TWI595036B - 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 the use of the composition, and more specifically relates to an aromatic system such as aniline, thiophene or pyrrole. When the π-conjugated polymer as a monomer component is a solvent-soluble polymer, the composite conductive polymer composition blended with the polymer emulsifier, a method for producing the same, a solution containing the composition, and the composition Use of a pigment-sensitized solar electric electrode or an antistatic film.

When high conductivity is imparted to the π-conjugated polymer, it is necessary to blend with the dopant. However, the polymer which is originally π-conjugated and developed is a structure in which the planarity of the polymer chain is high, and the crystallinity (overlapping) between the polymer chains by the affinity of the π bond is high. Moreover, the planarity of the blended π-conjugated polymer and the affinity by π-conjugation are further improved by the dopant, so that the overlap property is more remarkable. Therefore, it is difficult to dissolve (heat or solvent) and electrical conductivity of the π-conjugated polymer.

In addition, a polymer in which an alkyl group or an alkoxy group is introduced into a side chain of a π-conjugated polymer has been proposed (Patent Document 1), and it is actually intended to increase to s‧ m or less of 10 to ⁵ of a sufficient conductor. The electrical conductivity must be blended. As a result of the blending, the planarity of the conductive polymer is developed and the π-conjugated affinity is developed, and there is a problem that sufficient solvent solubility cannot be obtained.

When the use of the conductive polymer is considered, it is possible to dissolve by a solvent or melt by heat in view of ease of handling, and it is expected that a self-supporting film having sufficient electrical conductivity after film formation can be obtained or In the past, when these conductive polymers were used, film formation of a polymer film by electrolytic polymerization or vapor exposure on a substrate to be directly conductive, by an oxidizing agent and a conductive polymer precursor monomer The solution is immersed, heated, or the like to carry out film polymerization or the like, and then subjected to a treatment such as blending in the obtained polymer film.

However, at this time, the substrate must be a semiconductor or an electric conductor during electrolytic polymerization, and the corrosion resistance to the electrolyte is also desired, and the usable substrate is limited. Further, in the film polymerization by direct vapor, the oxidizing agent must be homogeneously present on the film to be a polymerization site, and it is not sufficient in terms of film formation control, and in the polymer condenser application used in these methods, When fine surface irregularities are formed when the surface area is to be enlarged, it is difficult to form a conductive polymer on a sufficiently homogeneous surface.

Therefore, attempts have been made to dissolve a conductive polymer in an organic solvent, and several means 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 having a main repeating thiophene unit. The polymer T and the water-dispersible powder of at least one other polyanionic polymer P. However, the method of Patent Document 2 is a method of obtaining a powder or a method of performing oxidative polymerization directly on the surface of a target coating, and it is impossible to dissolve the polymer obtained by the method in a solvent or water, and the like. The revealer is also only a dispersion with good water dispersibility, and is not molecularly soluble for organic solvents.

Further, as a more direct method for dispersing the solvent nanoparticle, various methods have been reviewed. Patent Document 4 discloses that polyaniline which is insoluble in a solvent in nature is pulverized to a nanometer level. A sulfonic acid anionic emulsifier such as SDS (dodecylbenzenesulfonic acid) or PTS (p-toluenesulfonic acid) having high affinity for polyaniline and a solvent is used as a dispersing agent, and is dispersed in a solvent at a nano level. The provision of the microdispersion solution is not substantially soluble in the solvent, so the surface of the coated film becomes convex and concave, and cannot be a self-standing film of polyaniline only (also referred to as a homogeneous film. If the film is formed by a combination of an adhesive or the like, it is impossible to form a film.

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

This patent document is a method for producing poly(extended ethylene dioxide substituted thiophene) (PEDOT) which can be dissolved or dispersed in water or an alcohol solvent in oxidative polymerization in the presence of polystyrenesulfonic acid (PSS) and an oxidizing agent. However, the PEDOT/PSS obtained therein is dispersed in water, but it is not completely dissolved, and it is difficult to suppress the overlap between some PEDOTs and the conductive polymer cannot be sufficiently dissolved.

Further, in Patent Document 6, it is disclosed that aniline or an aniline derivative is oxidatively polymerized in a solvent containing an organic acid or an inorganic acid in the presence of a highly hydrophobic anionic surfactant, and precipitated, separated, and purified. Thereafter, extraction is carried out 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 type, and aniline is subjected to hydrochloric acid chlorination before polymerization, and then substituted with an aniline salt by a sulfonic acid emulsifier, but it is actually difficult to perform sufficient salt exchange. Further, the polyaniline obtained by the synthesis method of the patent document is practically insoluble in a solvent, and has a problem that only a solvent dispersion liquid in a slightly dispersed state is obtained. Further, since the sulfonic acid-based emulsifier having the same amount or more as the aniline is used, the emulsifier other than the substantially blended emulsifier remains at 50% or more, and these emulsifiers must be taken out at the time of use, so that the washing step is relatively high. The complicated problem. Further, in the low-molecular emulsifier, it is very difficult to introduce a system which is effective in dissolving a solvent and inhibiting the stacking of polyaniline as a one-mole design, and it is assumed that it is temporarily dissolved in a solvent. The state of polyaniline also has a problem of immediate microaggregation due to stacking (crystallization of PANI).

Further, Patent Document 7 discloses a solution in which (A) a monomer having a sulfonic acid functional group and a radical polymerizable functional group and (B) a monomer formed from aniline or a derivative thereof is dissolved in water or an organic solvent. After emulsification, the sulfonic acid structure of the monomer of (A) is introduced into the monomer of (B), and the polymerization initiator is polymerized in the following coexistence to polymerize the monomers (A) and (B). A method of combining the polymer of (B) with the conductive polymer of the polymer state of (A).

However, in the method of the patent document, when an ammonium persulfate salt is used as a water-based oxidizing agent and a radical initiator, it is difficult to form a mesh-like structure of an ideal vinyl polymer and polyaniline as described in the present specification. Therefore, in the method of the patent document, there is actually a considerable amount of vinyl polymer not containing PANI, and conversely, a blended monomer not incorporated in a vinyl polymer exists in PANI, or has become very uneven and does not The problem of stable matter.

For example, Patent Document 8 discloses that an organic solvent dissolved in a substance which is substantially not mixed with water contains (a) a protonated substituted or unsubstituted polyaniline composite, and (b) a conductivity of a compound having a phenolic hydroxyl group. Polyaniline composition.

However, this patent document discloses that in the polymerization of a solvent/water/monomer/emulsifier, since the synthesis of polyaniline is carried out using a water-soluble oxidizing agent, the water-soluble aniline monomer is polymerized while being dispersed in the emulsifier. In the system of toluene, polyaniline is formed, and it is substantially impossible to develop a solvent which dissolves a little bit of water other than toluene. Further, in the invention of the patent document, in practice, the sodium diisooctylsulfosuccinate (AOT) used cannot sufficiently suppress the overlap of polyaniline, and therefore it is necessary to use a phenol (cresol) or the like in combination. Although it is not fully described in the specification, the technique described in Non-Patent Document 1 discloses that the affinity of the phenolic compound can be significantly improved by adjusting the supply strength in the polyaniline film, and in the polyaniline film. The improvement in conductivity is useful. In other words, by mixing a non-volatile additive such as a phenol which has good solubility in toluene and good compatibility with polyaniline, the conductivity of the dried coating film can be improved, and the phenol can also inhibit polyaniline in toluene-soluble. Stacking on each other, in the absence of these additives, such as the crystallographic control of the stereoscopically impaired polyaniline of AOT, it is impossible to obtain sufficient solubility, which can be obtained by the inventors' supplementary test. confirm.

