JP5567871B2 - Substrate with transparent conductive film and method for producing the same - Google Patents

Description

  The present invention relates to a substrate with a transparent conductive film provided with a transparent conductive film on the surface and a method for producing the same.

  Transparent conductive films are widely used as transparent electrodes in fields such as liquid crystal displays, PDPs, touch panels, organic ELs, and solar cells. In forming such a transparent conductive film that exhibits conductivity, in addition to a method of forming a film using a transparent and conductive material, a film containing a conductive filler in a transparent resin is used. There is a method of forming a transparent conductive film that exhibits conductivity while securing transparency by the shape and orientation of the conductive filler although it is colored by forming.

  Here, in general, since the conductive filler has many free electrons that exhibit conductive characteristics, the conductive filler is often colored by plasma resonance vibration absorption generated particularly from the visible light wavelength region. For this reason, for example, when a particulate conductive filler is contained, transparency is ensured in the visible range by reducing the particle size to the nano order. However, when the particle size is reduced, the surface area is increased, so that aggregation between particles of the conductive filler is likely to occur. In order to prevent this, it is necessary to modify the surface of the particles with a dispersant, but this dispersant hinders the conductivity of the transparent conductive film. In this case, it is possible to increase the conductivity by increasing the addition amount of the conductive filler, but on the contrary, the transparency is lowered, so that it is difficult to achieve both transparency and conductivity.

  One way to solve such a trade-off between transparency and conductivity is to change the shape of the conductive filler from particulate to fiber, increase the contact probability of the conductive filler, and mix the conductive filler. There are ways to reduce the amount. Particularly in recent years, a method for forming a transparent conductive film using a material such as carbon nanofiber or carbon nanotube has been reported. For example, as shown in Patent Document 1, a transparent conductive film is formed using vapor grown carbon fiber. There is an example of forming. However, since the carbon-based material has a specific resistance of about 50 S / cm, it is currently difficult to apply it to a transparent electrode that requires high conductivity.

On the other hand, Patent Document 2 proposes forming a transparent conductive film using metal nanowires. The conductivity of the metal nanowire is derived from the metal. For example, in the case of silver, it has a very excellent conductivity of 10 ⁻⁷ Ω · cm, so that it can be applied to a transparent electrode.

  Here, as one method of forming the transparent conductive film 4 containing the metal nanowires 2, there is a method of forming a film by applying a resin solution in which the metal nanowires 2 are dispersed on the surface of the transparent substrate 1, as shown in FIG. As shown in FIG. 2, the transparent conductive film 4 is formed as the transparent coating film 3 containing the metal nanowires 2. In this case, conductivity is imparted to the transparent conductive film 4 by contact between the metal nanowires 2.

JP 2002-266170 A Special table 2009-505358

  In the transparent conductive film 4 formed by containing the metal nanowire 2 in the transparent coating film 3 as described above, the metal nanowire 2 contained in the transparent coating film 3 is exposed, etc. Surface smoothness may be reduced. And when the smoothness of the surface of the transparent conductive film 4 is low in this way, it becomes easy to generate a leak current due to the influence of unevenness. For example, when an organic EL element is produced using a substrate with a transparent conductive film, the transparent conductive film It becomes difficult to form an organic light emitting layer with a uniform film thickness on the surface of the film 4, and it is difficult to produce a stable quality organic EL element.

  Moreover, in order to improve the electroconductivity of the transparent conductive film 4, it is necessary to increase content of the metal nanowire 2, However, When content of the metal nanowire 2 is increased, the smoothness of the surface of the transparent conductive film 4 will fall more. In addition, there is a problem that the haze of the transparent conductive film 4 increases and the light transmittance decreases.

  The present invention has been made in view of the above points, can prevent problems due to surface smoothness, and can increase conductivity without the need to increase the content of metal nanowires. It aims at providing the base material with an electrically conductive film, and its manufacturing method.

