JP2011124029A - Transparent conductive film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive film superior in transparency and high in conductivity, and its manufacturing method. <P>SOLUTION: The transparent conductive film comprises a CNT (carbon nanotube) 22 coated on a substrate 21 and a PEDOT/PSS 23 which exists on a part of the CNT 22, and contains at least PEDOT/PSS 23 of 10 parts weight against the CNT 22 of 100 parts weight. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transparent conductive film used for a transparent electrode and the like and a method for producing the same.

  Transparent conductive films are used in the fields of liquid crystal displays, electroluminescence displays, plasma displays, electrochromic displays, solar cells, touch panels and the like. As a material for the transparent conductive film, a conductive inorganic material such as ITO (indium-tin oxide) or a conductive organic material such as polyethylenedioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) is used. As a transparent conductive film using a conductive organic material, a transparent conductive film in which a carbon tube is blended at a predetermined ratio in a conductive layer containing PEDOT / PSS has been proposed (for example, see Patent Document 1).

  Such a transparent conductive film is formed by a wet process. In this wet process, a film is formed using a coating liquid in which a binder for improving the coating properties is added to a dispersion liquid in which PEDOT / PSS and carbon nanotubes are dispersed in a solvent. The transparent conductive film described in Patent Document 1 has improved conductivity and mechanical strength by adding carbon nanotubes.

JP 2008-50391 A

  By the way, when using a transparent conductive film for a touch panel etc., in order to prevent visual recognition of the pattern, it is desirable to use a transparent conductive film with high transparency and little coloring. However, PEDOT / PSS has a band gap in the vicinity of 1.5 eV and absorbs the red region of visible light. For this reason, the transparent conductive film using PEDOT / PSS has a problem of coloring blue when the film thickness is increased. On the other hand, if the transparent conductive film is thinned so as not to be colored, there is a problem that the conductivity of the transparent conductive film is lowered.

  Moreover, the transparent conductive film described in Patent Document 1 is formed using a coating solution to which a binder is added for improving the coating properties. However, when a binder is added to the transparent conductive film, conduction between PEDOT / PSS and carbon nanotubes is hindered by the binder, and there is a problem that the conductivity of the transparent conductive film is lowered. Thus, it has been difficult to improve both transparency and conductivity in the conventional transparent conductive film.

  This invention is made | formed in view of this point, and it aims at providing the transparent conductive film excellent in transparency and having high electroconductivity.

  The transparent conductive film of the present invention comprises a carbon nanotube coated on a substrate, and a conductive composition existing in a part on the carbon nanotube, and at least the above-mentioned 100 parts by weight of the carbon nanotube It contains 10 parts by weight of a conductive composition.

  According to this configuration, since the conductive composition is present in part on the carbon nanotube, the contact resistance between the molecular chains of the carbon nanotube can be reduced, so that a transparent conductive film having excellent conductivity can be realized. Moreover, since high electroconductivity is obtained even if it reduces the application quantity of an electroconductive composition, coloring of the transparent conductive film originating in an electroconductive composition can be reduced, and the transparent conductive film excellent in transparency is implement | achieved. it can.

  In the transparent conductive film of the present invention, the conductive composition exists in at least two regions on the carbon nanotube so as to be separated from each other.

  According to this configuration, since the conductive composition exists in at least two regions on the carbon nanotube so as to be separated, the contact resistance between the molecular chains of the carbon nanotubes in each region can be reduced, so that the conductivity is excellent. A transparent conductive film can be realized. Moreover, since high electroconductivity is obtained even if it reduces the application quantity of an electroconductive composition, coloring of the transparent conductive film originating in an electroconductive composition can be reduced, and the transparent conductive film excellent in transparency is implement | achieved. it can.

  The transparent conductive film of the present invention contains a base material, carbon nanotubes coated on the base material, and a conductive composition present on the base material. A conductive pattern is formed by a conductive region where the conductive composition is present on the carbon nanotube, and the conductive region contains at least 10 parts by weight of the conductive composition with respect to 100 parts by weight of the carbon nanotube. Features.

  According to this configuration, a conductive region having high conductivity is formed even if the amount of the conductive composition applied is reduced on the substrate, so that coloring derived from the conductive composition can be reduced, and the conductivity is high. A transparent conductive film having excellent transparency can be realized. Moreover, the area | region where electroconductivity differs can be arbitrarily formed on a base material by coating a carbon nanotube in the arbitrary area | regions on a base material. Furthermore, by applying the conductive composition to both the conductive region and the non-conductive region, the difference in coloring between the conductive region and the non-conductive region on the base material can be reduced, and a transparent conductive film excellent in transparency can be realized.

  In the transparent conductive film of the present invention, the conductive region preferably has a sheet resistance value in a range of 100Ω / □ to 10 KΩ / □.

  In the transparent conductive film of the present invention, the coverage of the carbon nanotubes by the conductive composition is preferably in the range of 5% to 50%.

  According to this configuration, the contact resistance between the molecular chains of the carbon nanotubes can be reduced by setting the coverage of the carbon nanotubes with the conductive composition within a predetermined range, so that a transparent conductive film having excellent conductivity can be realized. Moreover, since high electroconductivity is obtained even if it reduces the application quantity of an electroconductive composition, coloring of the transparent conductive film originating in an electroconductive composition can be reduced, and the transparent conductive film excellent in transparency is implement | achieved. it can.

  In the transparent conductive film of the present invention, the film thickness of the carbon nanotube is preferably in the range of 10 nm to 500 nm. With this configuration, the transparency of the transparent conductive film can be further improved.

  In the transparent conductive film of the present invention, the conductive composition preferably contains PEDOT / PSS. With this configuration, the conductivity of the transparent conductive film can be further improved by PEDOT / PSS having high conductivity.

  In the transparent conductive film of the present invention, the PEDOT / PSS film thickness is preferably in the range of 40 nm to 600 nm. With this configuration, a sufficient film thickness can be secured with respect to the carbon nanotube coating film, so that the conductivity of the transparent conductive film can be further improved.

  In the transparent conductive film of the present invention, the carbon nanotube is preferably patterned. According to this configuration, if only the carbon nanotubes are patterned in advance, even if the conductive composition is formed as a whole, the conductivity is improved only in the portions where the carbon nanotubes are present, and the other portions are not conductive. The transparent electrode pattern with improved properties can be easily formed.

The transparent conductive film of the present invention contains carbon nanotubes coated on a substrate and a compound represented by the following formula (1). According to this configuration, since the conductivity of the molecular chain of the carbon nanotube can be improved, a transparent conductive film having particularly high conductivity can be realized.

