A complex according to any one of the above. The complex according to any one of claims 1 to 7, wherein aminosulfonic acid is removed. An aqueous dispersion obtained by dispersing the composite according to any one of claims 1 to 8 in water. The method for producing an aqueous dispersion according to claim 9, wherein polystyrene sulfonic acid or a salt thereof and a thiophene derivative are oxidatively polymerized in the presence of dimethyl sulfoxide. The method for producing an aqueous dispersion according to claim 10, wherein the oxidative polymerization is chemical oxidative polymerization using ammonium peroxodisulfate and a ferric salt. Polystyrene sulfonic acid or a salt thereof obtained by polymerizing a monomer comprising styrene sulfonic acid or a salt thereof in the presence of amino sulfonic acid, and / or an amino sulfone after mixing amino sulfonic acid and polystyrene sulfonic acid or a salt thereof. The method for producing an aqueous dispersion according to claim 10 or 11, which is obtained by removing an acid. A coating composition comprising the aqueous dispersion according to claim 9 and dimethyl sulfoxide. An electrically conductive coating produced by applying and drying the coating composition according to claim 13 on a substrate surface.