With a transparent conductive film substrate according to the present invention, on a transparent substrate, a transparent conductive film-attached substrate having a transparent conductive film made of a transparent coating is provided that includes a metal nanowires, said transparent substrate are intermediate layer is formed made of a transparent resin between the transparent conductive film, the surface of the transparent conductive film, the surface of the transparent conductive film, wherein the metal nanowires have jumped is pressurized, the surface roughness Ra Formed on a smooth surface of 10 nm or less, the transparent resin is a resin that exhibits plasticity when at least the surface of the transparent conductive film is pressed, and the resin that exhibits the plasticity is a thermoplastic resin or a plastic in a semi-cured state It consists of a thermosetting resin or UV curable resin .

  Thus, by forming the surface of the transparent conductive film on a smooth surface with a surface roughness Ra of 10 nm or less, it is possible to suppress the occurrence of leakage current due to the influence of unevenness, and organic light emission formed on the transparent conductive film It becomes easy to make the film thickness of a layer uniform and the problem of the smoothness of the surface of the transparent conductive film formed with the transparent coating film containing metal nanowire can be avoided.

  According to the present invention, when the surface of the transparent conductive film is pressurized, the transparent resin of the intermediate layer is plastically deformed according to the unevenness of the surface of the transparent conductive film, and the surface of the transparent conductive film is smoothed well. The contact point between the metal nanowires contained in the transparent conductive film is increased by the compression of the transparent conductive film by pressurization, and the conductivity can be improved without increasing the content of the metal nanowires. Is.

  In the present invention, the intermediate layer contains translucent particles having a particle diameter of 0.3 to 1.2 times the film thickness of the intermediate layer.

  The translucent particles having this particle size contained in the intermediate layer partially enter the adjacent transparent conductive film, and limit the existence region of the metal nanowires in the transparent conductive film with the translucent particles. It is possible to increase the contact probability of the metal nanowires and secure a large number of contact points between the metal nanowires, and increase the conductivity of the transparent conductive film without having to increase the content of the metal nanowires. It is something that can be done.

In the present invention, the thermoplastic resin may be polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), Teflon (registered trademark: poly Tetrafluoroethylene (PTFE)), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), polyamide (PA), nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE) , Modified PPE, PPO), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), amorphous polyester resin (PET-G), glass fiber reinforced polyethylene terephthalate (GF-PET), cyclic polio Fin (COP), polyphenylene sulfide (PPS), polysulfone (PSF), polyethersulfone (PES), amorphous polyarylate (PAR), liquid crystal polymer (LCP), polyetheretherketone (PEEK), thermoplastic polyimide It is any one of (PI) and polyamideimide (PAI).
Moreover, in this invention, said translucent particle | grains are electroconductive particles, It is characterized by the above-mentioned.

  According to the present invention, conductivity can be obtained even when the metal nanowires contained in the transparent conductive film are in contact with the translucent particles contained in the intermediate layer, and the conductivity can be increased. Is.

  In the present invention, the translucent particle is a particle for controlling the refractive index.

  According to this invention, the refractive index of the intermediate layer can be adjusted by the translucent particles, and the refractive index of the intermediate layer is set between the transparent substrate and the transparent conductive film. It is possible to increase.

Moreover, the manufacturing method of the base material with a transparent conductive film which concerns on this invention is a transparent conductive film which consists of an intermediate layer which consists of transparent resin which exhibits plasticity on a transparent base material, and a transparent coating film containing a metal nanowire in this order. The surface of the transparent conductive film from which the metal nanowire protrudes is pressed to form a smooth surface with a surface roughness Ra of 10 nm or less. The transparent resin exhibiting plasticity is a thermoplastic resin or a semi-cured state. It is made of a thermosetting resin or UV curable resin having plasticity .