The transparent conductive film of the present invention preferably contains at least 10 parts by weight of a compound represented by the following formula (1) with respect to 100 parts by weight of the carbon nanotubes. According to this configuration, the conductivity of the transparent conductive film can be further improved.

  The manufacturing method of the transparent conductive film of this invention is characterized by including the process of coating a carbon nanotube on a base material, and the process of apply | coating a PEDOT / PSS dispersion liquid on the said carbon nanotube.

  According to this method, since PEDOT / PSS can be applied in a dispersion state on the carbon nanotube coating film, a transparent conductive film can be easily produced.

  The method for producing a transparent conductive film of the present invention includes a step of coating a carbon nanotube on a substrate, a step of applying a composition containing ethylenedioxythiophene and sulfonic acid on the carbon nanotube, and the carbon nanotube. And a step of polymerizing the composition.

  According to this method, since the composition is polymerized after the composition has permeated between the carbon nanotubes, a conductive composition is formed also between the carbon nanotubes, and a highly conductive transparent conductive film can be produced. it can. Moreover, since a composition is apply | coated on a base material with a low molecular compound, handling of a coating liquid becomes easy and a transparent conductive film can be manufactured easily.

In the method for producing a transparent conductive film of the present invention, in the step of coating the carbon nanotube on the substrate, the carbon nanotube is coated, and then the compound represented by the following formula (1) is added to the carbon nanotube. It is preferable to apply to.

  According to this method, since the compound represented by the above formula (1) is encapsulated in the carbon nanotubes coated on the substrate, a transparent conductive film having particularly high conductivity can be produced.

  The touch panel of the present invention is characterized by using the transparent conductive film.

  According to this configuration, since a transparent conductive film made of an organic material is used, it is possible to realize a highly practical touch panel that is not damaged even when the transparent conductive film is bent and deformed in accordance with an input operation. . Moreover, since the damage by deformation | transformation of a transparent conductive film can be prevented, the film thickness of a transparent conductive film can be formed thinly and a touch panel can be manufactured cheaply.

  According to the present invention, a transparent conductive film having excellent transparency and high conductivity can be provided.

(A) is the figure which showed typically the dispersion state of the molecular chain of CNT apply | coated on the base material, (b) is the typical enlarged view of the CNT molecular chain apply | coated on the base material. It is. (A) is a schematic diagram of the transparent conductive film which concerns on embodiment of this invention, (b) is an enlarged view of the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the structural formula of PEDOT / PSS of the transparent conductive film which concerns on embodiment of this invention. (A)-(c) is a figure which shows the manufacturing process of the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the example of a coating film of the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the sheet resistance value of the transparent conductive film which concerns on embodiment of this invention. (A) is a schematic diagram which shows the molecular chain of PEDOT / PSS which concerns on embodiment of this invention, (b) is a schematic diagram which shows the molecular chain of CNT on a base material. It is a figure which shows the polymerization reaction of EDOT. It is a schematic diagram which shows the bridge | crosslinking by the coupling agent of the transparent conductive film which concerns on embodiment of this invention. (A), (b) is a figure which shows the example of a coating film of the coupling agent of the transparent conductive film which concerns on embodiment of this invention. It is a schematic diagram which shows the example which added the dopant to CNT in the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the tendency of the sheet resistance value after dopant addition of the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the change of the sheet resistance value of the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the change of the sheet resistance value in the heat test of the transparent conductive film which concerns on embodiment of this invention. It is a figure which shows the absorption spectrum of the transparent conductive film which concerns on embodiment of this invention. It is a cross-sectional schematic diagram of the touch panel using the transparent conductive film which concerns on embodiment of this invention. It is an enlarged photograph of the transparent conductive film which concerns on the Example of this invention.

  In the field where a transparent conductive film is used, such as a touch panel, in order to improve the performance of the transparent conductive film, a transparent conductive film to which carbon nanotubes (CNTs) are added has been studied. CNT has electrical conductivity characteristics 1000 times or more that of copper, has a very high tensile strength of several tens of GPa, and has a molecular chain diameter as thin as a nanometer scale. For this reason, CNT is expected as a material that can realize a transparent conductive film having excellent transparency and high conductivity.

  The present inventors have intensively studied a transparent conductive film using CNTs. First, the present inventors examined the physical properties of CNT in detail. CNT has a main molecular unit of a graphene sheet in which a plurality of six-membered rings of carbon atoms are expanded in a planar shape, and has a cylindrical molecular chain formed by winding this graphene sheet in a cylindrical shape. The conductivity of CNT originates from the SP2 bond of the carbon atom of the graphene sheet, and has high conductivity toward the cylinder axis direction of the cylindrical molecular chain.

  Next, the present inventors investigated the physical properties of CNT when CNT was used for a transparent conductive film. The physical properties of CNT in the transparent conductive film will be described with reference to FIGS. FIG. 1A is a diagram schematically showing a dispersion state of molecular chains of CNTs coated on a substrate. Since CNT11 has low solubility in a solvent, when CNT11 is used for a transparent conductive film, it is coated on a substrate as a dispersion. As shown in FIG. 1A, the molecular chains of the CNTs 11 coated on the substrate are usually in a state where the molecular chains are dispersed in a complicated manner.

  FIG. 1B is a diagram schematically showing the difference between CNT molecules applied on a substrate. As shown in FIG.1 (b), CNT11 coated on the base material has a cylindrical molecular chain. The CNT11 molecular chain coated on the substrate is coated in a state in which a part of the molecular chain intersects, and is pressed onto the substrate by a press machine or the like. Here, the molecular chain of the CNT 11 pressure-bonded on the base material is pressed and deformed toward the base material surface.

  Therefore, the present inventors have made extensive studies on a transparent conductive film that can improve the conductivity of the CNT 11 by paying attention to the characteristics of the CNT 11 when the above-described CNT 11 is used for the transparent conductive film. As a result, the coating amount of the conductive composition can be reduced by applying the conductive composition so as to cover the CNT 11 coated on the base material with a predetermined amount, and it has excellent transparency and conductivity. It has been found that a high transparent conductive film can be obtained. That is, the CNTs 11 are connected to each other through the conductive composition by allowing the conductive composition to exist in a predetermined amount, for example, a sufficient amount for the coated CNT 11 to exhibit conductivity as a transparent conductive film. The conductivity can be increased. For this reason, the conductivity as a transparent conductive film can be exhibited even in a state where the molecular chain of the CNT 11 is pressed. Thus, coloring of a transparent conductive film can be prevented by restrict | limiting the quantity of a conductive composition to only sufficient quantity in order to show the electroconductivity as a transparent conductive film.

