TWI595038B - Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition - Google Patents

Description

Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition

The present invention relates to a composite conductive polymer composition, a method for producing the same, a solution containing the composition, and a use of the composition, and more specifically, for imparting solubility to a solvent such as aniline, thiophene or pyrrole A π-conjugated polymer having a heterocyclic compound as a monomer component, and a composite conductive polymer composition doped with a polymer compound, a method for producing the same, a solution containing the composition, and sensitizing the dye Application of solar electric electrodes or anti-static films.

When a high conductivity is imparted to a π-conjugated polymer, it is necessary to dope by a dopant. However, a polymer having a relatively high π-conjugated structure has a high planarity of a polymer chain, and has a structure having high crystallinity (stackability) between polymer chains formed by affinity of a π bond. Further, the π-conjugated polymer doped by the dopant is more remarkable in planarity and high affinity by π conjugate, and the stacking property is more remarkable. Therefore, the dissolution of the π-conjugated polymer (based on heat or solvent) and electrical conductivity are difficult problems.

Therefore, a polymer in which an alkyl group or an alkoxy group or the like is introduced into a side chain of a π-conjugated polymer has been proposed (Patent Document 1), but actually, in order to improve electrical conductivity, it can be sufficiently called a conductor. The negative 5th power of 10 is less than ‧ m and must be doped. When this doping is carried out, the planarity of the conductive polymer is developed and the π-conjugated affinity is developed, resulting in a problem that sufficient solvent solubility cannot be obtained.

When considering the use of a conductive polymer, it is preferable to use a solvent to dissolve or melt by heat, and to obtain sufficient electrical conduction after forming a film. A self-supporting film or a self-supporting formed body. Conventionally, when such a conductive polymer is used, a film formed by directly forming a polymer film on a substrate to be imparted with conductivity by electrolytic polymerization or vapor exposure is performed. Alternatively, the film is immersed in an oxidizing agent and a conductive polymer precursor monomer solution, followed by heating, and the like, and then the obtained polymer film is doped or the like.

However, at this time, in the electrolytic polymerization, the substrate must be a semiconductor or an electric conductor, and corrosion resistance to the electrolyte is also required, so that the substrate which can be used is limited. Further, in the film polymerization by direct vapor, it is necessary to uniformly present the oxidizing agent in the film to be a polymerization site, which is not sufficient in terms of film formation control, and is used in the polymer capacitor application used in such a method. In order to form a fine unevenness in order to increase the surface area, it is difficult to sufficiently form the conductive polymer on a homogeneous surface.

Therefore, attempts have been made to dissolve the conductive polymer in an organic solvent, and several means for achieving this have been proposed. Patent Document 2 discloses a method for producing a poly(3,4-disubstituted thiophene) in which a 3,4-disubstituted thiophene is polymerized using an inorganic high-iron salt and an oxidizing agent, and Patent Document 3 discloses a method. A water-dispersible powder mainly having a polymer T containing a repeating thiophene unit and at least one other polyanionic polymer P. However, the method of Patent Document 2 is a method of producing a powder or a method of oxidative polymerization directly on the surface of a subject, and the polymer obtained by the method cannot be dissolved in a solvent or water, and the like. The three are also only dispersions with good water dispersibility, not those whose molecules are soluble in organic solvents.

Further, various means for more direct solvent nano-dispersion have been discussed. In Patent Document 4, it is disclosed that a polyaniline which is substantially insoluble in a solvent is pulverized to a nanometer size to be micronized, and A sulfonic acid anionic emulsifier such as SDS (dodecylbenzenesulfonic acid) or PTS (p-toluenesulfonic acid) having a high affinity for polyaniline or a solvent is used as a dispersing agent and is co-dispersed in a solvent. Providing a nano-scale microdispersion solution, but it is not substantially soluble in a solvent, so the surface of the coated film is uneven, and it cannot constitute a self-supporting film of polyaniline (also referred to as a homogeneous film, which means If it is not formed by pinholes or the like, it is not formed, and if it is not combined with a binder, it cannot be film-formed after application.

Further, Patent Document 5 discloses a polythiophene having a molecular weight of a molecular weight of 2,000 to 500,000 and an oxidative chemical polymerization in the presence of a polyanion of polystyrenesulfonic acid; and a molecular weight of 2,000 to 500,000. And a polyanion derived from polystyrenesulfonic acid is contained in a mixed solvent of water or a mixed organic solvent of water and water to form a solution of polythiophene.

This patent document proposes to produce poly(dioxyethylene thiophene) (PEDOT) which can be dissolved or dispersed in water or an alcohol solvent by oxidative polymerization in the coexistence of polystyrenesulfonic acid (PSS) and an oxidizing agent. However, although the PEDOT/PSS obtained here is dispersed in water, it is not completely dissolved, and it is still difficult to suppress the stacking between a part of PEDOT, and the ability to dissolve the conductive polymer is still insufficient.

Further, Patent Document 6 discloses that an aniline or an aniline derivative is oxidatively polymerized and precipitated in a solvent containing an organic acid or an inorganic acid in the presence of a highly hydrophobic anionic surfactant. After separation and purification, it is extracted with an organic solvent which is not mixed with water to form an organic solution.

However, the emulsifier used in this patent document is a low molecular sulfonic acid system. Although aniline is chlorinated by hydrochloric acid before polymerization and then substituted with an aniline salt by a sulfonic acid emulsifier, it is practically difficult to initiate sufficient salt exchange. Further, the polyaniline obtained by the synthesis method of the present patent document does not actually dissolve in a solvent, and has a problem that only a solvent dispersion liquid in a slightly dispersed state can be obtained. Further, since a sulfonic acid-based emulsifier having an equivalent amount or more with respect to aniline is used, 50% or more of an emulsifier other than the substantially doped emulsifier remains, and it is necessary to remove the emulsifier when used. Therefore, there is a problem that the washing step is cumbersome. Further, in the low molecular weight emulsifier, it is very difficult to impart an effect of dissolving the solvent with respect to the solvent and the inhibitory effect of the polyaniline stack, and it is introduced into the design of one molecule, even if it is temporarily dissolved in the solvent of the polyaniline. The problem of microcoagulation caused by stacking (crystallization of PANI) occurs.

Further, Patent Document 7 discloses a method in which (A) a monomer having a sulfonic acid functional group and a radical polymerizable functional group and (B) a monomer composed of aniline or a derivative thereof are dissolved in water or organic. The solution obtained by the solvent is emulsified, and after introducing the sulfonic acid structure of the monomer of (A) into the monomer of (B), the monomers of (A) and (B) are coexisted in the following coexistence of the polymerization initiator. Polymerization is carried out to produce a conductive polymer in a state in which the polymer of (B) and the polymer of (A) are intertwined.