  Thus, when the surface of the transparent conductive film is pressurized, the transparent resin of the intermediate layer is plastically deformed according to the unevenness of the surface of the transparent conductive film, and the surface of the transparent conductive film can be smoothed. The surface of the film can be easily smoothed to a surface roughness Ra of 10 nm or less. Moreover, a transparent conductive film can be compressed by pressurizing in this way, the contact point of the metal nanowires contained in a transparent conductive film can be increased, and it is necessary to increase the content of metal nanowires In addition, the conductivity can be increased.

The present invention, pressurization of the pressurization by the hot roll of the pressure by hot pressing, is characterized in that performing at least one.

  When the transparent resin forming the intermediate layer exhibits thermoplasticity, the transparent resin of the intermediate layer can be easily plastically deformed by applying pressure with heating in this way, and the surface of the transparent conductive film Smoothing can be performed easily.

According to the present invention, by forming the surface of the transparent conductive film on a smooth surface having a surface roughness Ra of 10 nm or less, generation of leakage current due to the influence of unevenness can be suppressed, and the transparent conductive film is formed on the transparent conductive film. It becomes easy to make the film thickness of layers, such as an organic light emitting layer, uniform, and the problem of the smoothness of the surface of the transparent conductive film formed with the transparent coating film containing metal nanowire can be avoided. Then, by using a resin exhibiting plasticity as the transparent resin forming the intermediate layer, when the surface of the transparent conductive film is pressurized, the transparent resin of the intermediate layer is plastically deformed according to the irregularities on the surface of the transparent conductive film. are those surfaces of the transparent conductive film can and to Turkey as well smoothed, and in the compression of the transparent conductive film by pressure, the contact point of the metal nanowires each other contained in the transparent conductive film It is possible to increase the conductivity without having to increase the content of metal nanowires.

An example of embodiment of this invention is shown, (a) (b) is sectional drawing, respectively. Another example of embodiment of this invention is shown, (a) (b) is sectional drawing, respectively. It is sectional drawing which shows a prior art example.

  Embodiments of the present invention will be described below.

  FIG. 1 shows an example of an embodiment of the present invention, in which a transparent conductive film 4 is provided on a transparent substrate 1 through an intermediate layer 5. The intermediate layer 5 is formed in contact with the surface of one side of the transparent substrate 1, and the transparent conductive film 4 is formed in contact with the surface of the intermediate layer 5 on the side opposite to the transparent substrate 1.

  In the present invention, the transparent substrate 1 is not particularly limited in its shape, structure, size and the like, and can be appropriately selected according to the purpose. Examples of the shape of the transparent substrate 1 include a flat plate shape, a sheet shape, and a film shape, and the structure may be, for example, a single layer structure or a laminated structure, and may be selected as appropriate. be able to. There is no restriction | limiting in particular also about the material of the transparent base material 1, Any of an inorganic material and an organic material can be used suitably. Examples of the inorganic material forming the transparent substrate 1 include glass, quartz, and silicon. Examples of organic materials include acetate resins such as triacetyl cellulose (TAC); polyester resins such as polyethylene terephthalate (PET); polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, and polyimides. Resin, polyolefin resin, acrylic resin, polynorbornene resin, cellulose resin, polyarylate resin, polystyrene resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic resin Etc. These may be used individually by 1 type and may use 2 or more types together.

  In the present invention, the transparent substrate 1 may be a single substrate as described above, or may be one in which one or more hard coat layers are formed on the surface of the substrate. . Thus, when the transparent base material 1 is equipped with a hard-coat layer, the intermediate | middle layer 5 is formed on a hard-coat layer.

  In the present invention, the refractive index of the transparent substrate 1 becomes a problem at the contact interface portion with the intermediate layer 5 in the transparent substrate 1. Therefore, the refractive index of the transparent substrate 1 means the refractive index of the transparent substrate 1 itself if the transparent substrate 1 is a single substrate, and the transparent substrate 1 has a hard coat layer on the surface. If it has, it means the refractive index of the hard coat layer.

