JP2011222353A - Transparent conducting thin film, and transparent conducting film having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conducting thin film and a transparent conducting film which have an excellent electrical conductivity and are capable of keeping their film properties for a long time, namely have an excellent durability.SOLUTION: A transparent conducting thin film includes: a conducting polymer consisting of a conjugated system conducting polymer and a poly-anion and a salt having anion with five or more carbon atoms. Particularly, it is preferable that the content of the anion with five or more carbon atoms is 0.1-80 wt.% on the basis of the mass of the conducting polymer. Further, it is preferable that the anion contains fluorine and/or phosphorus.

Description

  The present invention relates to a transparent conductive thin film and a transparent conductive film having the same.

Conventionally, a transparent conductive film is suitably used as a transparent electrode such as a liquid crystal display or a transparent touch panel or an electromagnetic shielding material. As such a transparent conductive film, at least one surface of a transparent substrate film such as polyethylene terephthalate (PET) or triacetyl cellulose (TAC) is provided with indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), In ₂ O. It is well known that a mixed sintered body (ITO) of ₃ and SnO ₂ is provided by a dry process such as vacuum deposition, sputtering, or ion plating.

  However, the transparent conductive film usually has continuous processing and punching processing in a web shape, and is used and stored in a bent state during surface processing. Therefore, the transparent conductive film obtained by the dry process is used. In the case of the conductive film, cracks may occur during the processing step or storage, and the surface resistance may increase.

  On the other hand, a transparent conductive coating film layer formed by applying a conductive polymer on a transparent base film (wet process) has flexibility in the film itself, and problems such as cracks hardly occur. In addition, the method of obtaining a transparent conductive film by applying a conductive polymer has the advantage that the manufacturing cost is relatively low unlike the dry process, and the coating speed is generally high, so that the productivity is excellent. . In the transparent conductive film obtained by application of such a conductive polymer, polythiophene, polyaniline, polypyrrole, etc. that have been generally used so far have not been able to obtain high conductivity at the initial stage of development. Use has been limited to antistatic applications or the like, and the hue of the conductive coating layer itself has been a problem. However, these problems have recently been improved by improving the production method. For example, a conductive polymer (Patent Document 1) comprising a poly (3,4-dialkoxythiophene) obtained by oxidative polymerization of 3,4-dialkoxythiophene in the presence of a polyanion and a polyanion is a recent production method. (Patent Documents 2 to 5) and the like exhibit a very low surface resistance while maintaining a high light transmittance.

  Further, in the above conjugated conductive polymer thin film, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium By containing an electrolyte having chloride, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium chloride, 1-butyl-1-methylpyrrolidinium chloride or trifluoromethanesulfonyl group Studies have been made to improve conductivity. (Patent Documents 6 to 8, Non-Patent Document 1)

Japanese Patent Laid-Open No. 1-313521 JP 2002-193972 A JP 2003-286336 A JP-A-10-88030 JP 2004-58648 A JP 2007-96016 A JP 2009-205970 A WO2006 / 14701 pamphlet

Chem. Mater., 2007, 19, 2147-2149

  On the other hand, when a transparent conductive film is used as an electronic material, it is important that the transparent conductive layer can maintain its film characteristics over a long period of time. There is concern that the layer will be altered, absorb moisture, etc., and long-term stability will be reduced.

  Accordingly, an object of the present invention is to provide a transparent conductive thin film excellent in conductivity and capable of maintaining film characteristics over a long period of time, that is, excellent in durability and a transparent conductive film having the same. .

  As a result of intensive studies, the present inventors have found that the above problems can be solved by including a salt having a specific anion in a transparent conductive thin film using a conductive polymer. did.

That is, the present invention is a transparent conductive thin film containing a conductive polymer comprising a conjugated conductive polymer and a polyanion and a salt having an anion having 5 or more carbon atoms.
In the present invention, the content of an anion having 5 or more carbon atoms is 0.1 to 80% by mass based on the mass of the conductive polymer, and the anion contains a fluorine element, a phosphorus element, or both. Of these, by providing at least one of the aspects, a further excellent transparent conductive thin film can be obtained.
Furthermore, this invention includes the transparent conductive film which has one of the said transparent conductive thin films in the at least one surface of a base film.