However, in the method of this patent document, since ammonium persulfate is used as a water-based oxidizing agent and a radical initiator, it is practically difficult to form a mutual mesh of a desired ethylene-based polymer and polyaniline as described in the present specification. structure. Therefore, in this patent document method, there are actually many ethylene polymers which do not contain PANI, but instead there are many doping monomers which are not incorporated in the ethylene polymer in PANI, and there are compounds which become extremely heterogeneous and unstable. The problem.

Further, for example, in Patent Document 8, it is disclosed that (a) a protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent which is not substantially mixed with water, and (b) contains a phenolic hydroxyl group. A conductive polyaniline composition of the compound.

However, in this patent document, since the synthesis of polyaniline is carried out using a water-soluble oxidizing agent in a polymerization site of a solvent/water/monomer/emulsifier, it is essentially a water-soluble aniline monomer which is polymerized while being interposed. The emulsifier is dispersed in a system of toluene to form polyaniline, and is substantially insoluble in a solvent which is slightly soluble in water except for toluene. Further, in the invention of the patent document, in the sodium diisooctylsulfide succinate (AOT) actually used, since the stacking of polyaniline cannot be sufficiently suppressed, it is required to be used in combination with a phenol (cresol) or the like. Although the description in the specification is not sufficient, the technique described in Non-Patent Document 1 discloses that the affinity of the phenolic compound is remarkable by adjusting the body strength in the polyaniline film. It is used to enhance the conductivity of the polyaniline film. This can be considered by mixing non-volatile additives such as phenols which have good solubility with respect to toluene and good compatibility with polyaniline, thereby not only improving the conductivity of the dried coating film, but also phenols. It inhibits the stacking of polyanilines which are soluble in toluene. When these additives are not present, such as AOT, the stability of the solubility of polyaniline under steric hindrance cannot be achieved, and this is the case. The inventors' follow-up tests were also confirmed.

On the other hand, regarding the use of the conductive polymer composition, there are a counter electrode and an antistatic film for a dye-sensitized solar cell. Patent Document 10 discloses a counter electrode of a dye-sensitized solar cell in which a conductive polymer layer is provided on a plastic film provided with a transparent conductive layer.

However, in this patent document, although a dispersion containing a conductive polymer is applied and a solvent is removed to form a conductive polymer layer, the conductive polymer is a dispersed film of fine particles, so that it is dense with respect to the transparent conductive layer. Poorness is required, and plasma treatment or the like is required in advance to increase the surface energy of the transparent conductive layer. Further, in the examples of the patent documents, polystyrene sulfonic acid is used as a dispersing agent, but in this case, there is a sulfonic acid which is not doped into the doping of the conductive polymer, and the solvent is made into an aqueous solution. Therefore, when applied to a film substrate, the selectivity of the solvent and the surface of the film substrate becomes extremely large, and pinholes caused by the unevenness of the conductive polymer coating film are likely to occur, and the residual sulfonic acid group is coated. When the polarity of the film is increased, the durability of the acetonitrile or the ionic liquid or the like which is generally used in the electrolyte solution is deteriorated, peeling of the coating film is liable to occur, and for this reason, the transparent conductive film is generated in the electrolyte. The problem of iodine corrosion is a problem with regard to the long-term stability of the pole. The replacement of platinum is still insufficient for the extreme.

Further, Patent Document 11 discloses an antistatic film in which an antistatic material containing a polythiophene-based compound, an acidic polymer, and a sugar alcohol is applied onto a thermoplastic resin film.

However, in this patent document, since sugar alcohol is required as an essential component of an antistatic material, although the obtained antistatic film has good transparency and antistatic property, it uses only an acidic polymer such as polystyrenesulfonic acid. As a dopant for the polythiophene-based compound, the antistatic film absorbs moisture over time, and has a problem of poor adhesion and antistatic property.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Special Table 2002-539287

[Patent Document 2] Japanese Patent Laid-Open No. 01-313521

[Patent Document 3] Japanese Special Table 2004-514753

[Patent Document 4] Japanese Special Table 2007-518859

[Patent Document 5] Japanese Patent No. 2636968

[Patent Document 6] Japanese Special Open 2008-169255

[Patent Document 7] Japanese Special Opening 2007-314606

[Patent Document 8] Japan WO2005/052058

[Patent Document 9] Japanese Special Publication 2000-344823

[Patent Document 10] Japanese Patent Laid-Open No. 2006-155907

[Patent Document 11] Japanese Special Open 2008-179809

[Non-Patent Document 1] Y. Cao et al./Synthetic Metals 69 (1995) 187-190

Therefore, the object of the present invention is to provide a conductive polymer composition which is excellent in solubility in a solvent, and which can be a self-supporting film, that is, a homogeneous film or a molded body which does not cause pinholes, and the like, and a method for producing the same. .

In order to solve the above problems, the inventors of the present invention have conducted a follow-up study on the above-described prior art, and as a result, have clearly grasped the fact that the following elements are necessary for the synthesis, purification, and re-dissolution of a solvent from a conductive polymer. In other words, <1> in the polymerization site of the π-conjugated polymer, it is necessary to use a sufficient electrolyte solvent, and to stably and uniformly impart an anion site capable of undergoing oxidation, and <2> must control the growth of π in the polymerization. The stacking property of the conjugated polymer and imparting a stable monomer supply, <3> actively doping the π-conjugated polymer in the polymerization growth site, <4> in the process of doping Water and the like can be precipitated from the electrolyte solvent in the initial polymerization site, and <5> the π-conjugated polymer after polymerization can inhibit the stacking of the main chain skeleton by some stereoscopic molecular hindrance, <6> The barrier factor itself does not have crystallinity and can be melted by a solvent or heat.

Therefore, the present inventors have further studied and found that when a polymer compound which copolymerizes a specific monomer is used as an additive in the polymerization of a π-conjugated polymer, it has an emulsifier. The polymerization site is formed in a uniform state and functions as a dopant, and since it has a moderate steric hindrance to the π-conjugated polymer, it can be made to have a better solubility for a specific solvent. A composite conductive polymer composition. In addition, the present inventors have found that the composite conductive polymer composition can be applied to a counter electrode and an antistatic film for a dye-sensitized solar cell, and the like.

That is, the present invention is a composite conductive polymer composition which is doped with a polymer compound (A) obtained by polymerizing the following components (a-1) to (a-3). a π-conjugated polymer (β) having a compound selected from the following formulas (I) to (III) as a monomer component;

(a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group: 20 to 50 mol%;

(a-2) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%;

(a-3) alkyl (meth)acrylate: 30 to 60 mol%;

(In the formula, R ₁ to R ₇ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms).