  The hard coat layer can be formed using, for example, a reactive curable resin, that is, a hard coat coating material containing at least one of a thermosetting resin and an ionizing radiation curable resin.

  As the thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, etc. can be used. A crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, and a solvent can be added to these thermosetting resins as necessary.

  The ionizing radiation curable resin preferably has an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro resin. Acetal resin, polybutadiene resin, polythiol polyene resin, oligomers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohol, prepolymers, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, Monofunctional monomers such as methylstyrene and N-vinylpyrrolidone, as well as polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. Can be used. Furthermore, in order to make the ionizing radiation curable resin into an ultraviolet curable resin, it is preferable to incorporate a photopolymerization initiator therein. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones, and the like. In addition to the photopolymerization initiator, a photosensitizer may be used. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone.

In addition, by adding high refractive index particles, that is, ultrafine particles of high refractive index metal or metal oxide, to the hard coat coating material, the refractive index is adjusted by adding high refractive index particles to the hard coat layer. Also good. The high refractive index particles preferably have a refractive index of 1.6 or more and a particle size of 0.5 to 200 nm. The compounding quantity of high refractive index particle | grains is adjusted so that it may become the range of 5-70 volume% with respect to a hard-coat layer. Examples of the ultrafine particles of the high refractive index metal or metal oxide include one or more oxide particles selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Are, for example, ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.71), SnO. ₂ , ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O ₃ ( Examples thereof include fine powders having a refractive index of 1.63).

  After applying such a hard coat coating material on the base material and drying it as necessary, in the case of a hard coat coating material containing a thermosetting resin, it is heated and a hard coat coating containing an ionizing ray curable resin is applied. In the case of a material, a hard coat layer is formed by forming a cured film by irradiating ionizing rays such as ultraviolet rays. The coating method is not particularly limited, and various methods such as spin coating method, dip method, spray method, slide coating method, bar coating method, roll coater method, meniscus coater method, flexographic printing method, screen printing method, and bead coater method are available. Adopted.

  The refractive index of this hard coat layer is preferably in the range of 1.54 to 1.90. If this refractive index is less than 1.54, there is a risk that a sufficient antireflection effect may not be obtained particularly in an optical member for antireflection use. If this refractive index is greater than 1.90, the high refractive index of the hard coat layer may be lost. For this reason, a large amount of high refractive index particles is added to reduce the practicality such as wear resistance.

  The intermediate layer 5 provided on the transparent substrate 1 is formed of a resin having translucency, but a transparent resin 6 exhibiting plasticity is used. As described later, in the step of pressurizing the surface of the transparent conductive film 4, any material may be used as long as it exhibits plasticity, and it is not always necessary to show plasticity other than the pressurizing step. As the transparent resin 6 exhibiting such plasticity, a thermoplastic resin, a semi-cured thermosetting resin, a UV curable resin, or the like can be used.

  The thermoplastic resin can be used without particular limitation as long as it has transparency. For example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, Polystyrene (PS), polyvinyl acetate (PVAc), Teflon (registered trademark: polytetrafluoroethylene (PTFE)), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), polyamide (PA), nylon , Polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), amorphous polyester resin (PET-G), glass Phi -Reinforced polyethylene terephthalate (GF-PET), cyclic polyolefin (COP), polyphenylene sulfide (PPS), polysulfone (PSF), polyethersulfone (PES), amorphous polyarylate (PAR), liquid crystal polymer (LCP), Examples include polyetheretherketone (PEEK), thermoplastic polyimide (PI), and polyamideimide (PAI). When this thermoplastic resin is used in the form of a sheet, film, or plate, it can also serve as the transparent substrate 1 described above.

  In addition, as a thermosetting resin or a UV curable resin, it becomes a semi-cured state by the polymerization reaction of monomers and oligomers, and further by heating to cause a thermal polymerization reaction, or by irradiating with ultraviolet rays to cause a photopolymerization reaction, A completely curable resin is used.