  According to the present invention, it is possible to provide a transparent conductive thin film having excellent conductivity and excellent durability. Moreover, the transparent conductive film using this can be provided.

[Conductive polymer]
The conductive polymer in the present invention includes a conjugated conductive polymer and a polyanion.
(Conjugated conductive polymer)
The conjugated conductive polymer in the present invention contains at least one or more of polyaniline, polythiophene derivative, polypyrrole or a copolymer thereof in its structure. Any one of these conjugated conductive polymers may be included, and a form such as a copolymer, a blend, or a hybrid may be used.

で表される繰返し単位からなるからなるポリカチオン状のポリチオフェン（以下、“ポリ（３，４−ジ置換チオフェン）”）が好ましい。上記式中、Ｒ^１およびＲ^２は、相互に独立して水素原子または炭素数が１〜４のアルキル基を表すか、あるいは一緒になって任意に置換されていてもよい炭素数が１〜１２のアルキレン基を表す。Ｒ^１およびＲ^２が一緒になって形成される、置換基を有していてもよい炭素数が１〜１２のアルキレン基の代表例としては、１，２−アルキレン基（例えば、１，２−シクロヘキシレン、２，３−ブチレンなど）があげられる。この１，２−アルキレン基は、α−オレフィン類（例えば、エテン、プロペン、ヘキセン、オクテン、デセン、ドデセンおよびスチレン）を臭素化して得られる１，２−ジブロモアルカン類から誘導される。Ｒ^１およびＲ^２が一緒になって形成される炭素数が１〜１２のアルキレン基の好適な置換基は、メチル基、エチル基およびプロピル基が好ましく、エチル基が特に好適である。 Among these, as the conjugated conductive polymer in the present invention, the following general formula

A polycationic polythiophene (hereinafter referred to as “poly (3,4-disubstituted thiophene)”) consisting of repeating units represented by In the above formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or have 1 to 1 carbon atoms which may be optionally substituted together. 12 alkylene groups are represented. As a typical example of the alkylene group having 1 to 12 carbon atoms which may be substituted, which is formed by combining R ¹ and R ² , a 1,2-alkylene group (for example, 1, 2 -Cyclohexylene, 2,3-butylene, etc.). This 1,2-alkylene group is derived from 1,2-dibromoalkanes obtained by brominating α-olefins (for example, ethene, propene, hexene, octene, decene, dodecene and styrene). Suitable substituents of the alkylene group having 1 to 12 carbon atoms formed by R ¹ and R ² together are preferably a methyl group, an ethyl group and a propyl group, and particularly preferably an ethyl group.

(Polyanion)
In the present invention, the conjugated conductive polymer is used as a composite compound containing a polyanion (hereinafter sometimes referred to as a conductive polymer).
Examples of such polyanions include polymeric carboxylic acids (eg, polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.), polymeric sulfonic acids (eg, polystyrene sulfonic acid, polyvinyl sulfonic acid, etc.), and the like. These polymeric carboxylic acids and sulfonic acids may be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as acrylates and styrene. Among these polyanions, polystyrenesulfonic acid and all or a part of which are metal salts are particularly preferable from the viewpoint of increasing the conductivity improving effect. The number average molecular weight of the polyanion is suitably in the range of 1,000 to 2,000,000, particularly preferably in the range of 2,000 to 500,000.

[salt]
The transparent conductive thin film of this invention contains the salt which consists of the anion and cation mentioned later for the purpose of improving the electroconductivity and durability. The content of the salt is preferably such that the anion constituting the salt is 0.1 to 80% by mass with respect to the mass of the conductive polymer. By making content into the said numerical range, the improvement effect of electroconductivity and durability can be enlarged. When the content is less than 0.1% by mass, the effect of improving conductivity and durability tends to be small, and when it exceeds 80% by mass, the coating composition for forming a transparent conductive thin film is used. When a transparent conductive thin film is formed by coating on a substrate like a material film, the film hardness and transparency of the transparent conductive thin film tend to decrease. From such a viewpoint, the content is more preferably an amount such that the anion constituting the salt is 0.1 to 60% by mass with respect to the mass of the conductive polymer, and particularly preferably 20 to 55% by mass. It is.