Further, the present invention provides a method for producing a composite conductive polymer composition, which is characterized in that a polymer compound obtained by polymerizing the following components (a-1) to (a-3) is used. And coexisting with a compound selected from the above formulas (I) to (III) in an electrolytic matrix solvent, and performing chemical oxidative polymerization using an oxidizing agent;

(a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group: 20 to 50 mol%;

(a-2) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%;

(a-3) alkyl (meth)acrylate: 30 to 60 mol%.

Furthermore, the present invention is a composite conductive polymer composition solution which is an aromatic solvent selected from the group consisting of toluene, benzene and xylene and/or an ester selected from the group consisting of ethyl acetate, propyl acetate and butyl acetate. In the solvent, the composite conductive polymer composition is contained in an amount of 0.1 to 10% by mass in a dissolved state.

Further, the present invention is a counter electrode for a dye-sensitized solar cell, which is obtained by using the above composite conductive polymer composition.

Furthermore, the present invention is an antistatic film which is obtained by using the above composite conductive polymer composition.

In the presence of the polymer compound of the present invention, the composite conductive polymer composition obtained by the polymerization of an oxidizing agent can be stably dissolved in an aromatic solvent such as toluene or an ester solvent such as ethyl acetate.

Therefore, a conductive film can be easily produced by applying a solution in which the composite conductive polymer composition is dissolved in an aromatic solvent to a portion to be provided with conductivity and drying the solution.

The polymer compound (A) used in the present invention can be a monomer (s) having a sulfonic acid group and a polymerizable vinyl group as a component (a-1) in the presence of a polymerization initiator in accordance with a general method. -2) An aromatic group or an alicyclic group is polymerized with a monomer of a polymerizable vinyl group and an alkyl (meth)acrylate of the component (a-3).

The monomer having a sulfonic acid group and a polymerizable vinyl group of the component (a-1) is a monomer having a sulfonic acid group such as a styrenesulfonic acid group or a sulfoethyl group, and examples thereof include styrenesulfonic acid or styrene. a styrene sulfonate such as sodium sulfonate, potassium styrene sulfonate or calcium styrene sulfonate, 2-sulfoethyl (meth)acrylate or sodium 2-sulfonate (meth)acrylate, (methyl) a 2-sulfoethyl (meth)acrylate salt such as 2-sulfoethyl acrylate potassium salt or 2-sulfoethyl (meth)acrylate calcium salt.

Further, examples of the monomer having an aromatic or alicyclic group and a polymerizable vinyl group of the component (a-2) include benzyl (meth)acrylate and phenoxyethyl (meth)acrylate, Methyl)ethyl acrylate 2-methyl phthalate, ethyl 2-ethyl phthalate (ethyl) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, Dicyclopentenyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Morpholine ester, styrene, dimethyl styrene, naphthyl (meth) acrylate, vinyl naphthalene, vinyl n-ethyl carbazole, vinyl hydrazine, and the like.

Further, specific examples of the alkyl (meth)acrylate of the component (a-3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (methyl). Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl ester, isooctyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate.

In the production of the polymer compound (A) used in the present invention, the molar ratio of the monomer (a-1), the monomer (a-2) and the monomer (a-3) is important. In other words, the polymer compound of the present invention can be suitably formed by the hydrophilicity of the aromatic or alicyclic group and the hydrophilicity of the sulfonic acid group to form a conductive polymer compound. It can be dissolved in a solvent.

The compounding amount of the component (a-1) for producing the polymer compound (A) of the present invention is 20 to 50 mol%, preferably 25 to 40 mol%. Further, the compounding amount of the component (a-2) is 20 to 50 mol%, preferably 30 to 45 mol%. Further, the compounding amount of the component (a-3) is 30 to 60 mol%, preferably 35 to 50 mol%.

The polymer compound of the present invention may contain a polymerizable component other than the above monomers (a-1), (a-2) and (a-3). Examples of the polymerizable component include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Ester, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ( Methyl)acrylic acid, ethoxylated ethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, N, N-dimethylamine ethyl (meth) acrylate, vinyl pyridine, etc. The dosage is 0-20 mol%.

The polymerization of the component (a-1), the component (a-2), the component (a-3), and the polymerizable component added as necessary can be carried out by a generally known method. For example, after mixing the components, the polymerization initiator may be added thereto, and polymerization may be started by heating, light irradiation or the like to start polymerization.

The polymerization method which can be used for the production of the polymer compound (A) is not particularly limited as long as it can be carried out in a state where the component (a-2) is not separated from the monomer mixture, and for example, a solution polymerization method can be employed. , bulk (overall) polymerization, precipitation polymerization, and the like.

Further, the polymerization initiator used in the polymerization reaction is not particularly limited as long as it can be dissolved in the above respective components or the solvent used in the reaction. Examples of the polymerization initiator include oil-soluble peroxide-based thermal polymerization initiators such as benzamidine peroxide (BPO), and oil-soluble azo-based thermal polymerizations such as azobisisobutyronitrile (AIBN). A water-soluble azo-based thermal polymerization initiator such as a starter or azobiscyano shikimic acid (ACVA). Further, when the proportion of water in the solvent at the time of solution polymerization is large, a water-soluble peroxide-based thermal polymerization initiator such as ammonium persulfate or potassium persulfate or hydrogen peroxide water may be used. Further, it may be used in combination with a redox agent such as iron or an amine.

The range of use of such a polymerization initiator may be arbitrarily used in the range of 0.001 to 0.1 mol with respect to the above-mentioned compound 1 mol, and any method of collective input, drip input, and successive input may be used. . Further, in the case of bulk polymerization or solution polymerization using a small amount of a solvent (50 wt% or less with respect to a monomer), there is also a method of performing polymerization based on a mercaptan and a metal aromatic (Patent Document 9).

Further, the solvent used in the polymerization reaction may, for example, be an alcohol solvent such as methanol, ethanol, isopropanol or butanol; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; methyl cellosolve; A glycol solvent such as ethyl cellosolve, propylene glycol methyl ether or propylene glycol ethyl ether; a lactic acid solvent such as methyl lactate or ethyl lactate.

Further, in the polymerization, in addition to the polymerization initiator, a chain transfer agent may be used in combination, and when the molecular weight is to be adjusted, it may be suitably used. As the chain transfer agent which can be used, any compound can be used as long as it can be dissolved in the above monomer or solvent. For example, an alkylthiol such as dodecyl mercaptan or heptyl mercaptan can be suitably used; mercaptopropionic acid can be suitably used; (BMPA) a water-soluble thiol having a polar group; an oily radical inhibitor such as an α styrene dimer (ASD).