On the other hand, as a use of a conductive polymer composition, there is a counter electrode or 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, a dispersion containing a conductive polymer is applied, and a solvent is removed to form a conductive polymer layer. However, since the conductive polymer is a dispersed film of fine particles, adhesion to a transparent conductive layer is poor. The surface energy of the transparent conductive layer must be increased by plasma treatment or the like in advance. Further, in the examples of the patent documents, it is described that polystyrenesulfonic acid is used as the dispersing agent, and in this case, free sulfonic acid is added to the conductive polymer, and the solvent is applied as an aqueous solution to be applied to the film substrate. In the case of the above, the selectivity of the solvent and the surface of the film substrate is very large, and pinholes from the unevenness of the conductive polymer coating film are likely to be generated, and the polarity of the coating film is increased by leaving the sulfonic acid group in the electrolyte solution. The reason why the durability of acetonitrile or an ionic liquid or the like which is generally used is deteriorated, and peeling of the coating film is likely to occur, and the transparent conductive film is corroded by iodine in the electrolytic solution, and There is a problem with the long-term stability, which is not sufficient for the replacement of platinum.

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 to a thermoplastic resin film.

However, in this patent document, although the sugar alcohol is an essential component as an antistatic material, the antistatic film obtained is excellent in transparency or antistatic property, but is used as a blending agent for a polythiophene compound. An acidic polymer such as polystyrenesulfonic acid has a problem of reducing adhesion and antistatic property by temporally absorbing moisture of the antistatic film.

[Advanced technical literature]

[Patent Literature]

[Patent Document 1] Special Table 2002-539287

[Patent Document 2] Special Kaiping 01-313521

[Patent Document 3] Special Table 2004-514753

[Patent Document 4] Special Table 2007-518859

[Patent Document 5] Patent No. 2636968

[Patent Document 6] Special Opening 2008-169255

[Patent Document 7] Special Opening 2007-314606

[Patent Document 8] WO2005/052058

[Patent Document 9] Special Opening 2000-344823

[Patent Document 10] Special Opening 2006-155907

[Patent Document 11] Special Opening 2008-179809

[Non-patent literature]

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

In the present invention, it is an object of providing a homogeneous film which is excellent in solubility in a solvent, a self-standing film, that is, a pinhole or the like, a conductive polymer composition which is a molded body, a method for producing the same, and a method for producing the same.

The inventors of the present invention have tried to solve the above problems, and have added a test to review the results of the above-mentioned prior art. <1> It is necessary to use a sufficiently electrolytic solvent in the polymerization of a π-conjugated polymer, and it is necessary to provide a stable and uniform system for the anion to be oxidized. <2> It is necessary to control the superposition of the π-conjugated polymer during polymerization and to supply the stabilized monomer, and <3> the blending of the π-conjugated polymer in the case of these polymerization growth is Actively proceeding, <4> In these blending processes, it may be precipitated by an electrolytic qualification solvent in the initial polymerization state such as water, and <5> the π-conjugated polymer after polymerization may be caused by a stereoscopic molecular barrier. The overlap of the chain skeleton is suppressed. <6> These three-dimensional barrier factors are such that the substance itself does not have crystallinity, and can be purified from the initial stage of synthesis of the conductive polymer such as solvent or heat, to the solvent. The fact that the redissolution is necessary is made clear.

In addition, the present inventors further examined the results and found that the polymer compound which copolymerizes a specific monomer can be used as an additive in the polymerization of a π-conjugated polymer, and can exhibit a uniform state of the polymerization field as an emulsifier. In addition to the function of the blended material, the composite conductive polymer composition having excellent solubility in a specific solvent can be obtained because of its moderate steric hindrance to the π-conjugated polymer. In addition, the present inventors have found that the composite conductive polymer composition can be used in a dye-sensitized solar electric counter electrode or an antistatic film to complete the present invention.

That is, the present invention is to have the following components (a-1) and (a-2)

(a-1) 20 to 45 mol% of a monomer containing a sulfonic acid group and a polymerizable vinyl group

(a-2) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group 55 to 80 mol%

The polymer compound (A) as a constituent component is blended and will be selected from the following formulas (I) to (III)

A compound conductive polymer composition obtained by using a compound of the formula (wherein R ₁ to ₇ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) as a monomer constituent π-conjugated polymer (β).

Further, the present invention is to use the following components (a-1) and (a-2)

(a-1) monomer having a sulfonic acid group and a polymerizable vinyl group 20 to 45 mol%

(a-2) 55 to 80 mol% of a monomer having an aromatic or alicyclic group and a polymerizable vinyl group

The polymer compound (A) which is subjected to radical polymerization, and a compound which is selected from the above formulas (I) to (III) are present in an electrolytic matrix solvent, and are chemically oxidized and polymerized using an oxidizing agent to form a composite conductive polymer. A method of producing a composition.

Further, in the present invention, the composite conductive polymer composition is contained in an aromatic solvent selected from the group consisting of toluene, benzene, and xylene, and is dissolved in an amount of 0.1 to 10% by weight to form a solution of the composite conductive polymer composition.

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

Further, the present invention is an antistatic film formed using the above composite conductive polymer composition.

[Effects of the Invention]

In the presence of the polymer emulsifier of the present invention, the composite conductive polymer obtained by the polymerization of an oxidizing agent is stably dissolved in an aromatic solvent such as toluene.

Therefore, the solution of the composite conductive polymer is dissolved in an aromatic solvent, and applied to a portion where conductivity is required, and the conductive film can be easily obtained by drying.

Form of implementing the invention

The polymer compound (A) used in the present invention may have an aromatic group of the component (a-1) having a sulfonic acid group and a polymerizable vinyl group, and the component (a-2) according to a usual method. The alicyclic group is produced by radical polymerization of a monomer of a polymerizable vinyl group.

The monomer having a sulfonic acid group and a polymerizable vinyl group as the component (a-1) may, for example, be a monomer having a sulfonic acid group such as a styrenesulfonic acid group or a sulfoethyl group. a styrene sulfonate such as sodium styrenesulfonate or sodium styrenesulfonate, potassium styrenesulfonate or calcium styrenesulfonate, ethyl 2-sulfonic acid (meth)acrylate, or ethyl (meth)acrylate Ethyl 2-sulfonate such as sodium 2-sulfonate, potassium ethyl 2-sulfonate (meth)acrylate or calcium ethyl 2-sulfonate (meth)acrylate.

Further, examples of the monomer having an aromatic or alicyclic group and a polymerizable vinyl group as the component (a-2) include benzyl (meth) acrylate and phenoxyethyl (methyl). Acrylate, ethyl 2-methyl phthalate (meth) acrylate, ethyl 2-ethyl phthalate (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl ( Methyl) acrylate, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate Ester, (meth) acrylate morpholine, styrene, dimethyl styrene, naphthalene (meth) acrylate, vinyl naphthalene, vinyl n-ethyl carbazole, vinyl hydrazine, and the like.

In the production of the polymer compound (A) used in the present invention, the molar ratio of the component (a-1) to the component (a-2) is important. In other words, the polymer emulsifier of the present invention can be applied to the conductive polymer composition by appropriately balancing the hydrophobicity of the aromatic or alicyclic group and the hydrophilicity of the sulfonic acid group. Dissolved in a solvent.

The amount of the component (a-1) to be produced by using the polymer compound (A) used in the present invention is 20 to 45 mol%, preferably 25 to 40 mol%. Further, the amount of the component (a-2) is from 55 to 80 mol%, preferably from 60 to 75 mol%.

The polymer compound (A) of the present invention may contain a polymerizable component other than the above components (a-1) and (a-2). Examples of the polymerizable component include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Alkyl (meth) acrylate such as lauryl (meth) acrylate, (meth) acrylate, 2-hydroxy (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl acetoacetate (meth) acrylate, tetrahydro fluorenyl (meth) acrylate, N, N-dimethyl The amount of the aminoethyl (meth) acrylate or the like to be added is about 0 to 20 mol%.

The radical polymerization reaction of the above component (a-1), component (a-2), and optionally a polymerizable component may be carried out by a known method. For example, after mixing these components, a polymerization initiator is added thereto, and it can be produced by starting polymerization by heating, light irradiation, or the like.