  Such salts can be used singly or in combination of two or more. The salt is not particularly limited with respect to its production method, and for example, a salt obtained by a conventionally known production method may be used. The transparent conductive thin film of the present invention contains a salt having an anion, which will be described later, as an essential component, but when two or more kinds of salts are used, at least one of them is a salt having an anion defined by the present invention. What is necessary is just to make it content of this salt into the said numerical range.

Hereinafter, the anion and cation constituting the salt in the present invention will be described.
(Anion)
The anion constituting the salt in the present invention is an anion having 5 or more carbon atoms. When the anion is in such an embodiment, the conductivity and durability of the transparent conductive thin film can be increased. Thus, it is presumed that by using an anion having 5 or more carbon atoms, the hydrophobicity of the anion tends to be high, and thereby the above-mentioned effects are exhibited. From such a viewpoint, the number of carbon atoms is preferably 6 or more, and more preferably 7 or more. The upper limit of the carbon number is not particularly limited, but is preferably 12 or less from the viewpoint of salt stability.

  In addition, when such an anion contains a fluorine element in the skeleton, the chemical stability and hydrophobicity of the anion can be further increased, and the effect of improving the conductivity and durability of the transparent conductive thin film can be increased. . Moreover, the aspect which contains a phosphorus element in an anion center is preferable from higher electroconductivity and durability being obtained. As an anion in the present invention, an embodiment containing both a fluorine element and a phosphorus element is particularly preferable.

  Specific examples of such anions include tris (pentafluoroethyl) trifluorophosphate, tetracyanoborate, bis (oxalate (2-)-O, O ') borate, n-butyl sulfate, and n-hexyl sulfate. Octyl sulfate, p-toluenesulfonate, 2 (2-methoxyethoxy) ethyl sulfate, perfluorobutanesulfonate, and the like. Among these, tris (pentafluoroethyl) trifluorophosphate and tetracyanoborate are particularly preferable from the viewpoint of high stability and a large effect of improving durability.

(Cation)
The cation constituting the salt in the present invention is not particularly limited, and examples thereof include imidazolium derivatives, pyridinium derivatives, ammonium derivatives, pyrrolidine derivatives, sulfonium derivatives, and phosphonium derivatives.

  Examples of the imidazolium derivative include 1,3-dimethylimidazolium, 1,2,3-trismethylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- Propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 2,3-dimethyl-1-propylimidazolium, 1-hexyl-3-methylimidazolium 1-hexyl-2,3-dimethylimidazolium, 3-methyl-1-octylimidazolium, 1-benzyl-3-methylimidazolium, 1-cyanomethyl-3-methylimidazolium, 1- (2-hydroxy And ethyl) -3-methylimidazolium.

  Examples of pyridinium derivatives include N-butylpyridinium, N-butyl-3-methylpyridinium, N- (3-hydroxypropyl) pyridinium, N-ethyl-3-methylpyridinium, N-ethyl-3-hydroxymethylpyridinium, N- And hexyl-4-dimethylaminopyridinium.

  Examples of ammonium derivatives include tetramethylammonium, tetrabutylammonium, ethyl-dimethyl-propylammonium, N-ethyl-N, N-dimethyl-2-methoxyethylammonium, methyltrioctylammonium, and (2-hydroxyethyl) trimethyl. Ammonium, hydrazinocarbonylmethyltrimethylammonium, ethyldimethyl- (5-diisopropylpyramino-3-oxapentyl) -ammonium, ethyl-dimethyl-cyanomethyl and the like can be mentioned.