Further, the polymerization reaction is preferably carried out at a boiling point or lower of the solvent to be used (excluding the case of overall polymerization), and is preferably, for example, 65 ° C to 80 ° C. In the case of polymerization of the general literature or the polymerization of the patent document 9 based on the thiol and the metal scent, it is preferred to carry out the polymerization at 25 ° C to 80 ° C.

The polymer thus obtained can be purified as necessary to constitute the polymer compound (A). As an example of the purification method, an oily poor solvent such as hexane is used to remove oily low molecular impurities, residual monomers, and low molecular impurities, and then the polymer is polymerized by a poor aqueous solvent such as acetonitrile, methanol, ethanol or acetone. A method of removing water-based impurities and residues by precipitation or the like.

The reason why the purification is carried out is that the polymer compound (A) is introduced as a dopant into the conductive polymer composition to act as a stack inhibitor and a solvent solvent, and other polymerization initiator residues are added. The monomer, the oligomer, the heterogeneous composition, and the like remain as a residue after the polymerization, and the function of the conductive polymer composition is lowered, so that it must be removed. In addition, as a result of the purification, the non-uniform radical polymer is not mixed as in Patent Document 7, and the composition of the uniform conductive polymer composition and the polymer compound (A) can be exhibited. A soluble state that is homogeneously compatible.

The polymer compound (A) obtained above preferably has a weight average molecular weight in terms of GPC of 3,000 to 100,000. When the weight average molecular weight is less than 3,000, its function as a polymer compound is insufficient. On the other hand, when it exceeds 100,000, the solubility in the polymerization site (acid aqueous solution) at the time of synthesis of the conductive polymer may be insufficient, and the solvent solubility of the polymer compound itself may be deteriorated, possibly against the conductive polymer. Solubilization produces significant adverse effects.

The composite conductive polymer composition of the present invention is produced by the following method using the polymer compound (A) obtained above. In other words, the polymer compound (A) is dissolved in an electrolytic matrix solvent, and then the compound represented by the above formula (I) to formula (III) which is a raw material of the π-conjugated polymer (β) is added to the compound. This solution is then oxidized by an oxidizing agent, whereby the polymer compound (A) can be obtained by doping the compound represented by the above formula (I) to formula (III) as a monomer component. A composite conductive polymer composition of a π-conjugated polymer (β).

In the compound of the starting material, the compound represented by the formula (I) is an aniline whose substituent is a hydrogen atom or an alkyl group. Specific examples of the compound include aniline, o-toluidine, m-toluidine, 3,5-dimethylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethyl Aniline, 2-ethylaniline, 3-ethylaniline, 2-isopropylaniline, 3-isopropylaniline, 2-methyl-6-ethylaniline, 2-n-propylaniline, 2-methyl 5--5-isopropylaniline, 2-butylaniline, 3-butylaniline, 5,6,7,8-tetrahydro-1-naphthylaniline, 2,6-diethylaniline, and the like.

Further, the compound represented by the formula (II) is a thiophene whose substituent is a hydrogen atom or an alkyl group. Specific examples are thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-positive Octylthiophene and the like.

Further, the compound represented by the formula (III) is a pyrrole whose substituent is a hydrogen atom or an alkyl group, and specific examples thereof include pyrrole, 3-methylpyrrole, 3-heptylpyrrole, 3-n-octylpyrrole and the like.

An example of a specific method for producing a composite conductive polymer composition by the method of the present invention is to firstly obtain an ion-exchanged water as an electrolytic matrix solvent, and if necessary, acidification, and then obtain the polymer compound (A) obtained as described above. In addition, one or two or more kinds of the compounds of the formula (I) to the formula (III) of the starting materials are added thereto, and then an oxidizing agent is further added to carry out oxidative polymerization. Depending on the solubility of the polymer compound (A) in ion-exchanged water, a ketone solvent such as acetone or methyl ketone or an alcohol solvent such as methanol, ethanol or isopropanol; or a hydrophilicity such as acetonitrile may be used as appropriate. High organic solvent.

In the above reaction, in order to form the acidic matrix solvent into an acidic substance used for acidity, for example, hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride, iron (II) sulfate, or the like is used in an amount relative to The compound of the formula (I) to the formula (III) may be 0.5 to 3.0 mol in 1 mol.

In addition, the oxidizing agent used in the reaction should be appropriately adjusted depending on the difference in oxidation-reduction potential of the aromatic compound (monomer) forming the composite conductive polymer composition, and ammonium peroxodisulfate or peroxodisulfate can be used. Potassium, sodium peroxodisulfate, iron (III) chloride, iron (III) sulfate, iron (III) tetrafluoroborate, iron (III) hexafluorophosphate, copper (II) sulfate, copper (II) chloride, Copper (II) tetrafluoroborate, copper (II) hexafluorophosphate, and the like.

Further, the ratio of the polymer compound (A) to the compounds (I) to (III) in the reaction is not dependent on the nature of the finally obtained composite conductive polymer composition, and cannot be simply determined. For example, the number of the sulfonic acid groups in the polymer compound (A) and the molar ratio of the compounds (I) to (III) used are as follows.

That is, the polymer compound (A) coexists in an amount such that the molar ratio of the sulfonic acid group in the compound is 0.2 to 1.5 with respect to the compound 1 selected from the group consisting of the compounds (I) to (III). .

Further, the amount of the oxidizing agent is generally 1.5 to 2.5 moles (in terms of monovalent conversion) with respect to the compound (I) to (III) 1 mole, but the degree of oxidation (acidity) in the system is different. It is 1 mol or less with respect to the monomer 1 mol, and may be fully polymerized.

Further, the temperature at which the polymerization reaction of the composite conductive polymer composition is carried out is such that the calorific value after the oxidation reaction or the ease of hydrogen removal differs depending on the type of the compounds (I) to (III). The temperature range is also different.

In general, when the compound (I) is used, it is preferably 40 ° C or lower, and when the compound (II) is used, it is preferably 90 ° C or lower, and when the compound (III) is used, it is preferably 20 ° C or lower.

In addition, when the composite conductive polymer composition is to be subjected to high molecular weight, the reaction temperature may be relatively lowered, and the reaction time may be relatively increased. When the molecular weight is to be reduced, the reverse is required.

The polymer thus obtained can be further washed as necessary, and then formed into a composite conductive polymer composition of the object. As described later, the composition can be stably dissolved in an aromatic solvent such as toluene which does not dissolve the conventional conductive polymer composition, and an ester solvent such as ethyl acetate.

An example of the method of using the composite conductive polymer composition of the present invention obtained in this manner is a solution of a composite conductive polymer composition which is dissolved in an aromatic solvent and an ester solvent in a homogeneous state. The solution of the composite conductive polymer composition can be applied to a portion where the conductive film is to be formed, and then the aromatic solvent in the composition is volatilized by means of drying or the like to form a uniformity on the target portion. Conductive coating.