The polymerization method to be used in the production of the polymer compound (A) is not particularly limited as long as it can be carried out without separating the component (a-1) from the monomer mixture, and for example, it can be used. A solution polymerization method, a bulk polymerization method, a precipitation polymerization method, or the like.

In addition, the polymerization initiator used in the polymerization reaction is not particularly limited as long as it is the above-mentioned respective components or a solvent which can be dissolved in the reaction. Examples of the polymerization initiator include an oil-soluble peroxide-based thermal polymerization initiator such as benzoyl peroxide (BPO) and an oil-soluble azo heat such as azobisisobutyronitrile (AIBN). A water-soluble azo-based thermal polymerization initiator such as a polymerization initiator or azobiscyanojimic acid (ACVA). Further, when the ratio of water in the solvent for 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, a combination of a redox agent such as ferrocene or an amine may also be used.

The use range of these polymerization initiators can be arbitrarily used in the range of 0.001 to 0.1 mol per mol of the above-mentioned compound 1 mol, and any method including one input, drip input, and successive input can be used. Further, in the case of solution polymerization using a bulk polymerization or a small amount (50 wt% or less of a monomer), a polymerization method in which a thiol and a metal aromatic are combined may be used (Patent Document 9).

Further, as a solvent to be used in the above polymerization reaction, an alcohol solvent such as methanol, ethanol, isopropyl alcohol or butanol, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone or a methyl group may be mentioned. A solvent such as a diol solvent such as cyprosone, ethyl celecoxib, propylene glycol methyl ether or propylene glycol ethyl ether, or a lactic acid solvent such as methyl lactate or ethyl lactate.

Further, in the polymerization, a chain shifting agent may be used in addition to the polymerization initiator, and it may be suitably used if the molecular weight is to be adjusted. As the chain-transporting agent which can be used, any of the above monomers or a substance soluble in a solvent may be used, and for example, an alkanethiol such as dodecyl mercaptan or heptyl mercaptan may be suitably used. An oily radical inhibitor such as a water-soluble thiol having a polar group such as mercaptopropionic acid (BMPA) or an α-styrene dimer (ASD).

Further, the polymerization reaction is preferably carried out at a temperature below the boiling point of the solvent to be used (except in the case of bulk polymerization), and is preferably, for example, about 65 ° C to 80 ° C. However, when polymerization such as block polymerization or thiol and metal aryl is carried out as in Patent Document 9, it is preferably carried out at 25 ° C to 80 ° C.

The polymer thus obtained can be purified as necessary to obtain a polymer compound (A). As an example of the purification method, an oily weak solvent such as hexane is used, and after oily low molecular impurities, residual monomers, and low molecular impurities are taken out, the polymer is precipitated with an aqueous weak solvent such as acetonitrile, methanol, ethanol or acetone. A method of taking out water-based impurities and residues.

The reason why the purification is preferable is that the polymer compound (A) is introduced as a blending agent in the conductive polymer composition, and is used as a stack inhibitor, and the solvent acts as a solvent, so that it is used as a polymer. When the residue of the polymerization initiator, the monomer, the oligomer, the uneven composition, and the like remaining in the residue remain, the function of the conductive polymer composition is lowered, which is necessary. However, as a result of the purification, the heterogeneous radical polymer of Patent Document 7 is not mixed, and the composition of the polymer composition (A) which can exhibit a uniform conductive polymer composition can be melted together. Dissolved state.

The polymer compound (A) obtained above has a GPC-equivalent weight average molecular weight of 3,000 to 100,000. When the weight average molecular weight is less than 3,000, the function as a polymer emulsifier is not sufficient. On the other hand, when it is 100,000 or more, the solubility of the polymerizable polymer (acid aqueous solution) may be insufficient in the synthesis of the conductive polymer, and the solvent solubility of the polymer emulsifier itself may be deteriorated, or for the conductive polymerization. The solubilization of matter has a significant adverse effect.

The composite conductive polymer composition of the present invention is produced as follows by using the polymer compound (A) obtained as described above. In other words, the polymer compound (A) is dissolved in an electrolytic matrix solvent, and then the compound represented by the above formulas (I) to (III) which is a raw material of the π-conjugated polymer (β) is added to the solution, and further By oxidizing the oxidizing agent, a π-conjugated polymer (β) having a compound represented by the above formulas (I) to (III) as a monomer component can be blended with the polymer compound (A). A composite conductive polymer compound.

In the compound of the starting material, the compound represented by the formula (I) is an aniline wherein the 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, and 2 ,6-dimethylaniline, 2-ethylaniline, 3-ethylaniline, 2-isopropylaniline, 3-isopropylaniline, 2-methyl-6-ethylaniline, 2-n-propyl Aniline, 2-methyl-5-isopropylaniline, 2-butylaniline, 3-butylaniline, 5,6,7,8-tetrahydro-1-naphthylamine, 2,6-diethyl Alkyl aniline and the like.

Further, the compound represented by the formula (II) is a thiophene wherein the substituent is hydrogen or an alkyl group, and specific examples thereof include thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, and 3- Butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-n-octylthiophene.

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

As an example of a specific method of the composite conductive polymer composition produced by the method of the present invention, first, the ion-exchanged water is acidified as necessary, and then the polymer compound obtained as described above is added thereto (A). After that, one or two or more kinds of the compounds of the formulae (I) to (III) are added thereto, and a oxidizing agent is further added to carry out oxidative polymerization.

In addition, a ketone solvent such as acetone or methyl ethyl ketone, an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a hydrophilicity such as acetonitrile can be suitably used in combination with the solubility of the polymer compound (A) in ion-exchanged water. High organic solvent.

In the above reaction, examples of the acidic component to be used for making the electrolytic matrix solvent acidic include hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride, iron (II) sulfate, and the like. The compound of the formula (I) to (III) may be used in an amount of from 0.5 to 3.0 mol.

Further, the oxidizing agent used for the reaction must be appropriately adjusted by the oxidation-reduction potential of the aromatic compound (monomer) forming the composite conductive polymer composition, but ammonium peroxodisulfate or potassium peroxydisulfate can be used. Sodium peroxodisulfate, iron (III) chloride, iron (III) sulfate, iron (III) tetrafluoroborate, iron (III) hexafluoroantimonate, copper (II) sulfate, copper (II) chloride, tetrafluoroethylene Copper (II) borate, copper (II) hexafluoroantimonate, and the like.

Further, since the ratio of the polymer compound (A) to the compounds (I) to (III) in the reaction depends on the properties of the finally obtained composite conductive polymer composition, it is not necessarily determined, for example, preferably. In the example of the range, the molar ratio of the sulfonic acid group in the polymer compound (A) to the molar ratio of the compounds (I) to (III) to be used can be as follows.

In other words, the polymer compound (A) may be present in an amount of from 0.2 to 1.5 in terms of the molar ratio of the sulfonic acid group in the compound to the compound 1 selected from the group consisting of the compounds (I) to (III).

Further, the amount of the oxidizing agent used is generally 1.5 to 2.5 mol (1 valent conversion) for the compound (I) to (III) 1 mol, but by the degree of oxidation (acidity) in the system, for the single In the case of the body 1 mol, the polymerization can be sufficiently carried out even if it is 1 mol or less.

Further, in order to obtain the temperature of the polymerization reaction of the composite conductive polymer composition, the calorific value after the oxidation reaction or the ease of hydrogen removal differs depending on the types of the compounds (I) to (III), so the preferred 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.

Further, when the composite conductive polymer composition is subjected to high molecular weight, the reaction temperature may be relatively lowered, and the reaction time may be relatively extended. If the molecular weight is to be lowered, the reverse is only possible. .

The polymer thus obtained may be a composite conductive polymer composition of the object after further washing as necessary. This is a stable dissolution in an aromatic solvent such as toluene which does not dissolve the conductive polymer composition in the past.