  Examples of pyrrolidine derivatives include N-butyl-N-methylpyrrolidinium, N, N-dimethylpyrrolidinium, N- (methoxyethyl) -N-methylpyrrolidinium, N-methyl-N-octylpyrrolidinium, N-hexyl-N-methylpyrrolidinium, N- (6-aminohexyl) -N-methylpyrrolidinium and the like can be mentioned.

  Examples of other cations include guanidinium, triethylsulfonium, trihexyl (tetradecyl) phosphonium, 1- (2-methoxyethyl) -1-methyl-piperidinium, N- (methoxyethyl) -N-methylmorpholinium and the like.

[Transparent conductive thin film]
The transparent conductive thin film of the present invention contains the conductive polymer and the salt having an anion having 5 or more carbon atoms.

(Thickness)
The thickness of the transparent conductive thin film of the present invention is preferably 20 to 1000 nm. When the thickness is within the range, the effect of improving the conductivity can be increased, and at the same time, the transparency can be further increased. From such a viewpoint, the thickness is more preferably 50 to 700 nm, and particularly preferably 100 to 600 nm.

(Additive)
The transparent conductive thin film of the present invention can further contain an additive as long as the effects of the present invention are not impaired. Examples of such additives include film forming agents, crosslinking agents, solvents, binders, dopants other than salts contained in the transparent conductive thin film of the present invention, matting agents, surfactants, coating aids, dimensions. Resin component for improving stability, inorganic component, thickener, thickener, viscosity modifier, hardener, antistatic agent, dye, pigment, antifoggant, lubricant, antioxidant, adhesion The property imparting material etc. can be mentioned. The additives can be used alone or in combination of two or more.

  As the film forming agent, for example, a so-called silane coupling agent can be exemplified. In particular, an alkoxysilane having an epoxy group is preferable. The amount of the film-forming agent added is preferably 0.1 to 90% by mass, more preferably 0.2 to 80% by mass, and still more preferably 1 to 70% by mass based on the mass of the conductive polymer. By using such a film forming agent, a transparent conductive thin film can be formed uniformly. In addition, the effect of improving durability can be increased.

  When a surfactant is added, the addition amount is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.00, based on the mass of the conductive polymer. It is 5-8 mass%. By using the surfactant, the transparent conductive thin film can be formed uniformly.

[Base film]
In this invention, the said transparent conductive thin film can be provided on a base material, and electroconductivity can be provided to a base material.
As such a base material, an arbitrary material such as a plastic sheet, film or nonwoven fabric can be used depending on the application. In the present invention, a transparent conductive film can be formed by using a substrate film made of a plastic film as a substrate and providing the transparent conductive thin film on at least one surface thereof. Here, examples of the plastic include polyester, polystyrene, polyimide, polyamide, polysulfone, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, and mixtures and copolymers thereof, as well as phenol resin, epoxy resin, and ABS resin. Can do. Among these, a biaxially oriented polyester film is more preferable because it has excellent properties such as dimensional stability, mechanical properties, heat resistance, electrical properties, etc., and particularly polyethylene terephthalate film or polyethylene-2,6-naphthalate. The film is preferable because it has excellent mechanical properties such as a high Young's modulus and thermal properties such as good heat-resistant dimensional stability. Among them, it is preferable to use a polyethylene-2,6-naphthalate film, and in the method of impregnating with a salt described later, it is easy to adopt preferable heat drying conditions, and the effect of improving conductivity and durability is greatly increased. can do. The thickness of the polyester film is preferably 500 μm or less, and if it exceeds this, the rigidity becomes too strong, and the handleability of the obtained transparent conductive film tends to be lowered.

[Production method]
The transparent conductive thin film of the present invention includes a conjugated conductive polymer, a polyanion, a salt having an anion having 5 or more carbon atoms, and an additive that can be used as necessary, for example, a roll, a kneader, a Banbury mixer. A coating composition for forming a transparent conductive thin film obtained by mixing by mechanical stirring using a kneader, stirring by a stirrer, stirring using ultrasonic waves, or the like, such as a resin molded body or the substrate It is formed on a substrate like a film and dried. Alternatively, it can be formed by a spin coating method or the like.