  When using a resin that undergoes such a photopolymerization reaction or thermal polymerization reaction, a monomer or oligomer that undergoes a polymerization reaction directly or under the action of an initiator by irradiation with ionizing radiation such as visible light, ultraviolet light, or an electron beam. A monomer or oligomer having an acrylic group or a methacryl group can be used. Among them, a polyfunctional binder component is preferable in order to increase the scratch resistance and hardness by crosslinking.

  As one having one functional group in one molecule, specifically, for example, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy-diethylene glycol (meta ) Acrylate, methoxy-triethylene glycol (meth) acrylate, methoxy-polyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate phenoxyethyl (meth) acrylate, phenoxy-polyethylene glycol (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, -Hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl phthalate Acid, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Examples include cyclohexyl methacrylate, benzyl (meth) acrylate, (meth) acryloylmorpholine, and the like.

  As those having two or more functional groups, specifically, for example, polyethylene glycol diacrylate, glycerin triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, diester Examples thereof include pentaerythritol hexaacrylate, alkyl-modified dipentaerythritol hexaacrylate, and the compounds having a benzene ring include ethylene oxide-modified bisphenol A diacrylate, modified bisphenol A diacrylate, ethylene glycol diacrylate, and ethylene oxide propylene oxide-modified bisphenol. A diacrylate, propylene oxide tetramethylene oxide Modified bisphenol A diacrylate, bisphenol A- diepoxy - acrylic acid adduct, ethylene oxide-modified bisphenol F diacrylate, and polyfunctional acrylates or methacrylates such as polyester acrylates.

  1,2-bis (meth) acryloylthioethane, 1,3-bis (meth) acryloylthiopropane, 1,4-bis (meth) acryloylthiobutane, 1,2-bis (meth) acryloylmethylthiobenzene, The use of sulfur-containing (meth) acrylates such as 1,3-bis (meth) acryloylmethylthiobenzene is also effective for increasing the refractive index.

  Furthermore, in order to promote curing by ultraviolet rays or heat, a light or thermal polymerization initiator can be blended.

  Although what is generally marketed may be used as a photoinitiator, when it illustrates especially, benzophenone, 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one (Ciba Specialty Chemicals Co., Ltd. product " Irgacure 651 "), 1-hydroxy-cyclohexyl-phenyl-ketone (" Irgacure 184 "manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals' “Darocur 1173”, Lamberti's “Esacure KL200”), Oligo (2-hydroxy-2-methyl-1-phenyl-propan-1-one) (Lamberti's “Esacure KIP150” "), 2-hydroxyethyl-phenyl-2-hydride Xyl-2-methyl-1-propan-1-one (“Irgacure 2959” manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropane-1 -ON ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals Co., Ltd. " Irgacure 369 "), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (" Irgacure 819 "manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (2,6-dimethoxybenzoyl) -2,4 , 4-Trimethyl-pentylphosphine oxide (Ciba Specialty Chemical) ("CGI403" manufactured by Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (= TMDPO) ("Lucirin TPO" manufactured by BASF AG, "Darocur TPO" manufactured by Ciba Specialty Chemicals Co., Ltd.) Thioxanthone or a derivative thereof, and the like can be used, and one or a mixture of two or more of these can be used.

  Further, a tertiary amine such as triethanolamine, ethyl-4-dimethylaminobenzoate, isopentylmethylaminobenzoate or the like may be added for the purpose of photosensitization.

  As a polymerization initiator by heat, a peroxide such as benzoyl peroxide (= BPO) or an azo compound such as azobisisobutylnitrile (= AIBN) is mainly used.

  The blending amount of the photopolymerization initiator and the thermal polymerization initiator is usually preferably about 0.1 to 10 parts by mass with respect to 100 parts by mass of the composition (resin + metal nanowire).