When the composite conductive polymer composition solution is prepared, the composite conductive polymer composition is preferably dissolved in an aromatic solvent such as toluene, benzene or xylene, and/or 0.1 to 10% by mass. An ester solvent such as ethyl acetate, propyl acetate or butyl acetate.

In addition, in the solution of the composite conductive polymer composition, benzyl alcohol, phenol, m-cresol, o-cresol, 2-naphthalene may be added for the purpose of improving the stability of the solution and the conductivity in the coating state. An aromatic compound having a hydroxyl group such as an alkanol, 1-naphthyl alcohol, guaiacol or 2,6-dimethylphenol. The aromatic compound having a hydroxyl group is preferably added in an amount of 0.01 to 45 parts by weight based on 100 parts by weight of the solvent of the solution of the composite conductive polymer composition.

In addition, in the above-mentioned composite conductive polymer composition solution, for the purpose of improving the conductivity of the self-supporting film of the antistatic paint and the catalytic performance of the solar material for the solar cell, it may further contain copper, silver, aluminum, a metal such as platinum; a metal oxide such as titanium oxide, indium tin oxide, fluorine-doped tin oxide, aluminum oxide or cerium oxide; conductive polymer composition, carbon nanotube (CNT), fullerene, A carbon powder such as carbon black or a dispersion is used as a filler component. The powder or dispersion is preferably added in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the solid content of the solution of the composite conductive polymer composition.

Further, the composite conductive polymer composition can be used as a counter electrode for a dye-sensitized solar cell. In the counter electrode for a dye-sensitized solar cell, when the transparency is required, the composite conductive polymer composition may be laminated on one surface of the transparent substrate, or the translucent electrode may be disposed on the transparent substrate. The composite conductive polymer composition is laminated on the surface of the translucent electrode. Further, when transparency is not required, it can be formed by laminating a metal foil or the like. The thickness of the composite conductive polymer composition is generally in the range of 0.01 to 100 μm, preferably 0.1 to 50 μm.

The transparent substrate used in the dye-sensitized type of the present invention can be a film or a sheet having a light transmittance of usually 50% or more, preferably 80% or more. Examples of such transparent substrates include inorganic transparent substrates such as glass, polyethylene terephthalate (PET), polycarbonate (PC), polyphenylene sulfide compounds, polyfluorene, polyester fluorene, and poly(methyl). A polymer transparent substrate such as an alkyl acrylate, a polyethylene naphthalate (PEN), a polyether oxime (PES) or a polycycloolefin. Further, the metal foil is, for example, a metal foil of gold, platinum, silver, tin, copper, aluminum, stainless steel, nickel or the like.

The thickness of the transparent substrate is generally in the range of 200 to 7000 μm in the case of the inorganic transparent substrate, and is generally in the range of 20 to 4000 μm, preferably 20 to 2000 μm in the case of the polymer transparent substrate. In the case of a metal foil substrate, it is in the range of 0.1 μm to 1000 μm, preferably 1 μm to 500 μm. The polymer transparent substrate and the metal foil substrate having a thickness in this range can impart flexibility to the obtained dye-sensitized solar cell.

Further, a translucent electrode may be disposed on one surface of the transparent substrate as necessary. The translucent electrode used herein includes, for example, a film-shaped conductive metal electrode, a mesh-like conductive metal electrode, or the like.

The film-shaped conductive metal electrode is formed by forming tin oxide, tin-doped indium oxide (ITO), fluorine-doped alumina (FTO), or the like into a film shape. In the film-shaped conductive metal electrode, tin oxide, ITO, FTO, or the like can be formed on the surface of the transparent substrate by vapor deposition, sputtering, or the like. The thickness of the film-shaped conductive metal electrode is generally in the range of 0.01 to 1 μm, preferably 0.01 to 0.5 μm.

On the other hand, the mesh-shaped conductive metal electrode is formed by forming a conductive metal such as copper, nickel or aluminum into a mesh shape. Specifically, the mesh-shaped conductive metal electrode is made of a conductive metal such as copper, nickel or aluminum, and has a line width of, for example, 10 to 70 μm, preferably 10 to 20 μm, by a lithography technique. The width is generally 50 to 300 μm, preferably 50 to 200 μm. The thickness of the wire of the mesh-shaped conductive metal electrode at this time is substantially the same as the thickness of the conductive metal to be used, and is generally in the range of 8 to 150 μm, preferably 8 to 15 μm. The mesh-shaped conductive metal electrode can be attached to the surface of the transparent substrate by using an adhesive or the like.

When the counter electrode for a dye-sensitized solar cell is produced, a method in which a composite conductive polymer composition is laminated on one surface of the transparent substrate or a translucent electrode disposed on one surface of a transparent substrate, for example, The above-mentioned composite conductive polymer composition solution may be applied to one surface of the transparent substrate or to a translucent electrode disposed on one surface of the transparent substrate, and may be removed one or more times. The solvent in the solution.

For the application of the solution of the composite conductive polymer composition, a general application such as a dip coater, a micro bar coater, a roll coater, a knife coater, a die coater, or a gravure coater can be used. Known coating machine.

Further, the removal of the solvent can be carried out by natural drying according to standing, forced drying under heating by hot air or infrared rays.

In the counter electrode for a dye-sensitized solar cell, the composite conductive polymer composition used in the above is soluble in an organic solvent, and is compared with a dispersion in which a composite conductive polymer composition is dispersed by an aqueous medium. The coating step is easy to carry out and the productivity is preferred. Further, it is also possible to suppress deterioration of corrosion of the metal in the counter production stage caused by the acidic aqueous solution.

Further, in the above-mentioned composite conductive polymer composition for the dye-sensitized solar cell, the above-mentioned component (a-1), component (a-2) and component (a) are used in a specific range. -3) By polymerizing the polymer compound (A) obtained by the copolymerization, the adhesion to the transparent substrate or the translucent electrode or the metal foil can be improved, so that it can be used for a long period of time.

Further, in the above-mentioned composite conductive polymer composition for the dye-sensitized solar cell, the above-mentioned component (a-1), component (a-2) and component are used in a specific range. A-3) The polymer compound (A) having a suppressed acidity obtained by copolymerization is used, whereby the translucent electrode (conductive metal) is less likely to be corroded, and the durability against the electrolyte is improved. So it can be used for a long time.

In addition, the counter electrode of the dye-sensitized solar cell can be used as a uniform oxidation-resistant film by using a platinum electrode which is conventionally used as an electrode having oxidation resistance to an electrolytic solution. It is used for various metals, so it can be provided at low cost.