As an example of the method of using the composite conductive polymer composition of the present invention, the composite conductive polymer composition solution which is dissolved in a homogeneous state in an aromatic solvent is exemplified. The composite conductive polymer composition solution is applied to a portion where a conductive film is required to be formed, and then the aromatic solvent in the composition is volatilized by drying or the like to form a uniform conductive film in the target portion. .

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 to a level of from 0.1 to 10% by mass.

Further, in the above-mentioned composite conductive polymer composition solution, benzyl alcohol, phenol, m-cresol, o-cresol, and benzyl alcohol, phenol, m-cresol, and o-cresol may be further added for the purpose of improving the stability of the solution and improving the conductivity in the coating state. An aromatic compound having a hydroxyl group such as 2-naphthyl alcohol, 1-decalinol, o-methoxyphenol or 2,6-dimethylphenol. The compound having such a hydroxyl group is preferably added in an amount of from 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.

Further, in the above-mentioned composite conductive polymer composition solution, the conductivity of the self-supporting film which is an antistatic paint is improved, and the catalyst performance of the solar cell is improved, and copper, silver, and aluminum may be further contained. Metals such as platinum, such as platinum, titanium oxide, indium tin oxide, fluorine-doped tin oxide, aluminum oxide, cerium oxide, etc., conductive polymer composition, carbon nanotube (CNT), fullerene, carbon black A carbon powder or a dispersion is used as a filler component. These powders or dispersions are 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 composite conductive polymer composition solution.

Further, as the composite conductive polymer composition, a counter electrode for a dye-sensitized solar cell can be used. When the transparency of the dye-sensitized solar cell is required to be transparent, the composite conductive polymer composition is laminated on one surface of the transparent substrate, or a light-transmitting electrode is disposed on one surface of the transparent substrate, and the light is transmitted through the light-transmitting electrode. The electrode can be formed by laminating the above composite conductive polymer composition. Further, when transparency is not required, it can be formed by lamination by 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.

As the transparent substrate to be used, the light transmittance is usually 50% or more, and preferably 80% or more of a film or a sheet can be used. Examples of such a transparent plate include inorganic transparent substrates such as glass, polyethylene terephthalate (PET), polycarbonate (PC), polyphenylene sulfide, polyfluorene, polyester fluorene, and poly. A polymer transparent substrate such as an alkyl (meth) acrylate, polyethylene naphthalate (PEN), a polyether oxime (PES) or a polycycloolefin. Further, examples of the metal foil include metal foils such as gold, platinum, silver, tin, copper, aluminum, stainless steel, and nickel.

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 the range can impart flexibility to the obtained dye-sensitized solar cell.

Further, a light transmissive electrode may be disposed on one surface of the transparent substrate as necessary. Examples of the light transmissive electrode used herein include a film-shaped conductive metal electrode and a mesh-shaped conductive metal electrode.

The film-shaped conductive metal electrode is formed by forming tin oxide, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), or the like into a film shape. The film-shaped conductive metal electrode is formed on the surface of the transparent substrate by tin oxide, ITO, FTO or the like by vapor deposition or sputtering. 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 sieve shape. Specifically, a conductive metal such as copper, nickel or aluminum is used as the mesh-shaped conductive metal electrode. For example, by photolithography, the line width can be generally 10 to 70 μm, preferably 10 to 20 μm, pitch. It is formed by a sieve having a width of usually 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 slightly 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 surface of the transparent substrate of the mesh-shaped conductive metal electrode can be adhered with an adhesive or the like.

When the counter electrode for a dye-sensitized solar cell is produced, a method of laminating a composite conductive polymer composition on a light-transmitting electrode disposed on one surface of the transparent substrate or the transparent substrate may be, for example, a configuration. The composite conductive polymer composition solution is applied to the light-transmissive electrode on the transparent substrate sheet surface or the transparent substrate surface, and the solvent in the solution is removed one to several times.

The coating of the composite conductive polymer composition solution can be applied to a known coating such as dip coating, microrod coating, roll coating, comma coater, die coating, or gravure coating.

Further, the removal of the solvent can be carried out by a method such as natural drying by standing, forced drying under heating by hot air or infrared rays.

In the above-mentioned dye-sensitized solar cell, the above-mentioned composite conductive polymer composition is soluble in an organic solvent, and is therefore more soluble than a dispersion in which a conventional composite conductive polymer composition is dispersed in an aqueous medium. The coating step is easier and the productivity is better. Further, it is possible to suppress deterioration of metal corrosion at the time of producing a step from the counter electrode of the acidic aqueous solution.

Further, the above-mentioned composite conductive polymer composition using the dye-sensitized solar cell is extremely useful, and the component (a-1), component (a-2), and component (a-3) are used. The polymer compound (A) obtained by copolymerization in a predetermined range is excellent in adhesion to the transparent substrate or the light-transmitting electrode or the metal foil, and therefore can be used for a long period of time.

Further, the above-mentioned composite conductive polymer composition used in the above-described dye-sensitized solar cell is excellent in use, and the component (a-1), the component (a-2) and the component (a- are suppressed by use. 3) The polymer compound (A) having a degree of acidity obtained by copolymerization in a predetermined range can prevent the light-transmitting electrode (conductive metal) from being corroded, and the durability against the electrolytic solution can be improved, so that the polymer can be used for a long period of time. use.

In addition, the above-mentioned dye-sensitized solar cell is extremely useful, and a high-priced platinum electrode used as an electrode having oxidation resistance to a conventional electrolytic solution can provide a composite conductive polymer film as a uniform oxidation-resistant film, and can provide an inexpensive A variety of metals that can be used.

Further, the antistatic film formed using the composite conductive polymer composition is such that the composite conductive polymer composition is coated and dried separately, and the film is formed into a self-standing film to process a low-resistance antistatic film. . In addition, when the composite conductive polymer composition, the thermoplastic resin, and/or the thermosetting resin are mixed as necessary, the mold can be melt-kneaded by an extruder or an extruder or the like, and a T mold or the like can be used. (2) coating the composite conductive polymer composition solution on the surface of the thermoplastic resin, the thermosetting resin, and the glass film or on both sides of the film, and removing the solvent in the solution to form an antistatic layer. The method is obtained.

Examples of the thermoplastic resin used for the antistatic film include polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, and polyacrylonitrile. Styrene, polyacrylonitrile styrene, polymethacryl, polypropylene, saturated polyester, polyamide, polycarbonate, poly-derivative phenyl ether, polyphenylene sulfide, polyfluorene, polyacrylate Liquid crystal polymers, polyetheretherketone, polyamidimide, etc., also include polymer alloys or thermoplastic elastomers of these thermoplastic resins.

Examples of the thermosetting resin used for the antistatic film include polyphenol, polyepoxy, unsaturated polyester, polyurethane, polyimine, polyurea, polyoxyxylene resin, melamine resin, fluororesin, Alkyd resin, etc.

Further, the antistatic film is a polymer compound (A) obtained by copolymerizing the component (a-1), the component (a-2) and the component (a-3) in a predetermined range. It forms an anti-static film with less variation in performance under various high-humidity and low-humidity conditions and high permeability.

[Examples]

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

<molecular weight>

The measurement was carried out by GPC under the following conditions.

Device name: HLC-8120 (TOSOH system)

Pipe column: GF-1G7B+GF-510HQ (Asahipak: registered trademark, Showa Denko (share) system)

Reference material: polystyrene and sodium polystyrene sulfonate

Sampling concentration: 1.0mg/ml

Dissolved solution: 50mmol lithium chloride aqueous solution / CH ₃ CN=60/40wt

Flow rate: 0.6ml/min

Column temperature: 30 ° C

Detector: UV254nm

<surface resistance>

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

Example 1 (1) Polymerization of polymer compound (A-1) (2-sodium sulfoethyl methacrylate/benzyl methacrylate = 30/70):

21.7 g of 2-sodium sulfoethyl methacrylate and 100 g of benzyl methacrylate were placed in a four-necked beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. 150 g of ion-exchanged water and 300 g of isopropyl alcohol. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Next, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of polymer compound (A-1):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added by stirring with a stirrer, and then left to stand for 1 hour to remove an oil layer containing impurities. After removing the oil layer, 1 kg of methanol was added dropwise over 1 hour to precipitate a solid component. The precipitated solid component was separated by filtration, and dried at 100 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-1) (EP-1). The obtained polymer compound (A-1) (EP-1) was measured by gel permeation chromatography (GPC), and the weight average molecular weight (Mw) was 41,000.