  Moreover, you may use the monomer or oligomer which has cationic polymerizable functional groups, such as an epoxy group, a thioepoxy group, and an oxetanyl group. Further, if necessary, a photocationic initiator or the like can be used in combination. These are likewise preferably polyfunctional.

Further, general sol for thermal polymerization to a resin - gel materials can be mentioned, alkoxy shish orchid, sol such as alkoxy titanium - gel materials are preferred. Such a sol-gel material is a semi-cured state in which only the solvent is volatilized, and exhibits plasticity. Of these, alkoxysilane is preferred. The sol-gel material forms a polysiloxane structure. Specific examples of the alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyl. Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylto Trialkoxysilanes such as ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Examples include diethyldimethoxysilane and diethyldiethoxysilane. These alkoxysilanes can be used as a partial condensate thereof. Among these, tetraalkoxysilanes or partial condensates thereof are preferable. In particular, tetramethoxysilane, tetraethoxysilane or a partial condensate thereof is preferable.

  The transparent conductive film 4 provided on the intermediate layer 5 is formed by the transparent coating film 3 including the metal nanowires 2. Any metal nanowire 2 can be used, and there are no particular limitations on the means for producing the metal nanowires. For example, known means such as a liquid phase method or a gas phase method can be used. it can. There is no restriction | limiting in particular also in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing Ag nanowires, Adv. Mater. 2002, 14, P833-837, Chem. Mater. 2002, 14, P4736-4745, and Materials Chemistry and Physics vol. 114 p333-338 “Preparation of Ag nanorods with high yield by poly process” and the above-mentioned Patent Document 2 as a method for producing Au nanowires, and JP 2006-233252A as a method for producing Cu nanowires. Japanese Patent Laid-Open No. 2002-266007 and the like, and Japanese Patent Laid-Open No. 2004-149871 can be cited as a method for producing Co nanowires. In particular, the above Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in (1) can produce Ag nanowires easily and in large quantities in an aqueous system, and the conductivity of silver is the largest among metals. It can apply preferably as a manufacturing method.

  The average diameter of the metal nanowire 2 is preferably 200 nm or less from the viewpoint of transparency, and preferably 10 nm or more from the viewpoint of conductivity. It is preferable that the average diameter is 200 nm or less because a decrease in light transmittance can be suppressed. On the other hand, if the average diameter is 10 nm or more, the function as a conductor can be expressed significantly, and a larger average diameter is preferable because conductivity is improved. Therefore, the average diameter is more preferably 20 to 150 nm, and further preferably 40 to 150 nm. The average length of the metal nanowire 2 is preferably 1 μm or more from the viewpoint of conductivity, and is preferably 100 μm or less from the viewpoint of the effect on the transparency due to aggregation. More preferably, it is 1-50 micrometers, and it is still more preferable that it is 3-50 micrometers. The average diameter and average length of the metal nanowire 2 can be obtained from an arithmetic average of measured values of individual nanowire images obtained by taking an electron micrograph of a sufficient number of nanowires using SEM or TEM. The length of the metal nanowire 2 should originally be obtained in a state of being linearly stretched, but in reality, since it is often bent, the projected diameter of the metal nanowire 2 using an image analyzer from an electron micrograph And the projected area is calculated, assuming a cylindrical body (length = projected area / projected diameter). The number of metal nanowires to be measured is preferably at least 100 or more, and more preferably 300 or more metal nanowires 2 are measured.

  The metal nanowire 2 is used by being dispersed in a resin solution that forms a transparent coating film 3, and this resin solution is applied to the surface of the transparent substrate 1 to form a transparent conductive film 4 as will be described later. It is something that can be done. In the resin solution, as the resin for forming the transparent coating film 3, one that is polymerized by a polymerization reaction of monomers or oligomers is used.

  As such a resin, the resin that undergoes the photopolymerization reaction or the thermal polymerization reaction mentioned above as the transparent resin of the intermediate layer 5 can be used. A conductive polymer can also be used. Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, polytriphenylamine and the like.