  Furthermore, in the manufacturing process of the transparent conductive film, the present inventors apply the conductive composition in the monomer state on the CNT 11 and then polymerize the conductive composition, thereby improving the conductivity of the transparent conductive film. It has been found that it can be further improved, and that the conductivity of the transparent conductive film can be further improved by adding a compound having a specific structure as a dopant to the CNTs 11, and the present invention has been completed.

  That is, the present invention provides a coating of CNT11 on a substrate, and a conductive composition is present on the CNT11 in a sufficient amount to exhibit conductivity as a transparent conductive film. Both improvement of transparency and improvement of conductivity are realized.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 2A is a schematic diagram of the transparent conductive film according to the present embodiment. As shown in FIG. 2A, the transparent conductive film according to the present embodiment includes CNTs 22 coated on the base material 21 and PEDOT present on the base material 21 so as to cover a part of the CNTs 22. / PSS23. The CNT 22 is coated on the surface of the base material 21 in a state in which each molecular chain is dispersed. The PEDOT / PSS 23 is present on the base material 21 in an amount sufficient to show conductivity as a transparent conductive film. That is, a plurality of coating film regions are formed on the substrate 21 so as to be separated from each other. Thus, in this Embodiment, PEDOT / PSS23 is obtained by coating a part of CNT22 in at least 1 area | region, and a transparent conductive film with high electroconductivity is obtained.

  FIG. 2B is an enlarged view of the transparent conductive film according to the present embodiment. As shown in FIG. 2 (b), the PEDOT / PSS 23 applied to cover the CNTs 22 penetrates between the molecular chains of the intersecting CNTs 22 and conducts between the molecular chains of the CNTs 22 to reduce the contact resistance. . Further, as shown in FIGS. 2A and 2B, PEDOT / PSS 23 is coated on the base material 21 so as to cover a plurality of CNT22 molecular chains in the coating film region. As a result, the plurality of CNT22 molecular chains are electrically connected via the PEDOT / PSS23. As described above, in this embodiment, the PEDOT / PSS 23 conducts conduction between the molecular chains of the intersecting CNT 22 and between the plurality of CNT 22 molecular chains in the coating region of the PEDOT / PSS 23. Improves.

  In addition, when forming a transparent electrode pattern in this Embodiment, it is preferable that CNT22 is patterned by the base material 21. FIG. It is not easy to form and peel a photoresist with PEDOT / PSS23 applied, but it is relatively easy to pattern with only CNT22 having excellent chemical resistance. Even if the PEDOT / PSS 23 is formed on the entire surface later, the PEDOT / PSS 23 alone does not conduct in the portion where the CNT 22 is removed.

  In the present embodiment, the CNT 22 includes a single-layer CNT (SWNT) composed of one graphene sheet, a double-wall CNT (DWNT) composed of two graphene sheets, or a plurality of graphene sheets Any CNT of multi-wall CNT (MWNT) composed of a plurality of layers wound concentrically can be used. Among these, it is preferable to use single-walled CNTs from the viewpoint of the total light transmittance of the obtained transparent conductive coating film. Single-walled CNTs are preferable because the electrical conductivity is improved because the arrangement of carbon atoms is good and there are few structural defects. As the CNT 22, a part of the structure modified with an organic compound, a structure containing a metal atom or a cluster in the structure, or a composite (hybrid) with various organic compounds or inorganic compounds can be used. .

  Moreover, in this Embodiment, it is preferable that the diameter of CNT22 is 0.5 nm-150 nm from a viewpoint of suppressing scattering of visible light. More preferably, it is 0.5 nm to 20 nm. Moreover, the length of the molecular chain of CNT22 is preferably 0.05 μm to 5000 μm from the viewpoint of securing the contact point of the CNT22 molecular chain and improving the conductivity. More preferably, it is 1 micrometer-5000 micrometers.

  In the present embodiment, commercially available CNTs can be used as they are as the CNTs 22. Examples of such commercially available CNTs include, for example, trade name: SO-type manufactured by Meijo Nanocarbon Co., Ltd.

  Next, PEDOT / PSS 23 will be described with reference to FIG. In the present embodiment, a conductive composition mainly containing PEDOT / PSS23 is used from the viewpoint of improving the conductivity of the transparent conductive film. This PEDOT / PSS23 is a polymer complex of PEDOT24, which is a cationic polythiophene, and PSS25, which is a polyanion, as shown in FIG. PEDOT 24 is synthesized by oxidative polymerization from EDOT (2,3-ethylenedioxythiophene) which is a monomer. On the other hand, PSS25 is synthesized by addition polymerization from polystyrene sulfonate anion.

  In addition, as PEDOT / PSS23, you may use a commercially available PEDOT / PSS dispersion liquid (HEC Starck company make, brand name: Clevios PH510).

  In the present embodiment, the conductive composition is not limited to PEDOT / PSS23 as long as it is a conductive composition, and various conductive compositions can be used. For example, as the cationic polythiophene, only a 3,4-disubstituted thiophene shown in FIG. 3 may be used as a repeating unit, and the repeating unit of 3,4-disubstituted thiophene mainly contains and can be polymerized therewith. Another monomer may be included as a subsidiary component. Further, 3,4-disubstituted thiophene may have various substituents.

  Examples of the polyanion constituting the conductive composition include polymer carboxylic acids such as polyacrylic acid, polymethacrylic acid, and polymaleic acid; polymer sulfonic acids such as polystyrene sulfonic acid and polyvinyl sulfonic acid, and the like. be able to. In addition, polyanions such as polymeric carboxylic acids and sulfonic acids are homopolymers polymerized only from anionic monomers such as vinyl carboxylic acids and vinyl sulfonic acids, copolymers consisting of a plurality of types of anionic monomers, and It may be a copolymer of other monomers copolymerizable with an anionic monomer.

  In this Embodiment, it is preferable to contain PEDOT / PSS23 in 10 weight part-1000 weight part with respect to CNT22 and 100 weight part. If PEDOT / PSS23 is 1000 weight part or less, coloring of the transparent conductive film derived from PEDOT / PSS23 can be reduced more, and the transparency of a transparent conductive film can be improved. Moreover, if PEDOT / PSS23 is 10 weight part or more, the contact resistance between the molecular chains of CNT22 will be reduced and the electroconductivity of PEDOT / PSS23 can be improved. PEDOT / PSS23 is preferably used in the range of 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of CNT22, and more preferably in the range of 10 parts by weight to 500 parts by weight from the viewpoint of reducing coloring of the transparent conductive film. It is more preferable.