Further, the antistatic film obtained by using the above composite conductive polymer composition can be processed into a low-resistance antistatic film because the composite conductive polymer composition can be coated and dried to form a self-supporting film. . Further, when the composite conductive polymer composition is mixed with the thermoplastic resin and/or the thermosetting resin as necessary, for example, by using a T die or the like, it is possible to use an extruder or an extruder. (2) a method of forming a film by melt-kneading, and (2) applying the solution of the composite conductive polymer composition to one side or both sides of a thermoplastic resin, a thermosetting resin, and a film made of glass, and It is produced by a method of removing a solvent in a solution to form an antistatic film or the like.

The thermoplastic resin used in the above antistatic film is, for example, polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, polyacrylonitrile butadiene styrene, poly Acrylonitrile styrene, polymethacrylic acid, polyacrylic acid, saturated polyester, polyamine, polycarbonate, polyfunctional phenyl ether, polyphenylene sulfide compound, polyfluorene, polyacrylate, liquid crystal polymer, polyether ether Ketones, polyamidoximines, and the like, also contain polymer alloys or thermoplastic elastomers of such thermoplastic resins.

The thermosetting resin used in the above antistatic film of the present invention is, for example, polyphenol, polyepoxy, unsaturated polyester, polyurethane, polyimine, polyurea, decyl oxide resin, melamine. Resin, fluororesin, alkyd resin, and the like.

Further, the antistatic film is obtained by copolymerizing the polymer (A) obtained by copolymerizing the component (a-1), the component (a-2) and the component (a-3) in a specific range. It can form an antistatic film with less uniformity in performance under various high humidity and low humidity environment conditions and high transmittance.

[Examples]

The invention is illustrated in more detail by the examples, but the invention is not limited by the examples. The molecular weight and surface resistance values in this example were determined by the following methods.

<molecular weight>

It was measured by GPC under the following conditions.

Device name: HLC-8120 (manufactured by Tosoh Corporation)

Column: GF-1G7B+GF-510HQ (Asahipak: registered trademark, manufactured by Showa Denko)

Reference material: polystyrene and sodium polystyrene sulfonate

Sample concentration: 1.0mg/ml

Dissolution: 50 mM aqueous solution of lithium chloride / CH ₃ CN=60/40wt

Flow rate: 0.6ml/min

Column temperature: 30 ° C

Detector: UV254nm

<surface resistance value>

The probes of the low resistivity meter Loresta GP and PSP type manufactured by DIA Instruments were used for measurement by a four-terminal four-probe method.

Example 1

(1) Polymer compound (2-NaSEMA/BzMA/2-EHMA=30/40/30)

The amount of 2-sulfoethyl methacrylate sodium salt (2-NaSEMA) was 50 g, benzyl methacrylate (BzMA) 55 g, 2-ethylhexyl methacrylate (2-EHA) 47 g, water 150 g and different 300 g of propanol was placed in the flask. After raising the temperature to the reflux temperature, 0.7 g of azobisisobutyronitrile (AIBN) was added to carry out polymerization. The reaction was carried out for 18 hours under reflux.

(2) Refining of polymer compounds

After 500 g of hexane was added to the polymer solution obtained in the above (1), impurities in the oil layer were removed by liquid separation extraction. 1 kg of methanol was dropped into the water layer after separation for 1 hour to precipitate a solid fraction, and the solid fraction was filtered. The obtained solid matter was dried at 100 ° C for 24 hours under reduced pressure, and then pulverized with hydrazine to obtain a powder (α-1) of a polymer compound. The obtained polymer was measured by GPC, and as a result, Mw was 38,000.

(3) Re-dissolution of polymer compounds

16.1 g of the polymer compound obtained in the above (2), 200 g of ion-exchanged water, and 6 g of a 35% hydrochloric acid aqueous solution were weighed into a flask, and the mixture was heated and stirred at 60 ° C to obtain a uniform aqueous polymer compound solution.

(4) Polyaniline polymerization

After cooling the aqueous solution of the polymer compound obtained in the above (3), 4.65 g of aniline was weighed and added thereto. After the mixture was stirred and dissolved, it became a uniform emulsion. Further, 30 g of water and 10 g of ammonium peroxodisulfate were weighed and mixed, and the mixture was dropped into a flask containing the emulsion at 0 ° C for 2 hours. After the completion of the dropwise addition, the mixture was returned to room temperature (25 ° C) and stirred for 48 hours.

(5) Polyaniline refining

The polymerization solution after completion of the reaction was filtered, and the obtained crystals were redispersed in water, washed, and filtered again. The aqueous solid matter obtained by the above-described washing was washed four times, and dried under reduced pressure at 40 ° C for 96 hours to obtain a dried polyaniline (composite conductive polymer composition) (β-1). . The volatile matter of the composite conductive polymer composition was measured, and as a result, the volatile matter was 2% or less.

(6) Polyaniline dissolution

5 g of the composite conductive polymer composition obtained in the above (5), 47 g of toluene, and 48 g of ethyl acetate were weighed and placed in a flask, and stirred and dissolved to obtain a composite conductive polymer composition solution. .

(7) Coating evaluation

The solution of the composite conductive polymer composition obtained in the above (6) was applied onto a glass substrate, and dried at 90 ° C to obtain a green uniform coating film (γ-1). The surface resistivity of this coating film was 60 k?/?.

Comparative example 1

(1) Comparative polymer compound (2-NaSEMA/BzMA/2-EHMA=30/10/60)

50 g of 2-NaSEMA, 13.8 g of BzMA, 94 g of 2-EHA, 150 g of ion-exchanged water, and 300 g of isopropyl alcohol were weighed and placed in a flask. After raising the temperature to the reflux temperature, 0.7 g of AIBN was added to carry out polymerization. The reaction was carried out for 18 hours under reflux.

(2) Refining of polymer compounds

After about 500 g of hexane was added to the polymer solution obtained in the above (1), impurities in the oil layer were removed by liquid separation extraction. 1 kg of methanol was dropped into the water layer after separation for 1 hour to precipitate a solid fraction, and the solid fraction was filtered. The obtained solid matter was dried at 100 ° C for 24 hours under reduced pressure, and then pulverized with hydrazine to obtain a powder of the polymer compound (α-6). The molecular weight of the obtained polymer was measured by GPC, and as a result, Mw was 35,000.

(3) Re-dissolution of polymer compounds

16.7 g of the above polymer compound, 200 g of ion-exchanged water, and 6 g of a 35% hydrochloric acid aqueous solution were weighed into a flask, and the mixture was heated and stirred at 60 ° C to obtain a uniform aqueous polymer compound solution.