(3) Polyaniline polymerization and purification:

The polymer compound (A-1) (EP-1) obtained in the above (2) was placed in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet tube, a reflux condenser, an inlet, and a thermometer, and 15.6 g of the polymer compound (A-1) (EP-1) obtained in the above (2). 200 g of ion-exchanged water and 6 g of a 35% hydrochloric acid aqueous solution were heated at 60 ° C, stirred for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and after stirring, it became a homogeneous emulsion. 50 g of iron (III) sulfate was dissolved in 150 g of ion-exchanged water, and it was dropped into a beaker kept at 25 ° C for 10 hours. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the polymerization reaction was continued for 48 hours.

The polymerization solution after the completion of the polymerization reaction was separated by filtration, and the obtained solid component was again dispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried at 40 ° C for 96 hours under reduced pressure to obtain a composite conductive polymer composition (E-1). The volatile matter of the composite conductive polymer composition (E-1) was measured and found to be 2% or less. Further, the volatile polymer composition was placed in a hot air circulation type dryer at 105 ° C for 3 hours, and the mass loss rate before and after (the same applies hereinafter).

(4) Coating evaluation:

5 g of the composite conductive polymer composition (E-1) obtained in the above (3) and 95 g of toluene were placed in a beaker, and stirred at room temperature to obtain a toluene solution of the composite conductive polymer composition (E-1). liquid. The appearance of the solution was yellow-green.

The toluene solution was continuously dried using a doctor blade, and after drying to a thickness of 10 μm, it was applied on a glass substrate and dried to obtain a green uniform coating film. The surface resistivity of the coating film was 100 k?/?.

Example 2 (1) Polymerization of polymer compound (A-2) (2-sodium sulfoethyl methacrylate/cyclohexyl methacrylate = 35/65):

60.3 g of 2-sodium sulfoethyl methacrylate and 88.6 g of cyclohexyl methacrylate were placed in a four-necked beaker having a capacity of 1000 cm ³ with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an input port, and a thermometer. 150 g of ion-exchanged water and 300 g of isopropyl alcohol. The mixture in the beaker was heated to reflux temperature by introducing nitrogen into the beaker. 0.7 g of azobisisobutyronitrile was continuously added to the beaker, and polymerization was carried out for 20 hours while maintaining the reflux state to obtain a polymer.

(2) Purification of polymer compound (A-2):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After removing the oil layer, 1 kg of methanol was added dropwise over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 100 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-2) (EP-2). The Mw of the obtained polymer compound (A-2) (EP-2) was 45,000.

(3) Polyaniline polymerization and purification:

The polymer compound (A-2) (EP-2) obtained in the above (2), 13.1 g, ion, was placed in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet tube, a reflux condenser, an inlet, and a thermometer. 200 g of water and 6 g of a 35% hydrochloric acid aqueous solution were exchanged, and the mixture was stirred at 60 ° C for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and the mixture was stirred to form a uniform emulsion. 10 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the inside of the beaker was kept at 0 ° C and dripped for 10 hours. After the completion of the dropwise addition, the mixture was returned to room temperature (25 ° C), and polymerization was continued for 48 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and then filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried under reduced pressure at 40 ° C for 96 hours to obtain a composite conductive polymer composition (E-2). The volatile matter of the composite conductive polymer composition (E-2) was measured to obtain a volatile matter of 2% or less.

(4) Coating evaluation:

5 g of the composite conductive polymer composition (E-2) obtained in the above (3), 90 g of toluene, and 5 g of methyl ethyl ketone were placed in a beaker, and stirred at room temperature to obtain a composite conductive polymer composition (E). -2) Toluene ‧ methyl ethyl ketone solution. The appearance of the solution was yellow-green.

The composite conductive polymer composition (E-2) solution was applied to a glass substrate by using a doctor blade to have a thickness of 10 μm after drying, and then dried to obtain a green uniform coating film. The surface resistivity of the coating film was 250 k?/?.

Example 3 (1) Polymerization of polymer compound (A-3) (2-sodium sulfoethyl methacrylate/phenoxyethyl methacrylate = 35/65):

60.3 g of 2-sodium sulfoethyl methacrylate and phenoxyethyl methacrylate 108.6 were placed in a four-pot beaker having a capacity of 1000 cm ³ with a stirrer, a nitrogen gas introduction tube, a reflux cooler, an input port and a thermometer. g, 150 g of ion-exchanged water and 300 g of isopropyl alcohol. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 20 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of polymer compound (A-3):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 100 ° C under reduced pressure for 36 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-3) (EP-3). The Mw of the obtained polymer compound (A-3) (EP-3) was 44,000.

(3) Polyaniline polymerization:

The polymer compound (A-3) (EP-3) 14.9 g, ion-exchanged water 200 g, 35% was placed in a four-a-tube beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet tube, a reflux condenser, an inlet, and a thermometer. 6 g of an aqueous hydrochloric acid solution was stirred at 60 ° C for 3 hours while heating, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and the mixture was stirred to form a uniform emulsion. 10 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the inside of the beaker was kept at 5 ° C and dripped for 8 hours. After the completion of the dropwise addition, the room temperature (25 ° C) was reproduced and the polymerization was continued for 36 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried at 30 ° C for 110 hours under reduced pressure to obtain a composite conductive polymer composition (E-3). As a result of measuring the volatile matter of the composite conductive polymer composition (E-3), the volatile matter was 1% or less.

(4) Coating evaluation:

5 g of the composite conductive polymer composition (E-3) obtained in the above (3) and 95 g of toluene were placed in a beaker, and stirred at room temperature to obtain a toluene solution of the composite conductive polymer composition (E-3). The appearance of the solution was yellow-green.

The toluene solution of the composite conductive polymer composition (E-3) was applied to a toluene solution to have a thickness of 10 μm after drying, and was applied onto a glass substrate, followed by drying to obtain a green uniform coating film. The surface resistivity of the coating film was 500 k?/?.

Example 4 (1) Polymerization of polymer compound (A-4) (sodium p-styrenesulfonate/benzyl methacrylate = 40/60):

67 g of sodium p-styrenesulfonate, 85.9 g of benzyl methacrylate, and 150 g of ion-exchanged water were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. Isopropyl alcohol 300g. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of polymer compound (A-4):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 70 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-4) (EP-4). The Mw of the obtained polymer compound (A-4) (EP-4) was 31,000.

(3) Polyaniline polymerization:

The polymer compound (A-4) (EP-4) obtained in the above (2) was charged with 11.8 g and ion exchange in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet, a reflux condenser, an inlet, and a thermometer. After 100 g of water and 6 g of a 35% hydrochloric acid aqueous solution were stirred at 60 ° C for 3 hours by heating, 100 g of saturated brine was added thereto, and the mixture was cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and the mixture was stirred to form a uniform emulsion. 10 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the inside of the beaker was kept at 0 ° C and dripped for 8 hours. After the completion of the dropwise addition, the mixture was kept at 0 ° C, and the polymerization reaction was continued for 30 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated five times to obtain a solid matter containing water. The solid was dried at 30 ° C for 110 hours under reduced pressure to obtain a composite conductive polymer composition (E-4). As a result of the volatile matter of the composite conductive polymer composition (E-4), the volatile matter was 1% or less.

(4) Coating evaluation:

5 g of the composite conductive polymer composition (E-4) obtained in the above (3), 70 g of toluene, and 25 g of cyclopentanone were placed in a beaker, and stirred at room temperature to obtain a composite conductive polymer composition (E-4). ) a toluene solution. The appearance of the solution was yellow-green.