  Next, a method for manufacturing a transparent conductive film according to the present embodiment will be described with reference to FIGS. In the method for producing a transparent conductive film according to the present embodiment, PEDOT / PSS 23 is applied so as to coat a part of CNT 22 coated on base 21 and a step of coating CNT 22 on base 21. Process.

  As shown in FIG. 4A, first, a CNT22 dispersion is applied to the substrate 21 to coat the CNT22. Next, as shown in FIG. 4B, a PEDOT / PSS23 dispersion is applied so as to cover the CNT 22 coated on the substrate 21. Next, the coating film is preliminarily dried (prebaked) at 90 ° C. for 10 minutes, and finally dried (baked) at 120 ° C. for 20 minutes to produce a transparent conductive film.

  Examples of the base material 21 include metals, glass, ceramics, inorganic materials such as silicon wafers, polyimide, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyamideimide, and liquid crystal polymer heat resistant resin. Organic materials can be used. Among these, it is preferable to use a heat-resistant organic material. Moreover, as the base material 21, either hydrophobic or hydrophilic material may be used. The use of a hydrophobic material is preferable because the affinity between CNT22 and PEDOT / PSS23 is improved in the step of drying the coating liquid after coating. The material of the base material 21 can be arbitrarily selected according to the affinity with the dispersion liquid of CNT22 and PEDOT / PSS23 and the film thickness of the transparent conductive film to be formed.

  As a dispersion medium of CNT22, various solvents, such as a dispersion medium containing water, alcohol, toluene, acetone, ether, and a solvent combining them, can be used. In addition, you may mix | blend additives, such as a coupling agent, a crosslinking agent, a stabilizer, an antisettling agent, a coloring agent, an electric charge preparation agent, a lubricant, with CNT22 dispersion liquid. The CNT22 dispersion is prepared, for example, by mixing CNT22, a surfactant, and a solvent using a mixing and dispersing machine (for example, a ball mill, a roll mill, a homogenizer, etc.) that is commonly used for coating production. Further, when the substrate 21 is a resin, the CNT 22 can be firmly held on the substrate 21 by using a component that dissolves the surface of the substrate 21.

  The application of the CNT22 dispersion to the substrate 21 can be performed by known application conditions such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, screen printing, inkjet printing, pad printing, or Examples thereof include roll coating. In addition, by forming an adhesive layer on the base material 21 in advance, the CNT 22 can be reliably held by the substrate 21. In addition, the CNT 22 can be reliably held by the base material 21 by pressing the CNT 22 to the base material 21 after applying the CNT 22. In particular, when the base material 21 is a resin substrate, it can be more firmly held on the substrate by pressure bonding at a temperature higher than the softening temperature of the resin. The electrical conductivity of the transparent conductive film can be improved by press-bonding the CNT 22 onto the substrate. Note that a transparent insulator is formed on the transparent conductive film including the CNT 22 and PEDOT / PSS 23 thus formed. Thus, a transparent conductive film can be protected by forming a transparent insulator.

  The film thickness of the CNT 22 is preferably in the range of 10 nm to 500 nm, more preferably in the range of 20 nm to 200 nm, from the viewpoint of conductivity. When the film thickness of CNT22 is 20 nm or more, the conductivity of the transparent conductive film is further improved.

  Application of the PEDOT / PSS23 dispersion can be performed under the same application conditions as the CNT22 dispersion. In the present embodiment, the PEDOT / PSS23 dispersion was applied by an air brush (trade name: Spraywork HG, manufactured by Tamiya Co., Ltd.) so that the respective coating film regions are separated from each other at a plurality of points.

  The film thickness of PEDOT / PSS23 is preferably in the range of 40 nm to 600 nm, and more preferably in the range of 60 nm to 300 nm, from the viewpoint of conductivity and transparency of the transparent conductive film. If the film thickness of PEDOT / PSS23 is 40 nm or more, the conductivity of the transparent conductive film greatly increases from the conductivity of CNT22 alone.

  Moreover, in this Embodiment, if the area of the coating-film area | region of PEDOT / PSS23 is a range which satisfy | fills the weight ratio of PEDOT / PSS23 with respect to CNT22 mentioned above, it will not specifically limit, For example, a dot-like fine area An infinite number of regions may be formed, or a small number of coating regions having a wide area may be formed.

  In the above-described example, the example in which the PEDOT / PSS 23 is coated after the CNT 22 is coated has been described. However, as illustrated in FIG. After applying PEDOT / PSS 23 so as to be separated from each other, CNT 22 may be coated on substrate 21.

  Next, an example of a coating film of the transparent conductive film according to the present embodiment will be described with reference to FIG. In the example shown in FIG. 5, conductive regions 41 and 42 in which the CNTs 22 are patterned and non-conductive regions 43 in which the CNTs 22 are not patterned are formed on the base material 21, and the PEDOTs are spaced apart so that the density of the coating region is uniform. This is an example in which / PSS23 is applied over the entire surface of the substrate 21. By coating in this way, in the conductive regions 41 and 42 in which the CNTs 22 on the substrate 21 are patterned, the conductivity is improved by PEDOT / PSS23. On the other hand, the non-conductive region 43 in which the CNT 22 is not patterned can be left without conductivity because the PEDOT / PSSs 23 that are spaced apart from each other are not connected. As described above, the conductive regions 41 and 42 and the non-conductive region 43 whose conductivity is improved in a desired region on the substrate 21 can be arbitrarily formed by performing only the patterning of the CNT 22 without performing the patterning of the PEDOT / PSS 23. Can be formed. Moreover, the visibility of a transparent conductive film can be reduced by apply | coating PEDOT / PSS23 on the whole surface of the base material 21 so that the density of a coating-film area | region may become equal.

  In the example shown in FIG. 5, the embodiment in which the PEDOT / PSS 23 is applied after the CNT 22 is patterned on the base material 21 is described. However, the patterning of the CNT 22 on the base material 21 and the coating film of the PEDOT / PSS 23 are described. The order of is not particularly limited. For example, the CNT 22 may be patterned after coating the substrate 21 with PEDOT / PSS 23, or the patterning of the CNT 22 on the substrate 21 and the coating of PEDOT / PSS 23 may be performed alternately.