  It is preferable to adjust and set the compounding quantity of the metal nanowire 2 to a resin solution so that the metal nanowire 2 may contain 0.01-90 mass% in the transparent conductive film 4. As for content of the metal nanowire 2, 0.1-30 mass% is more preferable, More preferably, it is 0.5-10 mass%.

Here, it is essential that the resin solution contains a solvent for dissolving or dispersing solid components such as resin solids and metal nanowires 2, but the type of the solvent is not particularly limited. For example, alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene Or mixtures thereof can be used. Among these, it is preferable to use a ketone-based organic solvent, and when a resin solution is prepared using a ketone-based solvent, it can be easily and uniformly applied, and the evaporation rate of the solvent is moderate and dry after coating. Since it is difficult to cause unevenness, a transparent conductive film 4 having a uniform thickness and a large area can be easily obtained. In addition to the above organic solvent, water may be used as the solvent, or an organic solvent and water may be used in combination. The amount of the solvent can uniformly dissolve and disperse each of the above solid components so that the concentration does not cause aggregation during storage after preparing the resin solution and is not too dilute during coating. Adjust as appropriate. Prepare a high-concentration resin solution by reducing the amount of solvent used within the range that satisfies this condition, store it in a state that does not take up the volume, take out the necessary amount at the time of use, and adjust the solvent to a concentration suitable for coating work. It is preferable to dilute with. When the total amount of the solid content and the solvent is 100 parts by mass, the amount of the solvent is preferably set to 50 to 99.9 parts by mass with respect to 0.1 to 50 parts by mass of the total solids, and more preferably By using 70 to 99.5 parts by mass of the solvent with respect to 0.5 to 30 parts by weight of the total solid content, a resin solution that is particularly excellent in dispersion stability and suitable for long-term storage can be obtained. .

  The transparent conductive film 4 can be formed by coating a resin solution in which the metal nanowires 2 are dispersed on the surface of the intermediate layer 5 provided on the transparent substrate 1 to form a film. It can be performed by any method such as spin coating, screen printing, dip coating, die coating, casting, spray coating, gravure coating.

  As described above, the intermediate layer 5 and the transparent conductive film 4 can be laminated and provided on the transparent substrate 1 as shown in FIG. At this time, since the metal nanowire 2 is contained in the transparent conductive film 4, the metal nanowire 2 jumps out of the surface of the transparent conductive film 4, and the surface of the transparent conductive film 4 has unevenness and is not smooth. There are many cases.

  In the present invention, the surface of the transparent conductive film 4 is pressurized after the step of forming the intermediate layer 5 and the transparent conductive film 4. The process of pressurizing the surface of the transparent conductive film 4 includes passing the transparent base material 1 on which the intermediate layer 5 and the transparent conductive film 4 are laminated through a heat roll having a smooth outer peripheral surface, or forming a pressurized surface on a smooth surface. This is performed by pressing the surface of the transparent conductive film 4 with a hot press.

  When the surface of the transparent conductive film 4 is pressed while being heated with a hot roll or a hot press in this way, when the transparent resin 6 forming the intermediate layer 5 is a thermoplastic resin, it is softened by heating and exhibits plasticity. When the transparent resin 6 forming the intermediate layer 5 is a thermosetting resin or a UV curable resin, these resins are in a semi-cured state and soften by heating to exhibit plasticity. Accordingly, if the surface of the transparent conductive film 4 has irregularities, pressure stress concentrates on the convex portions of the surface of the transparent conductive film 4, so the transparent resin 6 in the portion corresponding to the convex portions of the intermediate layer 5. The transparent resin 6 exhibiting plasticity of the intermediate layer 5 is plastically deformed in the reverse pattern of the irregularities on the surface of the transparent conductive film 4, and this transparent resin 6 The surface of the transparent conductive film 4 can be smoothed by plastic deformation.