(4) Polyaniline polymerization

After cooling the aqueous solution of the polymer compound obtained in the above (3), 4.65 g of aniline was weighed and added thereto. After the mixture was stirred and dissolved, it became a uniform emulsion. Further, 30 g of ion-exchanged water and 10 g of ammonium peroxodisulfate were weighed and mixed, and the mixture was dropped into a flask containing the emulsion at 0 ° C for 2 hours. After the completion of the dropwise addition, the mixture was returned to room temperature (25 ° C) and stirred for 30 hours.

(5) Polyaniline refining

The polymerization solution after completion of the reaction was filtered, and the obtained crystals were redispersed in water, washed, and filtered again. The aqueous solid matter obtained by the above-described washing was washed four times, and dried under reduced pressure at 40 ° C for 96 hours to obtain a dried polyaniline (comparative conductive polymer composition) (β-7). . The volatile content of the conductive polymer composition was measured and found to be 2% or less of the volatile matter.

(6) Polyaniline dissolution

5 g of the comparative conductive polymer composition obtained in the above (5), 47 g of toluene, and 48 g of ethyl acetate were weighed and placed in a flask, and the mixture was stirred but not dissolved, and a comparatively conductive portion which produced a part of the precipitate was obtained. A finely divided solution of a polymeric composition.

(7) Coating evaluation

The finely dispersed solution of the comparative conductive polymer composition obtained in the above (6) was filtered with a 200 mesh filter, and the filtrate was applied onto a glass substrate and dried to obtain a uniform film as a fine particle film (γ). -7) However, the film was peeled off when it was rubbed with a finger, and it was not able to be a uniform self-supporting coating film as obtained in Example 1, and its surface resistance value was 1 M?/?.

Examples 2 to 5 and Comparative Examples 2 to 4

The polymer compounds α-2 to α-5 were prepared by the methods shown in the following Table 1 by the methods shown in (1) and (2) of Example 1. Further, the comparative polymer compounds α-7 to α-9 were prepared by the method shown in the first table by the methods shown in (1) and (2) of Comparative Example 1. The molecular weight of each of the polymer compounds and the solubility in water, as shown in the first table, are shown in the first example and the comparative example 1.

Examples 6 to 10 and Comparative Examples 5 to 10

Using the polymer compounds α-2 to α-5 obtained in Examples 2 to 5, by the methods shown in (3) and (4) of Example 1, the composite conductivity was high in the composition of the second table. Molecular composition β-2 to β-6 (In the preparation of β-4, when redissolving the polymer compound, 100 g of ion-exchanged water and 100 g of saturated brine of 25° C. were used instead of 200 g of ion-exchanged water). Further, using the comparative polymer compounds α-7 to α-9 obtained in Comparative Examples 2 to 4, the comparison was made with the composition of the second table by the methods shown in (1) and (2) of Comparative Example 1. Conductive polymer composition β-8~β-13. In the second table, the examples obtained in Example 1 and Comparative Example 1 show the monomer composition of each conductive polymer, the type and amount of the polymer compound used, the amount of hydrochloric acid used, the oxidizing agent used, and the oxidizing agent used therefor. Amount and reaction conditions (reaction temperature and reaction time).

Examples 11 to 15 and Comparative Examples 11 to 16

The composite conductive polymer compositions β-1 to β-6 obtained in Examples 1 and 6 to 10 were dissolved in various aromatic solvents according to the methods shown in (6) and (7) of Example 1. After drying with an ester solvent, a composite conductive polymer composition film of γ-2 to γ-6 is formed. In addition, the comparative conductive polymer composition obtained in Comparative Examples 1 and 5 to 10 was similarly dissolved in various aromatic solvents and/or ester solvents, and then dried to attempt to form a film (γ). -8~γ-13). The third table shows the state of dissolution of each conductive polymer composition with respect to a solvent, the state of the dried film produced using the same, and the surface resistance value thereof. In the table, the film obtained in Example 1 and Comparative Example 1 and the film (γ-17) when water was used as a solvent were also shown.

From the results, it is understood that the composite conductive polymer composition obtained by oxidizing an aromatic compound using the polymer compound (α-1 to α-5) of the present invention can be dissolved in an aromatic solvent and an ester. The solvent obtained by volatilizing these solvents has high conductivity.

On the other hand, the comparative conductive polymer composition obtained by using the polymer compound having a composition different from that of the polymer compound of the present invention has no solubility with respect to the aromatic solvent or the ester solvent, and the prepared coating is used. The film has almost no conductivity.

Example 16 to Example 22 and Comparative Example 12 to Comparative Example 14

The counter electrode (open copper mesh electrode) and the counter electrode substrate (PET film having a thickness of 80 μm) used in Example 1 of the Japanese International Publication No. WO/2009/013942 were replaced with a thickness of 5 μm after drying. In the method, the solution of the composite conductive polymer composition prepared in Examples 1 to 4 or the solution of the conductive polymer composition prepared in Comparative Example 2 was applied onto a SUS foil, an ITO PEN film, a glass substrate, or the like using a doctor blade. A dye-sensitized solar cell element was produced by forming an ITO glass substrate or an FTO glass substrate.

The obtained dye-sensitized solar cell element was evaluated using Solar Simulator YSS-80A manufactured by Yamashita Denso Co., Ltd. The element characteristics of the unit area of 1 cm ² were investigated for the IV characteristics under irradiation of AM 1.5 (1 sun; 100 mW/cm ² ), thereby estimating the short-circuit current, the open voltage, the full factor, and the power generation efficiency of the unit. The fourth table shows the result.

From the above results, it is understood that the dye-sensitized solar cell element obtained by using the composite conductive polymer composition of the present invention exhibits high photoelectric conversion efficiency.

Example 23 to Example 24 and Comparative Example 15 to Comparative Example 16

The solution of the composite conductive polymer composition prepared in Examples 1 and 2 or the solution of the conductive polymer composition prepared in Comparative Example 2 was adjusted to 2.5% again by spin coating. This was applied to a glass substrate having a thickness of 1000 μm and a PET film substrate of 100 μm under conditions of 4000 rpm to 15 sec, and the solvent was removed by a hot air dryer to prepare an antistatic film having an antistatic layer. The measurement was carried out by a stylus type surface shape measuring device (Dektak 6M; manufactured by ULVAC Co., Ltd.), and as a result, the thickness of the antistatic layer was about 25 nm.

With respect to the obtained antistatic film, the surface resistance value was evaluated after standing under the following conditions. The fifth table shows the results of this evaluation.

Condition (1): 192 hr at 23 ° C, 50% RH

Condition (2): 168 hr at 40 ° C, 80% RH

From the above results, it is understood that the antistatic film of the present invention sufficiently exhibits antistatic characteristics even when used in an environment of high temperature and high humidity.