The toluene solution of the composite conductive polymer composition (E-4) was applied to a glass substrate by using a doctor blade to have a thickness of 10 μm after drying, and then dried to obtain a green uniform coating film. The surface resistivity of the coating film was 120 k?/?.

Example 5 (1) Polymerization of polymer compound (A-5) (sodium p-styrenesulfonate/benzyl methacrylate = 40/60):

67 g of sodium p-styrenesulfonate, 85.9 g of benzyl methacrylate, and 150 g of ion-exchanged water were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. Isopropyl alcohol 300g. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of polymer compound (A-5):

The whole amount of the obtained polymer solution was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 70 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-5) (EP-5). The Mw of the obtained polymer compound (A-5) (EP-5) was 31,000.

(3) Polythiophene polymerization:

The polymer compound (A-5) (EP-4) obtained in the above (2) was charged into a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet, a reflux condenser, an inlet, and a thermometer, and ion exchange was carried out. 200 g of water and 4.8 g of a 35% hydrochloric acid aqueous solution were stirred at 60 ° C for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 3.2 g of thiophene was added to the emulsifier solution, and the mixture was stirred to form a uniform emulsion. 24.8 g of iron (III) chloride was dissolved in 100 g of ion-exchanged water, and the inside of the beaker was kept at 90 ° C and dripped for 10 hours. After the completion of the dropwise addition, the temperature was maintained at 90 ° C, and the polymerization reaction was continued for 72 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried under reduced pressure at 40 ° C for 96 hours to obtain a composite conductive polymer composition (E-5). As a result of measuring the volatile matter of the composite conductive polymer composition (E-5), the volatile matter was 0.5% or less.

(4) Coating evaluation

5 g of the composite conductive polymer composition (E-5) obtained in the above (3), 70 g of toluene, and 25 g of cyclopentanone were placed in a beaker, and stirred at room temperature to obtain a composite conductive polymer composition (E-5). Toluene ‧ methyl ethyl ketone solution. The appearance of the solution was dark green.

A solution of the composite conductive polymer composition (E-5) was applied to a glass substrate by applying a doctor blade to a thickness of 10 μm after drying, followed by drying to obtain a black-green uniform coating film. The surface resistivity of the coating film was 30 k?/?.

Example 6 (1) Polymerization of polymer compound (A-6) (sodium p-styrenesulfonate/BzMA=40/60)

67 g of sodium p-styrenesulfonate, 85.9 g of benzyl methacrylate, and 150 g of ion-exchanged water were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. Isopropyl alcohol 300g. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. 0.7 g of azobisisobutyronitrile was continuously placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state.

(2) Purification of polymer compound (A-6)

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 70 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-6) (EP-6). The Mw of the obtained polymer compound (A-6) (EP-6) was 31,000.

(3) Polymerization of polypyrrole (polymer compound (A-6) 50%, hydrochloric acid 1.2 times)

The polymer compound (A-6) (EP-6) obtained in the above (2) was charged with 11.8 g of the polymer (A-6) obtained in the above (2) in a four-necked beaker having a capacity of 500 cm ^{3 of} a stirrer, a nitrogen gas inlet tube, a reflux condenser, an inlet, and a thermometer. 6 g of a 35% hydrochloric acid aqueous solution was stirred at 60 ° C for 3 hours by heating, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 3.3 g of pyrrole was introduced into the emulsifier solution, and the mixture was stirred to form a uniform emulsion. 10.0 g of ammonium peroxodisulphate was dissolved in 30 g of ion-exchanged water, and the mixture was dropped in a beaker kept at 0 ° C for 10 hours. After the end of the dropwise addition, the temperature was maintained at 0 ° C, and the polymerization was continued for 30 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried under reduced pressure at 40 ° C for 72 hours to obtain a composite conductive polymer composition (E-6). As a result of measuring the volatile matter of the composite conductive polymer composition (E-6), the volatile matter was 1% or less.

(4) Coating evaluation

5 g of the composite conductive polymer composition (E-6) obtained in the above (3), 90 g of toluene, and 5 g of methyl ethyl ketone were placed in a beaker, and stirred at room temperature to obtain a composite conductive polymer composition (E-5). ) toluene ‧ methyl ethyl ketone solution. The appearance of the solution was black.

A solution of the composite conductive polymer composition (E-6) was applied to a glass substrate by applying a doctor blade to a thickness of 10 μm after drying, followed by drying to obtain a black uniform coating film. The surface resistivity of the coating film was 70 k?/?.

Comparative example 1 (1) Polymerization of a comparative polymer compound (A-7) (2-sodium sulfoethyl methacrylate/benzyl methacrylate = 15/85):

25.9 g of 2-sodium sulfoethyl methacrylate and 121.4 g of benzyl methacrylate were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. 100 g of ion-exchanged water and 400 g of isopropyl alcohol. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of comparative polymer compound (A-7):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 70 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-7) (CP-1). The Mw of the obtained polymer compound (A-7) (CP-1) was 35,000.

(3) Polyaniline polymerization (50% of polymer compound (A-7) and 1.2 times of hydrochloric acid)

30.2 g of the polymer compound (A-7) (CP-2) obtained in the above (2), and ion exchange, were placed in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet, a reflux condenser, an inlet, and a thermometer. 200 g of water and 6 g of a 35% hydrochloric acid aqueous solution were weighed in a beaker, and heated and stirred at about 60 ° C, but insoluble matter remained and could not be completely dissolved.

Further, 4.65 g of aniline was added to the beaker, and after stirring, it became an uneven emulsion in which insoluble matter remained. 10.0 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the mixture was dropped in a beaker kept at 0 ° C for 10 hours. After the completion of the dropwise addition, the temperature was maintained at 0 ° C. After the polymerization reaction was continued for 10 hours, white crystals were observed in the reaction mixture, and a part thereof became agglomerate. Therefore, 50 g of water was added thereto, and the mixture was returned to room temperature, followed by stirring for 36 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried under reduced pressure at 40 ° C for 72 hours to obtain a polymer (C-1). As a result of measuring the volatile matter of the polymer (C-1), the volatile matter was classified into 1% or less.

(4) Coating evaluation:

5 g of the polymer (C-1) and 95 g of toluene obtained in the above (3) were placed in a beaker, and stirred at room temperature, but the polymer (C-1) was not dissolved, and a part of a finely dispersed solution in which a precipitate was produced was obtained.

The dispersion of the polymer (C-1) was filtered through a 200-mesh filter, and the filtrate was dried using a doctor blade to have a thickness of 10 μm after drying. The film was applied to a glass substrate and dried to obtain a uniform particle film. The film was formed into a film having a peeling effect when rubbed with a finger, and the film was not able to be a uniform self-standing film obtained in Examples 1 to 6, and the surface resistance value was 10 ⁷ Ω/□ or more.

Comparative example 2 (1) Polymerization of a comparative polymer compound (A-8) (2-sodium sulfoethyl methacrylate/benzyl methacrylate = 70/30):

120.9 g of 2-sodium sulfoethyl methacrylate and 42.8 g of benzyl methacrylate were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an input port, and a thermometer. 100 g of ion-exchanged water and 400 g of isopropyl alcohol. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of comparative polymer compound (A-8):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 100 ° C under reduced pressure for 30 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-8) (CP-2). The Mw of the obtained polymer compound (A-8) (CP-2) was 49,000.

(3) Polyaniline polymerization:

The polymer compound (A-8) (CP-2) obtained in the above (2) was charged with 14.4 g and ion exchange in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet tube, a reflux condenser, an inlet, and a thermometer. 200 g of water and 6 g of a 35% hydrochloric acid aqueous solution were stirred at 60 ° C for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and after stirring, it became a uniform emulsion. 10.0 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the mixture was dropped in a beaker kept at 0 ° C for 10 hours. After the end of the dropwise addition, the temperature was maintained at 0 ° C, and the polymerization was continued for 30 hours.