  In the present embodiment, the conductive regions 41 and 42 indicate regions where the sheet resistance value is in the range of 100 Ω / □ to 10 KΩ / □. The sheet resistance value of the conductive regions 41 and 42 is preferably in the range of 200Ω / □ to 5 kΩ / □. Further, the nonconductive region 43 refers to a region having a sheet resistance value in a range of 500 KΩ / □ or more. The sheet resistance value is a value measured with a four-probe sheet resistance measuring device under normal temperature and humidity conditions.

  Moreover, in this Embodiment, the contact resistance between the molecular chains of CNT22 is reduced because the coverage of CNT22 by PEDOT / PSS23 on the base material 21 surface is in the range of 5% to 50%. The conductivity of the film is improved. When the coverage is 5% or more, the sheet resistance value is reduced and it can be suitably used as a transparent electrode. The coverage of CNT22 by PEDOT / PSS23 is preferably in the range of 5% to 50%, more preferably in the range of 10% to 40%.

  Next, the present inventors examined in detail about the sheet resistance value of the transparent conductive film which concerns on this Embodiment. The contents investigated by the present inventors will be described with reference to FIG. FIG. 6 shows a change in sheet resistance when a PEDOT / PSS 23 is applied for a predetermined time with an air brush on a transparent conductive film in which only the CNT 22 is coated on a substrate. As shown in FIG. 6, the sheet resistance value of the transparent conductive film obtained by patterning only the CNT 22 is 100%, but the sheet resistance value is reduced to about 40% by applying PEDOT / PSS23 with an air brush for 1 second. descend. Moreover, it turns out that sheet resistance value falls further by lengthening the coating time by an air brush.

  Thus, according to this Embodiment, the electroconductivity of a transparent conductive film can be improved by coating PEDOT / PSS23 on CNT22 coated on the base material 21. FIG. Moreover, since electroconductivity improves even if the application quantity of PEDOT / PSS23 is small, the influence of coloring originating in PEDOT / PSS23 can be reduced and a transparent conductive film with high transparency can be obtained. Moreover, since PEDOT / PSS23 can be coated by coating with an air brush or the like, PEDOT / PSS23 can be applied in a dispersion state, and a transparent conductive film can be easily formed.

  In the transparent conductive film according to the present embodiment, an insulating film such as a protective film may be provided on the coated transparent conductive film.

  In addition, in the transparent conductive film according to the present embodiment, the present inventors coated EDOT, which is a PEDOT 24 precursor, on the base material 21, and then oxidized and polymerized EDOT on the base material 21 to synthesize PEDOT 24. It has been found that the conductivity of the transparent conductive film can be further improved. The details will be described below.

  First, the fine shape of PEDOT / PSS 23 and the fine shape of CNT 22 in the coating liquid will be described with reference to FIGS. 7 (a) and 7 (b). Fig.7 (a) is the figure which showed typically the molecular chain of PEDOT / PSS23 in a coating liquid. FIG. 7B is a diagram schematically showing the molecular chain of the CNT 22 on the surface of the base material 21.

  As shown to Fig.7 (a), PEDOT / PSS23 contains PEDOT24 which the EDOT oxidatively polymerized and PSS25 which the styrenesulfonate anion polymerized. PEDOT24 is an oligomer having a degree of polymerization of about 10 to 40, and has a molecular chain of about 3 nm (L1 in FIG. 7A). On the other hand, PSS25 is a polymer having a large degree of polymerization and a molecular weight of about 400,000, and has a long molecular chain.

  PEDOT / PSS23 becomes a thread-like polymer complex due to the interaction between the molecular chains of the anionic PSS25 molecular chain having a long molecular chain and the cationic PEDOT 24 having a short molecular chain. The polymer complex aggregates into a spherical shape having a diameter of about 30 to 60 nm (L2 in FIG. 7A) in water to form colloidal particles.

  On the other hand, as shown in FIG. 7B, the CNT 22 coated on the substrate 21 has a molecular chain having a diameter of about 1 nm to 3.5 nm (L3 in FIG. 7B). Thus, since the molecular chain of CNT22 is thin with respect to the diameter of the colloidal particle of PEDOT / PSS23, the space | interval formed between the molecular chains of CNT22 becomes small with respect to the diameter of the colloidal particle of PEDOT / PSS23. For this reason, when the dispersion of PEDOT / PSS23 is applied so as to cover the CNT22 of the substrate 21, it becomes difficult for the PEDOT / PSS23 to enter between the molecular chains of the CNT22, and the resistance between the contacts of the CNT22 by the PEDOT / PSS23 is reduced. It is conceivable that the reduction is less likely to occur.

  Therefore, the present inventors applied EDOT in the state of EDOT, which is a raw material monomer of PEDOT 24, and oxidized and polymerized EDOT on the substrate to convert it into PEDOT 24, thereby improving the conductivity of the transparent conductive film. I found that it can be improved.

  FIG. 8 is a diagram showing a synthesis reaction of PEDOT24. As shown in FIG. 8, PEDOT 24 is synthesized by oxidative polymerization of EDOT 26 in a monomer state and ferric p-toluenesulfonate (Fe-pTS) 27 as an oxidizing agent. Since EDOT 26 is dispersed and dissolved in water or an organic solvent in a single molecule state, it is easy to enter between the CNT22 molecular chains. Moreover, since the coating liquid which melt | dissolved EDOT26 becomes low viscosity and low surface energy, it becomes easy to osmose | permeate between CNT22 molecular chains.

  Thus, in this embodiment, EDOT26, which is a precursor of PEDOT24, is applied onto CNT22 in a monomer state, and EDOT26 is oxidatively polymerized with EDOT26 penetrating between the molecular chains of CNT22. It is also formed between the molecular chains. For this reason, between the CNT22 molecular chains is conducted by PEDOT 24, the contact resistance is reduced, and the conductivity of the transparent conductive film is improved.

  Next, the manufacturing method of the transparent conductive film which superposes | polymerizes EDOT26 on a base material and synthesize | combines PEDOT24 with the base material 21 mentioned above is demonstrated. In this case, the process of coating CNT22 on the substrate, the process of applying a composition containing EDOT26 and an oxidizing agent on CNT22, and the process of oxidative polymerization of the composition applied on CNT22 are mainly performed. Including.

  First, as in the case of using the above-described PEDOT 24, the base material 21 is coated with CNT22. Subsequently, the coating liquid containing the composition which mixed EDOT26, the oxidizing agent, the dopant, etc. in the water / alcohol mixed solvent is prepared. Next, the transparent coating film is formed by coating the prepared coating solution on the substrate 21 and drying. The EDOT 26 coated on the substrate 21 is oxidatively polymerized and converted to PEDOT 24 in the drying process.