  By adding a solvent at the time of mixing the above components, the film forming property of the transparent conductive thin film can be enhanced. Examples of the solvent include water, alcohols such as methanol, ethanol, propanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, propylene carbonate, ethylene carbonate, vinylene carbonate, and methylpropyl carbonate. Carbonate esters, ethyl propionate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, esters such as methyl acetate, ethyl acetate, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, glycol ether, tetrahydrofuran Examples of such ethers, and compounds obtained by introducing a substituent such as fluorine into these ethers. A solvent can be used individually or in combination of 2 types or more, respectively.

  Further, a coating composition for forming a transparent conductive thin film, comprising a conjugated conductive polymer, a polyanion, and an additive that can be used as necessary, is formed on a substrate such as the base film. After applying and drying to form a transparent conductive thin film, such a layer is washed with a dispersion in which a salt having an anion having 5 or more carbon atoms is dispersed, and the transparent conductive thin film is impregnated with the salt. The transparent conductive thin film of the present invention can be produced.

  The dispersion medium in the dispersion is not particularly limited, and examples thereof include water, alcohols such as methanol, ethanol, propanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, propylene carbonate, and ethylene carbonate. , Carbonates such as vinylene carbonate and methylpropyl carbonate, ethyl propionate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, esters such as methyl acetate, ethyl acetate, ethylene glycol, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, glycol ether, ethers such as tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethyl Setokishido, N- polar solvent such as methyl pyrrolidone, a compound obtained by introducing a substituent such as those in the fluorine and the like. A solvent can be used individually or in combination of 2 types or more, respectively.

  The salt concentration in the dispersion is preferably 5 to 50% by mass, and can be satisfactorily impregnated with the salt. From such a viewpoint, the concentration is more preferably 5 to 20% by mass, and particularly preferably 5 to 15% by mass.

  The time for impregnating the transparent conductive thin film into the dispersion is preferably 1 to 10 minutes, and more preferably 2 to 5 minutes. After impregnation, heat drying is performed. Such heat drying conditions are preferably a temperature of 80 to 180 ° C. for 5 to 120 seconds, and more preferably a temperature of 120 to 170 ° C. for 10 to 40 seconds. By performing impregnation and heat drying under such conditions, it becomes easy to bring the amount of salt in the transparent conductive thin film into a preferable range, and the effect of improving conductivity and durability can be increased.

[Transparent conductive film]
The transparent conductive film of the present invention has the transparent conductive thin film on at least one surface of the base film.

(Surface resistivity)
The transparent conductive film of the present invention preferably has a surface resistivity on the surface of the transparent conductive thin film of 100,000 Ω / □ or less. The surface resistivity is more preferably 10,000 Ω / □ or less, particularly preferably 5,000 Ω / □ or less. When the surface resistivity is in the above numerical range, it can be suitably used as a transparent electrode such as a liquid crystal display or a transparent touch panel, a transparent electrode of a solar cell, or an electromagnetic shielding material. The lower limit of the surface resistivity is not particularly limited and is preferably low. However, if the surface resistivity is too low, the cost increases, so the substantial lower limit is 5Ω / □ or more.

(conductivity)
As for the transparent conductive film of this invention, it is preferable that the electrical conductivity in the surface of a transparent conductive thin film is 5 S / cm or more. The conductivity is more preferably 10 S / cm or more, and particularly preferably 20 S / cm or more. It is preferable for the conductivity to be in the above numerical range since high conductivity can be obtained. Higher conductivity is preferable, and the upper limit is not particularly limited, but is substantially 2000 S / cm or less from the viewpoint of cost.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, each evaluation in an Example followed the following method.

(1) Surface resistivity It measured based on JISK7194 using Mitsubishi Chemical Corporation Lorester MCP-T600. The measurement was performed at five arbitrary points, and the average value thereof was defined as the surface resistivity (Ω / □).