The obtained reaction liquid (CS-2) was a homogeneous solution. The reaction liquid (CS-2) was dried in a hot air circulating dryer at 80 ° C to recover a solid component. The obtained solid component was redispersed in isopropyl alcohol (IPA), washed, and filtered again. The IPA was washed and filtered four times to obtain a solid containing water. The solid was dried under reduced pressure at 40 ° C for 72 hours to obtain a polymer (C-2). As a result of measuring the volatile matter of the polymer (C-2), the volatile matter was 2% or less.

(4) Coating evaluation:

5 g of the polymer (C-2) obtained in the above (3) and 95 g of toluene were placed in a beaker, and stirred at room temperature, but the polymer (C-2) was not dissolved, and a part of a finely dispersed solution in which a precipitate was produced was obtained.

The dispersion of the polymer (C-2) was filtered through a 200-mesh filter, and the filtrate was dried using a doctor blade to have a thickness of 10 μm after drying. The film was applied to a glass substrate and dried to obtain a fine particle film. The uniform film was a film having a surface which was peeled off when rubbed with a finger, and the film was not able to be a uniform self-standing film obtained in Examples 1 to 6, and the surface resistance value was 10 ⁷ Ω/□ or more.

Further, the reaction liquid (CS-2) was applied directly onto a glass substrate, and after application to a thickness of 10 μm after drying, it was dried to obtain a non-uniform coating film having a surface resistance of 10 ⁶ Ω/□ or more.

Comparative example 3 (1) Polymerization of a comparative polymer compound (A-9) (2-sodium sulfoethyl methacrylate/2-ethylhexyl methacrylate = 35/65):

2-Sodium sulfoethyl methacrylate 60.3 g, 2-ethylhexyl methacrylate 104.4 was placed in a four-pot beaker having a capacity of 1000 cm ³ with a stirrer, a nitrogen inlet tube, a reflux cooler, an inlet, and a thermometer. g, 100 g of ion-exchanged water and 400 g of isopropyl alcohol. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 20 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of comparative polymer compound (A-9):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After the oil layer was removed, 1 kg of methanol was dropped over 1 hour to precipitate a solid component. The precipitated solid component was filtered, and dried at 100 ° C under reduced pressure for 30 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-9) (CP-3). The Mw of the obtained polymer compound (A-9) (CP-3) was 42,000.

(3) Polyaniline polymerization:

The polymer compound (A-9) (CP-3) obtained in the above (2) was placed in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet tube, a reflux condenser, an inlet, and a thermometer, and ion exchange was carried out. 200 g of water and 6 g of a 35% hydrochloric acid aqueous solution were stirred at 60 ° C for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and after stirring, a uniform emulsion was obtained. 10.0 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the inside of the beaker was kept at 0 ° C and dripped for 10 hours. After the end of the dropwise addition, the temperature was maintained at 0 ° C, and the polymerization was continued for 30 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried under reduced pressure at 40 ° C for 72 hours to obtain a polymer (C-3). As a result of measuring the volatile matter of the polymer (C-3), the volatile matter was 1% or less.

(4) Coating evaluation

5 g of the polymer (C-3) and 95 g of toluene were placed in a beaker, and the mixture was stirred at room temperature, but the polymer (C-3) was not dissolved, and a part of a finely dispersed solution in which a precipitate was formed was obtained.

The dispersion of the polymer (C-3) was filtered through a 200-mesh filter using a doctor blade to have a thickness of 10 μm after drying, and applied to a glass substrate, followed by drying to obtain a microparticle film. The uniform film was a film having a surface which was peeled off when rubbed with a finger, and the film was not able to be a uniform self-standing film obtained in Examples 1 to 6, and the surface resistance value was 10 ⁷ Ω/□ or more.

Comparative example 4 (1) Comparison of polymerization of polymer compound (A-10) (sodium polystyrene sulfonate):

150 g of sodium p-styrenesulfonate, 150 g of ion-exchanged water, and 300 g of isopropyl alcohol were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutyronitrile was placed in a beaker, and polymerization was carried out for 18 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of comparative polymer compound (A-10):

The whole amount of the polymer solution obtained in the above (1) was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After removing the oil layer, the aqueous layer was concentrated in a distiller. The obtained solid was dried under reduced pressure at 100 ° C for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-10) (CP-4). The Mw of the obtained polymer compound (A-10) (CP-4) was 32,000.

(3) Polyaniline polymerization (50% of polymer compound (A-10) and 1.2 times of hydrochloric acid):

The polymer compound (A-10) (CP-4) obtained in the above (2) was placed in a four-necked beaker having a capacity of 500 cm ³ in a mixer, a nitrogen inlet tube, a reflux condenser, an inlet, and a thermometer, and ion exchange was carried out. 200 g of water and 6 g of a 35% hydrochloric acid aqueous solution were stirred at 60 ° C for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and a uniform emulsion was obtained by stirring. 10.0 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the inside of the beaker was kept at 0 ° C and dripped for 10 hours. After the end of the dropwise addition, the temperature was maintained at 0 ° C, and the polymerization was continued for 30 hours.

The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid component was redispersed in water, washed, and filtered again. The water washing and filtration were further repeated four times to obtain a solid matter containing water. The solid was dried under reduced pressure at 40 ° C for 72 hours to obtain a polymer (C-4). As a result of measuring the volatile matter of the polymer (C-4), the volatile matter was 1% or less.

(4) Coating evaluation:

5 g of the polymer (C-4) obtained in the above (3) and 95 g of toluene were placed in a beaker, and stirred at room temperature, but the polymer (C-4) was not dissolved to obtain a finely dispersed solution in which a precipitate was formed.

The dispersion of the polymer (C-4) was filtered through a 200-mesh filter, and the filtrate was applied to a glass substrate by using a doctor blade to have a thickness of 10 μm after drying, followed by drying to obtain a microparticle film. The film was uniform, but the film was peeled off when rubbed with a finger, and the film was not able to be a uniform self-standing film obtained in Examples 1 to 6, and the surface resistivity was 10 ⁷ Ω/□ or more.

Comparative Example 5 (1) Comparison of polymerization of polymer compound (A-11) (sodium polystyrene sulfonate):

150 g of sodium p-styrenesulfonate, 150 g of ion-exchanged water, and 300 g of isopropyl alcohol were placed in a four-aluminum beaker having a capacity of 1000 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Further, 0.7 g of azobisisobutylate was placed in a beaker, and polymerization was carried out for 20 hours while maintaining a reflux state to obtain a polymer.

(2) Purification of comparative polymer compound (A-11):

The whole amount of the obtained polymer solution was transferred to a beaker of 2000 cm ³ , and 500 g of hexane was added thereto while stirring with a stirrer, followed by standing for 1 hour to remove an oil layer containing impurities. After removing the oil layer, the aqueous layer was concentrated in a distiller. The obtained solid was dried at 100 ° C under reduced pressure for 24 hours. The obtained dried product was pulverized in a mortar to obtain a powder of the polymer compound (A-11) (CP-5). The Mw of the obtained polymer compound (A-11) (CP-5) was 32,000.

(3) Polyaniline polymerization:

20.6 g of the polymer compound (A-11) (CP-3), 300 g of ion-exchanged water, and 35% of the above-mentioned polymer compound (A-11) (CP-3) were placed in a four-aluminum beaker having a capacity of 500 cm ³ equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer. 10 g of an aqueous hydrochloric acid solution was heated at 60 ° C for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform.

Further, 4.65 g of aniline was added to the emulsifier solution, and the mixture was stirred to form a uniform emulsion. 10.0 g of ammonium peroxodisulfate was dissolved in 30 g of ion-exchanged water, and the mixture was dropped in a beaker kept at 0 ° C for 10 hours. After the completion of the dropwise addition, the temperature was maintained at 0 ° C for further 30 hours.