  As the oxidizing agent, various oxidizing agents such as p-toluenesulfonic acid ferric acid (Fe-pTS) 27 shown in FIG. 8 can be used. As the dopant, additives such as a crosslinking agent, a stabilizer, an anti-settling agent, a colorant, a charge adjusting agent, and a lubricant can be used.

  In addition, in the transparent conductive film which concerns on this Embodiment, the mechanical strength and moisture resistance of a transparent conductive film can be improved by addition of a coupling agent. With reference to FIG. 9, the effect | action of the coupling agent in the transparent conductive film which concerns on this Embodiment is demonstrated.

  As the coupling agent, for example, an alkoxysilane containing an epoxy group is used. When an alkoxysilane containing an epoxy group is used as a coupling agent, as shown in FIG. 9, the PEDOT / PSS 23 coated on the substrate 21 reacts with the coupling agent to crosslink 28 between the molecular chains. (Three-dimensional cross link) is formed. By this cross-linking 28, the bond between the PEDOT / PSS 23 molecular chains is strengthened, and the mechanical strength and moisture resistance of the transparent conductive film are improved.

  Next, with reference to FIG. 10 (a) and FIG.10 (b), the coating film example of the transparent conductive film at the time of using a coupling agent for the transparent conductive film using PEDOT / PSS23 is demonstrated. FIG. 10A shows an example in which PEDOT / PSS 23 and a coupling agent 29 are mixed and coated. In this case, the coupling agent 29 is uniformly applied to the base material 21. On the other hand, FIG. 10B shows an example in which the coupling agent 29 is applied after the PEDOT / PSS 23 is applied to the substrate 21. Thus, the coupling agent 29 may be mixed and applied with PEDOT / PSS23, or may be applied onto the transparent conductive film coated with PEDOT / PSS23.

  In addition, the present inventors have found that the conductivity of the transparent conductive film can be further improved by adding a dopant having a specific structure to the transparent conductive film containing CNT22. The details will be described below.

  FIG. 11 is a schematic diagram showing the CNT 22 to which the dopant 30 according to the present embodiment is added. As shown in FIG. 11, when the dopant 30 is added to the CNT 22, the dopant 30 is included inside the CNT 22 in an ideal case. Here, by adding an electron-withdrawing compound or an electron-donating compound as the dopant 30, the electronic properties of the CNT 22 change and the conductivity of the transparent conductive film is improved. In this Embodiment, electroconductivity can be improved, without reducing the performance of a transparent conductive film by using TCNQ-F4 shown by following formula (1) as the dopant 30 added to CNT22.

  In this Embodiment, it is preferable that the addition amount of TCNQ-F4 shown by said Formula (1) is the range of 10 to 200 weight part with respect to CNT22 and 100 weight part. When the amount of TCQN-F4 added is 10 parts by weight or more, the conductivity of the transparent conductive film is improved. Moreover, when the addition amount of TCQN-F4 is 200 or less, the fall of the performance of a transparent conductive film can be suppressed. The amount of TCNQ-F4 added is preferably 10 to 200 parts by weight, and more preferably 20 to 150 parts by weight.

  Next, the manufacturing method of the transparent conductive film using TCNQ-F4 shown by said Formula (1) is demonstrated. First, a CNT22 dispersion is applied to the substrate 21 to coat the CNT22. Next, a TCNQ-F4 solution dissolved in ethanol to a concentration of 0.01% by weight is prepared, and the prepared TCNQ-F4 solution is applied to the CNTs 22 coated on the substrate 21. Next, by evaporating ethanol, a transparent conductive film in which TCNQ-F4 acts in CNT22 is formed.

  Next, the present inventors investigated in detail about the transparent conductive film to which the dopant 30 was added. As a result, it was found that by adding the dopant 30 to the transparent conductive film according to the present embodiment, the sheet resistance value is reduced to half or less. Further, the transparent conductive film to which the dopant 30 is added has almost no change in sheet resistance even when washed with IPA (isopropyl alcohol), and the increase in sheet resistance is slight even when heated. It was found that there was little coloring of the conductive film. Hereinafter, the contents investigated by the present inventors will be described with reference to FIGS.

  First, the inventors examined the change in the sheet resistance value of the transparent conductive film before and after the addition of the dopant 30. FIG. 12 is a diagram showing a change in the sheet resistance value of the transparent conductive film after the dopant 30 is added. As shown in FIG. 12, when the sheet resistance value R1 of the transparent conductive film to which the dopant 30 was not added was 100%, the sheet resistance value R2 of the transparent conductive film after the addition of the dopant 30 was reduced to about 35%. Furthermore, the sheet resistance value R3 of the transparent conductive film obtained by coating PEDOT / PSS23 on the transparent conductive film after addition of the dopant 30 was reduced to about 17%. From these results, it can be seen that the conductivity of the transparent conductive film is improved by the addition of the dopant 30, and the conductivity is further improved by coating the PEDOT / PSS23.

  Next, the inventors investigated the durability of the transparent conductive film to which the dopant 30 was added. FIG. 13 is a diagram showing a tendency of change in sheet resistance value with respect to IPA cleaning of the transparent conductive film to which the dopant 30 is added. In addition, in FIG. 13, the tendency of the change of a sheet resistance value is shown typically. As shown in FIG. 13, the sheet resistance value R4 of the transparent conductive film to which the dopant 30 is not added shows a high value, whereas the sheet resistance value R5 of the transparent conductive film after the addition of the dopant 30 is significantly reduced. I understand. Further, it can be seen that the sheet resistance value R6 when this transparent conductive film is washed with IPA (isopropyl alcohol) is equivalent to the sheet resistance value R5 before washing, and hardly changes before and after washing with IPA. In addition, the sheet resistance value R7 of the transparent conductive film obtained by re-adding the dopant 30 with respect to the transparent conductive film after IPA cleaning was substantially equal to the sheet resistance value R6 before the dopant 30 was added again. Further, the sheet resistance value R8 when this transparent conductive film was washed again with IPA slightly increased compared to the sheet resistance value R7 before washing. From this result, it can be seen that the transparent conductive film to which the dopant 30 is added does not substantially flow out of the dopant 30 even when washed with IPA and exhibits a low sheet resistance value.

  Next, the present inventors investigated the stability at 80 ° C. of the transparent conductive film to which the dopant 30 was added. FIG. 14 is a diagram showing a sheet resistance value change rate at 80 ° C. of the transparent conductive film to which the dopant 30 is added. As shown in FIG. 14, when the transparent conductive film to which the dopant 30 was added was heated to 80 ° C., the sheet resistance value change rate was about 20% at the start of the test, whereas the sheet resistance even after 60 hours passed. The value change ratio was slightly increased to about 25%. From this result, it can be seen that the transparent conductive film to which the dopant 30 is added has a small resistance value change ratio even when the heating test is performed.