(2) Thickness measurement A film sample was cut into 2 mm in the longitudinal direction and 2 cm in the width direction, fixed to an embedded capsule, and then embedded with an epoxy resin (Refotech Co., Ltd. Epomount). The embedded sample was cut perpendicularly in the width direction with a microtome (LETAC ULTRACUT UCT) to form a 5 nm thick thin film slice. Using a transmission electron microscope (Hitachi S-4300), the film was observed and photographed at an acceleration voltage of 100 kV, and the thickness of each layer was measured from the photograph.

(3) Conductivity Calculate the conductivity based on the following equation from the surface resistivity (Ω / □) obtained in (1) above and the thickness (nm) of the transparent conductive thin film obtained in (2) above. did.
1 / (thickness × surface resistivity) × 10 ⁷ = conductivity (S / cm)

(4) Durability Evaluation of Transparent Conductive Thin Film After the transparent conductive film was treated for 24 hours at a temperature of 105 ° C. and a relative humidity of 100% RH, the surface resistivity was measured by the same method as in (1) above. The change rate of the surface resistivity after the treatment with respect to the surface resistivity before the treatment was determined according to the following formula, and if the change rate of the surface resistivity was 20% or less, it was regarded as acceptable.
Rate of change(%)
= (| Surface resistivity after treatment−surface resistivity before treatment | / surface resistivity before treatment) × 100

[Adjustment of coating composition]
In this example, the following materials were used.
Conductive polymer: 0.5% by mass of poly (3,4-ethylenedioxythiophene) as a conjugated conductive polymer and polystyrene sulfonic acid (number average molecular weight Mn = 150,000) 0.8 as a polyanion An aqueous dispersion of a conductive polymer (BaytronP: Bayer AG, solid content concentration: 1.3% by mass) was used.
Salt: guanidinium tris (pentafluoroethyl) trifluorophosphate (manufactured by Merck & Co., Inc.) was used.
Film-forming agent: 3-glycidoxypropyltrimethoxysilane (concentration 100% by mass) was used.
Surfactant: Plus Coat RY-2 (manufactured by Kyoyo Chemical Co., Ltd., concentration 10% by mass) was used.
These materials were mixed at a ratio shown in Table 1 and diluted with a solvent shown in Table 1 to obtain a coating composition for forming a transparent conductive thin film.

[Example 1, Comparative Example 1]
Using a Meyer bar, a coating composition for forming the transparent conductive thin film obtained above on a base film (biaxially oriented PEN film, manufactured by Teijin DuPont Films, trade name Q65F-100) Coating was performed and drying was performed at 150 ° C. for 120 seconds to obtain a transparent conductive film. The properties of this transparent conductive film are shown in Table 1.
In addition, the solid content ratio of each component in the coding composition of Example 1 is conductive polymer / salt / film-forming agent / surfactant = 100/60/50 / 7.7, and in the transparent conductive thin film The anion content is 53% by mass based on the mass of the conductive polymer. The thickness of the transparent conductive thin film was as shown in Table 1.

[Example 2]
The film prepared in Comparative Example 1 is impregnated in an aqueous solution containing 10% by weight of a salt (guanidinium tris (pentafluoroethyl) trifluorophosphate) (temperature 23 ° C.) for 3 minutes, and then heated at 150 ° C. for 30 seconds. Thus, a conductive film was obtained. The properties of this film are shown in Table 2.
The transparent conductive thin film obtained in Example 2 contained 25% by mass of anions based on the mass of the conductive polymer. In addition, this content was calculated | required by quantifying N atom by TOFSIMS. The thickness of the transparent conductive thin film was as shown in Table 2.

Claims (4)

  A transparent conductive thin film comprising a conductive polymer composed of a conjugated conductive polymer and a polyanion, and a salt having an anion having 5 or more carbon atoms.   The transparent conductive thin film according to claim 1, wherein the content of an anion having 5 or more carbon atoms is 0.1 to 80% by mass based on the mass of the conductive polymer.   The transparent conductive thin film according to claim 1 or 2, wherein the anion contains fluorine element or phosphorus element, or both.   The transparent conductive film which has the transparent conductive thin film of any one of Claims 1-3 in the at least one surface of a base film.