Industrial availability:

In the composite conductive polymer composition of the present invention, a polymer compound (A) having a highly hydrophobic aromatic ring or an alicyclic group as a main component is used as a dopant, so that it can be stably dissolved in aroma such as toluene. A family solvent or an ester solvent such as ethyl acetate.

Further, the conductive polymer having the composite conductive polymer composition thus obtained is dissolved in an aromatic solvent or an ester solvent to form a composition solution, and the conductive film can be easily formed to be electrically conductive. It is a part of sex, so it can be used extremely favorably in the field of electronic parts and the like.

Further, the dye-sensitized solar electric electrode or the antistatic film using the composite conductive polymer composition of the present invention has better performance.

Claims (18)

A composite conductive polymer composition obtained by polymerizing the following components (a-1) to (a-3), which is doped to be selected from the following formula ( a compound of I) to (III) which is a π-conjugated polymer (β) which is a monomer component and is soluble in toluene or ethyl acetate; (a-1) has a sulfonic acid group and a polymerizable vinyl group. Monomer: 20 to 50 mol%; (a-2) monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%; (however, 50% of hydrogen is removed by a halogen group) Substituted carbon compound having 2 to 30 carbon atoms) (a-3) alkyl (meth)acrylate: 30 to 60 mol%; (In the formula, R ₁ to R ₇ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). The composite conductive polymer composition of claim 1, wherein the monomer having a sulfonic acid group and a polymerizable vinyl group of the component (a-1) is selected from the group consisting of sodium styrene sulfonate and styrene sulfonic acid. (meth) propylene A group of 2-sulfonic acid sodium salt and 2-sulfoethyl (meth)acrylate. The composite conductive polymer composition according to claim 1 or 2, wherein the monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group of the component (a-2) is selected from (methyl) Benzyl acrylate, phenoxyethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene oxyl hexahydrophthalate Ethyl ester, neopentyl glycol benzoate (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, hydroxyethylated o-phenolate (meth)acrylate, (methyl) O-phenylphenol glycidyl ether acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate , a group of dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinylpyridine and (meth)propenylmorpholine By. The composite conductive polymer composition according to claim 1 or 2, wherein the alkyl (meth)acrylate of the component (a-3) is selected from the group consisting of methyl (meth)acrylate and (meth)acrylic acid. Ethyl ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isopropyl (meth)acrylate, (A) Base) butyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate and octadecyl (meth) acrylate Group of people. A method for producing a composite conductive polymer composition, comprising: polymer compound (A) obtained by polymerizing the following components (a-1) to (a-3), and a polymer compound selected from the group consisting of the following components (a-1) to (a-3) The following compounds of the formulae (I) to (III) are coexisted in an electrolytic matrix solvent, and subjected to chemical oxidative polymerization using an oxidizing agent to obtain a composite conductive polymer composition soluble in toluene or ethyl acetate; (a-1) Monomer having a sulfonic acid group and a polymerizable vinyl group: 20 to 50 mol%; (a-2) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%; 50% of hydrogen is a carbon compound having 2 to 30 carbon atoms substituted by a halogen group) (a-3) alkyl (meth)acrylate: 30 to 60 mol%; (In the formula, R ₁ to R ₇ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). The method for producing a composite conductive polymer composition according to claim 5, wherein the monomer having a sulfonic acid group and a polymerizable vinyl group of the component (a-1) is selected from sodium styrene sulfonate and benzene. Ethylene sulfonic acid, sodium 2-sulfoethyl (meth)acrylate and 2-sulfoethyl (meth)acrylate Group of people. The method for producing a composite conductive polymer composition according to claim 5 or 6, wherein the component (a-2) has an aromatic group or a monomer having an alicyclic group and a polymerizable vinyl group, (methyl group) The acrylic monomer is selected from the group consisting of benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(methyl)propenyloxyethyl phthalate, and hexahydroortylene. 2-(Methyl)propenyloxyethyl formate, neopentyl glycol benzoate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, hydroxy (meth)acrylate Ethylated o-phenolate, o-phenylphenol glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Tertiary butyl cyclohexyl methyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, vinyl pyridine and A group of methyl) acryloyl morpholine. The method for producing a composite conductive polymer composition according to claim 5 or 6, wherein the alkyl (meth)acrylate of the component (a-3) is selected from methyl (meth)acrylate, (A) Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate , (butyl) (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate and octadecyl (meth) acrylate The group of esters. A method for producing a composite conductive polymer composition according to claim 5 or 6, wherein the compound is selected from the group consisting of the formulae (I) to (III) In the case of the material, the polymer compound (A) is allowed to coexist in such a manner that the sulfonic acid molar ratio is 0.2 to 1.5. The method for producing a composite conductive polymer composition according to claim 5 or 6, wherein the oxidizing agent is selected from the group consisting of ammonium peroxodisulfate, potassium peroxydisulfate, sodium peroxodisulfate, and iron (III) chloride. , iron (III) sulfate, iron (III) tetrafluoroborate, iron (III) hexafluorophosphate, copper (II) sulfate, copper (II) chloride, copper (II) tetrafluoroborate, copper hexafluorophosphate (II) And an oxidizing agent in the form of ammonium oxydisulfate. The method for producing a composite conductive polymer composition according to claim 5 or 6, wherein the electrolytic matrix solvent is ion-exchanged water. The method for producing a composite conductive polymer composition according to claim 5, wherein the compound selected from the formulae (I) to (III) is added in an amount of from 0.5 to 3.0 mol. The chemical components of hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride and iron (II) sulfate are subjected to chemical oxidation polymerization. A composite conductive polymer composition solution which is dissolved in an aromatic solvent selected from the group consisting of toluene, benzene, and xylene, and/or an ester solvent selected from the group consisting of ethyl acetate, propyl acetate, and butyl acetate. In the state, the composite conductive polymer composition of any one of claims 1 to 4 is contained in an amount of 0.1 to 10% by mass. A composite conductive polymer composition solution in which 0.01 to 45 parts by weight of an aromatic compound having a hydroxyl group is mixed with 100 parts by weight of a solvent of the solution of the composite conductive polymer composition of claim 13 Made. The composite conductive polymer composition solution of claim 14 wherein the aromatic compound having a hydroxyl group is selected from the group consisting of benzyl alcohol, phenol, m-cresol, o-cresol, 2-naphthyl alcohol, 1-naphthalene. a group of alkanols, guaiacols and 2,6-dimethylphenol. The composite conductive polymer composition solution according to any one of claims 13 to 15, which further comprises a metal, an oxidized metal, a conductive polymer composition, a carbon powder or a dispersion. A counter electrode for a dye-sensitized solar cell, which is obtained by using the composite conductive polymer composition according to any one of claims 1 to 4. An antistatic film obtained by using the composite conductive polymer composition according to any one of claims 1 to 4.