The resulting reaction solution (CS-5) was a homogeneous solution. The reaction liquid (CS-5) was dried in a hot air circulating dryer at 80 ° C to recover a solid component. The obtained solid component was redispersed in water and washed, and filtered again. The water was washed four times and filtered to obtain a solid containing water. The solid was dried under reduced pressure at 100 ° C for 72 hours to obtain a polymer (C-5). As a result of measuring the volatile matter of the polymer (C-5), the volatile matter was 1% or less.

(4) Coating evaluation:

5 g of the polymer (C-5) and 95 g of toluene were placed in a beaker, and stirred at room temperature, but the polymer (C-5) was not dissolved at all.

Next, 5 g of the polymer (C-5) and 95 g of ion-exchanged water were placed in a beaker, and stirred at room temperature to obtain an aqueous dispersion in which one part of the polymer (C-5) was dissolved.

The aqueous dispersion of the polymer (C-5) was filtered through a 200-mesh filter, and the filtrate was subjected to a doctor blade to have a thickness of 10 μm after drying, and applied to a glass substrate, followed by drying to obtain a green uniformity. Coating film. The surface resistance value of the coating film was measured to obtain 3 MΩ/□.

Example 7 to Example 11 and Comparative Example 6 to Comparative Example 9

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

The obtained dye-sensitized solar cell element was evaluated using Solar Simulator YSS-80A manufactured by Yamashita Electric Co., Ltd. For cell 1cm ² area of the element, the survey ^{AM1.5 (1sun; 100mW / cm 2} ) IV characteristics under the irradiation cell in order to assess the short-circuit current, open-circuit voltage, fill factor and power generation efficiency. The results are shown in Table 1.

From the above results, it was revealed that the dye-sensitized solar cell element formed using the composite conductive polymer composition of the present invention has high photoelectric conversion efficiency.

Example 14 to Example 15 and Comparative Example 9 to Comparative Example 10

The solution of the composite conductive polymer composition prepared in Examples 1 and 2 or the conductive polymer composition solution prepared in Comparative Example 2 was again adjusted to a solid content of 2.5%, and these were subjected to spin coating. The glass substrate having a thickness of 1000 μm and the PET film substrate having a thickness of 100 μm were coated at 4000 rpm to 15 sec, and the solvent was removed by a hot air dryer to produce an antistatic film forming an antistatic layer. Further, the film thickness of the antistatic layer was measured by a stylus type surface measuring device (Dektak 6M: manufactured by ULVAC), and 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 evaluation results are shown in Table 2.

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

Condition (2): 168 hours 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

The composite conductive polymer composition of the present invention is a user of a polymer compound (A) having a highly hydrophobic aromatic ring or an alicyclic group as a main component, and can be stably dissolved in an aromatic solvent such as toluene. Become possible.

Therefore, the composite conductive polymer obtained by dissolving the composite conductive polymer composition thus obtained in an aromatic solvent in a transparent state forms a composition solution, and a conductive film can be easily formed on a portion where conductivity is required. In the field of electronic parts and the like, it can be used under extremely favorable conditions.

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

Claims (17)

A composite conductive polymer composition characterized in that a polymer compound (A) having the following components (a-1) and (a-2) as a constituent component is blended and is selected from the following formula (I)~ The compound of (III) is a π-conjugated polymer (β) as a monomer component, and is soluble in toluene; (a-1) 20 to 45 mol% of a monomer containing a sulfonic acid group and a polymerizable vinyl group. (a-2) 55 to 80 mol% of a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group (however, 50% of the hydrogen removed is a carbon compound having 2 to 30 carbon atoms substituted by a halogen group) (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 according to claim 1, wherein the component (a-1) is a single selected from the group consisting of styrenesulfonic acid or a salt thereof or ethyl 2-sulfonic acid (meth)acrylate or a salt thereof. body. The composite conductive polymer composition according to claim 1, wherein the component (a-2) is selected from the group consisting of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; Ethyl ethyl 2-methyl phthalate, ethyl 2-ethyl phthalate (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, Dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) A group of acrylate morpholine, styrene, dimethyl styrene, naphthalene (meth) acrylate, vinyl naphthalene, vinyl n-ethyl carbazole and vinyl fluorene. The composite conductive polymer composition according to any one of the items 1 to 3, wherein the polymer compound (A) has a GPC-equivalent weight average molecular weight of 3,000 to 100,000. A method for producing a composite conductive polymer composition, characterized in that a polymer compound (A) of the following components (a-1) and (a-2) is polymerized by radical polymerization, and is selected from the following (I) to (III) a compound coexisting in an electrolytic matrix solvent, and performing a chemical oxidative polymerization using an oxidizing agent to obtain a composite conductive polymer composition soluble in toluene; (a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group 20 ~45 mol% (a-2) 55 to 80 mol% of a monomer having an aromatic or alicyclic group and a polymerizable vinyl group (however, 50% of the hydrogen removed is a carbon having 2 to 30 carbon atoms substituted by a halogen group) Compound) (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 component (a-1) is selected from the group consisting of styrenesulfonic acid or a salt thereof, ethyl 2-sulfonic acid (meth)acrylate, and sulfonate. A monomer having a sulfonic acid group and a polymerizable vinyl group in a group of an acid or a salt thereof. The method for producing a composite conductive polymer composition according to claim 5, wherein the component (a-2) is selected from the group consisting of benzyl (meth) acrylate and phenoxy ethyl (meth) acrylate. , ethyl 2-methyl phthalate (meth) acrylate, ethyl 2-ethyl phthalate (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (methyl) Acrylate, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( A group of methyl acrylate morpholine, styrene, dimethyl styrene, naphthalene (meth) acrylate, vinyl naphthalene, vinyl n-ethyl carbazole, and vinyl fluorene. Such as the compounding of any of items 5 to 7 of the patent application scope In the method for producing a conductive polymer composition, in the case of the compound 1 selected from the group consisting of the formulae (I) to (III), the polymer compound (A) is allowed to coexist until the sulfonic acid molar ratio becomes 0.2 to 1.5. . The method for producing a composite conductive polymer composition according to any one of the items 5 to 7, wherein the oxidizing agent is selected from the group consisting of ammonium peroxydisulfate, potassium peroxydisulfate, and sodium peroxodisulfate. Iron (III) chloride, iron (III) sulfate, iron (III) tetrafluoroborate, iron (III) hexafluoroantimonate, copper (II) sulfate, copper (II) chloride, copper (II) tetrafluoroborate, An oxidizing agent in the form of copper (II) hexafluoroantimonate and ammonium monooxydisulfate. The method for producing a composite conductive polymer composition according to any one of claims 5 to 7, wherein the electrolytic matrix solvent is ion-exchanged water. The method for producing a composite conductive polymer composition according to any one of claims 5 to 7, wherein the chemical oxidative polymerization is for 1 mol of the compound selected from the formulae (I) to (III). It is carried out by adding 0.5 to 3.0 mol of an acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride and iron (II) sulfide. A composite conductive polymer composition solution characterized by the composite conductive polymer composition according to any one of claims 1 to 4 in an aromatic system selected from the group consisting of toluene, benzene and xylene The solvent is contained in a dissolved state of 0.1 to 10% by mass. A composite conductive polymer composition solution characterized by dissolving a composite conductive polymer composition as claimed in claim 12 100 parts by weight of the solvent of the liquid is obtained by mixing an aromatic compound having a hydroxyl group in an amount of 0.01 to 45 parts by weight. The composite conductive polymer composition solution according to claim 13, 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, A compound in the group of 1-naphthyl alcohol, o-methoxyphenol and 2,6-dimethylphenol. The composite conductive polymer composition solution according to any one of claims 12 to 14, further comprising a metal, a metal oxide, a conductive polymer composition, a carbon powder or a dispersion. A counter electrode for a dye-sensitized solar cell, which is characterized by using the composite conductive polymer composition according to any one of claims 1 to 4. An antistatic film characterized by using the composite conductive polymer composition according to any one of claims 1 to 4.