  Next, the present inventors investigated the coloring of the transparent conductive film according to the present embodiment. FIG. 15 is a diagram showing an absorption spectrum of a transparent conductive film M1 using only CNT22, a transparent conductive film M2 using CNT22, and PEDOT / PSS23, and a transparent conductive film M3 added with CNT22, PEDOT / PSS23, and a dopant 30. . As shown in FIG. 15, it can be seen that the absorption spectrum in the visible light region is flat for any of the transparent conductive films M1 to M3, and the transparent conductive film is less colored. From this result, it can be seen that the transparent conductive film according to the present embodiment is less colored, and even if a dopant is added to the transparent conductive film, there is no influence such as coloring.

  As described above, in this embodiment, the addition of the dopant 30 can improve the conductivity without affecting the physical properties of the transparent conductive film, so that a transparent conductive film having particularly high conductivity can be realized.

  Next, an application example of the transparent conductive film according to the present embodiment will be described with reference to FIG. The transparent conductive film according to the present embodiment can be applied to uses such as a touch panel, for example.

  FIG. 16 is a cross-sectional view of a resistive film type touch panel in which the transparent conductive film according to the present embodiment is used. As shown in FIG. 16, the touch panel includes a lower panel plate 101 and an upper panel plate 102 provided to face the lower panel plate 101. A first transparent conductive film 103 is provided on the upper surface of the lower panel plate 101, and a second transparent conductive film 104 is provided on the lower surface of the upper panel plate 102 so as to face the first transparent conductive film 103. The lower panel plate 101 and the upper panel plate 102 are connected via a spacer 105.

  As the lower panel plate 101 and the upper panel plate 102, various polymer materials such as polyethylene and polyester can be used. As the first transparent conductive film 103 and the second transparent conductive film 104, the transparent conductive film according to this embodiment described above is used. In addition, the first transparent conductive film 103 and the second transparent conductive film are preferably configured by changing the composition ratio of the materials so that the electrical conductivity differs.

  Next, the operation of the touch panel according to the present embodiment will be described. First, a coordinate input operation is performed from the lower panel plate 101 and the upper panel plate 102 with a finger or a touch pen. By this input operation, the panel plates 101 and 102 of the touch panel are bent and deformed, and the first transparent conductive film 103 and the second transparent conductive film 104 come into contact with each other. The contact between the first transparent conductive film 103 and the second transparent conductive film 104 energizes the first transparent conductive film 103 and the second transparent conductive film 104. The input coordinates are specified by detecting energization between the first transparent conductive film 103 and the second transparent conductive film 104.

  In the touch panel according to the present embodiment, a transparent conductive film obtained by applying PEDOT / PSS23 to the CNT 22 described above is used for the first transparent conductive film 103 and the second transparent conductive film 104. Since this transparent conductive film can be directly formed on the lower panel plate 101 and the upper panel plate 102 by a coating film, a touch panel can be easily manufactured. Moreover, since the transparent conductive film which concerns on this Embodiment is comprised with the organic material, it can bend and deform | transform with a flexible substrate. For this reason, for example, compared with the case where the first transparent conductive film 103 and the second transparent conductive film 104 are made of an inorganic material such as ITO, the first transparent conductive film 103 and the second transparent conductive film 104 are damaged due to bending deformation. Therefore, a highly durable touch panel can be realized. Moreover, since a transparent conductive film is not damaged even if it coats thinly compared with the transparent conductive film comprised with an inorganic material, a touch panel can also be made thin. Furthermore, since the damage due to the deformation of the transparent conductive film can be prevented, the thickness of the transparent conductive film can be reduced, and the touch panel can be manufactured at low cost.

  Next, examples performed for clarifying the effects of the present invention will be described. The present invention is not limited to the following examples.

  In this example, the transparent conductive film according to the present embodiment and the transparent conductive film according to the comparative example were produced, and various physical properties were evaluated under the following conditions. Below, various physical property measurement conditions are shown.

<Evaluation of transparent electromembrane>
The transparent conductive film was evaluated according to the following conditions.

<Total light transmittance (only transparent conductive film)>
The total light transmittance of the transparent conductive film was measured using a UV-visible spectrum meter.

<Area resistance test>
The area resistance test of the transparent conductive film was carried out by measuring the surface resistance of the transparent conductive film using a 4-probe area resistance meter (Mitsubishi Chemical Corporation, LORESTA EP MCP-1360) and measuring the sheet resistance (sheet resistance value) did.

  In the following Examples and Comparative Examples, the transparent conductive film (Example 1) formed by applying a conductive composition after coating CNTs on a substrate, and the production conditions of the conductive composition were changed. A transparent conductive film (Example 2) was formed. Furthermore, the transparent conductive film which added the dopant was created, and the performance was evaluated (Example 3). Moreover, the transparent conductive film produced without adding a dopant was created with respect to Example 3, and the performance was evaluated.

Example 1
<Preparation of substrate>
The substrate was prepared as follows. First, a base material (material: PET) was cut into a 40 mm square in a clean room (length 40 mm × width 40 mm × thickness 0.2 mm). Next, this PET film was attached to a glass wafer (φ100 mm × thickness 1.1 mm) to prepare a conductive thin film substrate.
<CNT coating solution preparation>
A CNT coating solution was prepared by dispersing 0.01 g of CNT (trade name: SO-Type, manufactured by Meijo Nanocarbon Co., Ltd.) in 100 g of ethanol.

<PEDOT / PSS coating solution preparation process>
A PEDOT / PSS aqueous dispersion (manufactured by H.C. Starck, trade name: Clevios PH510) was used as a coating solution. Next, 5% by weight of DMSO was added to the coating solution as an enhancer. After mixing and dissolving, the coating solution was filtered with a 0.45 μm filter in a clean room to prepare a PEDOT / PSS dispersion.

<CNT application process>
Using a spin coater (manufactured by Mikasa Co., Ltd.), CNTs were coated on the substrate under the conditions of a rotation speed of 1400 rpm and a rotation time of 20 seconds.

<PEDOT / PSS coating process>
Using an air brush (Tamiya Co., Ltd., spray work HG), PEDOT was applied onto the substrate under the condition of a coating time of 2 seconds. A photograph of PEDOT coated on the substrate is shown in FIG. As shown in FIG. 17, PEDOT / PSS was applied so as to be scattered on the substrate.

<Drying process>
The obtained thin film was pre-dried at 90 ° C. for 10 minutes, and then main-dried at 120 ° C. for 20 minutes to produce a transparent conductive film. The film thickness of the obtained transparent conductive film was 200 nm. The total light transmittance was 85%, and the sheet resistance value was 2.7 KΩ / □.

  Next, the Example which produced the transparent conductive film which apply | coated EDOT on the base material, and was oxidatively polymerized on the base material is demonstrated.

(Example 2)
<Preparation of substrate>
A substrate was prepared in the same manner as in Example 1.
<EDOT coating process>
80 g of 0.2 g EDOT, 2.5 g of 50 wt% p-toluenesulfonic acid ethanol solution, and 30% aqueous solution in which ferric sulfate as an oxidizing agent and sodium persulfate (1: 1) are mixed are gradually mixed. The reaction was carried out at about 30 ° C. for about 30 minutes. This solution was collected with a 5 ml pipette and applied onto a CNT-coated substrate prepared in the same manner as in Example 1 using an air brush.

<Drying process>
The obtained thin film was pre-dried at 90 ° C. for 10 minutes, and main drying was performed at 120 ° C. for 20 minutes. The film thickness of the obtained transparent electrode film was 155 nm. The total light transmittance was 85%, and the sheet resistance value was 700Ω / □.

  From the above results, it was found that PEDOT: PSS of the in-situ system using monomer EDOT (prepared by oxidative polymerization of PEDOT on a base material) was a better transparent electrode film.

  Next, as Example 3, a transparent conductive film in which a dopant was added to CNT was produced. Moreover, the transparent conductive film which does not add a dopant as a comparative example was produced.

(Example 3)
<Preparation of substrate>
A substrate was prepared in the same manner as in Example 1.

<Preparation of CNT coating solution>
A CNT coating solution was prepared in the same manner as in Example 1.

<Preparation of dopant solution>
A dopant solution was prepared by dissolving 1 part by weight of tetracyanoquinodimethane (TCNQ-F4) tetrafluoride in 100,000 parts by weight of ethanol.

<PEDOT / PSS coating solution preparation process>
A PEDOT / PSS dispersion was prepared in the same manner as in Example 1.

<CNT application process>
In the same manner as in Example 1, a CNT solution was applied to the substrate to form a CNT film.

<Doping process>
After 1 ml of the dopant solution was dropped onto the CNT film with respect to the area of the CNT film of 20 cm ² , ethanol was evaporated at room temperature.

<PEDOT / PSS coating process>
PEDOT was applied on the substrate in the same manner as in Example 1.

<Drying process>
Drying was performed in the same manner as in Example 1.

(Comparative Example 1)
Other preparation methods were the same as in Example 3 except that there was no doping step.

  As a result of evaluating the transparent conductive film prepared in Example 3 and Comparative Example 1, it was found that the sheet resistance value of the transparent conductive film to which the dopant was added was significantly reduced.

  As described above, according to the transparent conductive film according to the present embodiment, by applying PEDOT / PSS23 on CNT 22 after coating CNT 22 on base material 21, the transparency is high and the conductivity is high. High transparent conductive film can be realized. Moreover, the electroconductivity of a transparent conductive film can further be improved by apply | coating EDOT of a monomer state and performing oxidative polymerization on a base material. Furthermore, the electroconductivity of a transparent conductive film can be improved by adding a dopant to CNT.

  The embodiment disclosed this time is illustrative in all respects and is not limited to this embodiment. The scope of the present invention is shown not by the above description of the embodiments but by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

  The present invention is applicable to devices using various transparent conductive films, such as transparent electrodes and electromagnetic wave shields used in liquid crystal displays, electroluminescent displays, plasma displays, electrochromic displays, solar cells, touch panels, electronic papers and the like.

11 CNT
21 Base material 22 CNT
23 PEDOT / PSS
24 PEDOT
25 PSS
26 EDOT
28 Cross-linking 29 Coupling agent 30 Dopant 101 Lower panel plate 102 Upper panel plate 103 First transparent conductive film 104 Second transparent conductive film 105 Spacer

Claims (15)

  Carbon nanotubes coated on a substrate, and a conductive composition present in a part of the carbon nanotubes, and at least 10 parts by weight of the conductive composition with respect to 100 parts by weight of the carbon nanotubes. A transparent conductive film characterized by containing.   2. The transparent conductive film according to claim 1, wherein the conductive composition is separated from at least two regions on the carbon nanotube.   A base material, a carbon nanotube coated on the base material, and a conductive composition present on the base material, wherein the conductive composition is formed on the carbon nanotube on the base material. A transparent conductive film characterized in that a conductive pattern is formed by a conductive region in which an object is present, and the conductive region contains at least 10 parts by weight of the conductive composition with respect to 100 parts by weight of the carbon nanotubes.   The transparent conductive film according to claim 3, wherein the conductive region has a sheet resistance value in a range of 100 Ω / □ to 10 KΩ / □.   The transparent conductive film according to any one of claims 1 to 4, wherein a coverage of the carbon nanotubes by the conductive composition is in the range of 5% to 50%.   The transparent conductive film according to any one of claims 1 to 5, wherein the carbon nanotube has a film thickness in a range of 10 nm to 500 nm.   The transparent conductive film according to claim 1, wherein the conductive composition contains PEDOT / PSS.   8. The transparent conductive film according to claim 1, wherein the thickness of the PEDOT / PSS is in the range of 40 nm to 600 nm.   The transparent conductive film according to claim 1, wherein the carbon nanotube is patterned. A transparent conductive film comprising carbon nanotubes coated on a substrate and a compound represented by the following formula (1).
The transparent conductive film according to claim 1, comprising at least 10 parts by weight of a compound represented by the following formula (1) with respect to 100 parts by weight of the carbon nanotubes.
  A method for producing a transparent conductive film, comprising: a step of coating a carbon nanotube on a substrate; and a step of applying a PEDOT / PSS dispersion on the carbon nanotube.   Coating a carbon nanotube on a substrate, applying a composition containing ethylenedioxythiophene and sulfonic acid on the carbon nanotube, and polymerizing the composition on the carbon nanotube; The manufacturing method of the transparent conductive film characterized by including these. In the step of coating the carbon nanotubes on the substrate, the compound represented by the following formula (1) is coated on the carbon nanotubes after coating the carbon nanotubes. The manufacturing method of the transparent conductive film of Claim 13.
A touch panel using the transparent conductive film according to claim 1.