  The smoothness of the surface of the transparent conductive film 4 is set such that the surface roughness Ra (arithmetic average roughness of JIS B 0601) is 10 nm or less. When the surface roughness Ra is 10 nm or less, it is possible to prevent a leak current from being generated due to surface irregularities. For example, when an organic EL element is produced using a substrate with a transparent conductive film, an organic light emitting layer can be formed with a uniform film thickness on the surface of the transparent conductive film 4, and an organic EL with stable quality. An optical device such as an element or a solar cell can be manufactured.

  Here, in the case where the transparent resin 6 forming the intermediate layer 5 is a thermosetting resin, the transparent conductive film 4 is heated after being deformed plastically in the process of applying pressure while heating with a hot roll or a hot press. The transparent resin 6 can be brought into a completely cured state as the thermal polymerization proceeds. Of course, after the step of pressurizing the transparent conductive film 4 with a hot roll or a hot press, heating may be performed so that the transparent resin 6 is completely cured. When the transparent resin 6 forming the intermediate layer 5 is a UV curable resin, after the step of pressing the transparent conductive film 4 with a hot roll or a hot press, the transparent resin 6 is completely cured by irradiating with ultraviolet rays. can do.

  Further, when the surface of the transparent conductive film 4 is pressurized as described above, even if the metal nanowires 2 protrude from the surface of the transparent conductive film 4, the metal nanowires 2 become transparent as shown in FIG. It is pushed into the transparent coating film 3. Although the metal nanowire 2 is likely to protrude greatly from the surface of the transparent conductive film 4, the metal nanowire 2 can be pushed into the transparent coating film 3 of the transparent conductive film 4 by pressurizing the surface of the transparent conductive film 4. . Moreover, since the transparent conductive film 4 is compressed by pressurization, the metal nanowires 2 in the transparent conductive film 4 come close to each other, and the contact points between the metal nanowires 2 increase. Accordingly, the conductivity of the transparent conductive film 4 can be increased without increasing the content of the metal nanowire 2.

  Further, when the transparent conductive film 4 is pressed while being heated as described above, the vicinity of the interface where the transparent coating film 3 of the transparent conductive film 4 and the transparent resin 6 of the intermediate layer 5 are in contact with each other is softened and fused. Layer 10 is formed. Even if the refractive indexes of the transparent conductive film 4 and the intermediate layer 5 are different, the fusion layer 10 formed between the transparent conductive film 4 and the intermediate layer 5 has a refractive index between them, The refractive index of the fusion layer 10 changes so as to be close to the refractive index of the transparent conductive film 4 on the transparent conductive film 4 side and close to the refractive index of the intermediate layer 5 on the intermediate layer 5 side. . Therefore, reflection of light between the transparent conductive film 4 and the intermediate layer 5 can be suppressed, and the light transmittance can be increased.

  FIG. 2 shows another embodiment of the present invention, wherein the intermediate layer 5 contains translucent particles 7. The translucent particles 7 are not particularly limited as long as they have translucency such as transparency, and examples thereof include silica, alumina, magnesium fluoride, calcium fluoride, cerium fluoride, aluminum fluoride, Acrylic particles, styrene particles, urethane particles, styrene acrylic particles and crosslinked particles thereof, melamine-formalin condensate particles, PTFE (polytetrafluoroethylene) particles, PFA (perfluoroalkoxy resin) particles, FEP (tetrafluoroethylene) -Hexafluoropropylene copolymer) particles, PVDF (polyfluorovinylidene) particles, ETFE (ethylene-tetrafluoroethylene copolymer) -containing fluorine-containing polymer particles, silicone resin particles, glass beads, and the like. . These may be used alone or in combination of two or more. The translucent particles 7 may be solid particles, or may be hollow particles having a structure in which one outer shell covers a single cavity, or porous particles. Furthermore, the shape of the translucent particles 7 may be spherical or irregular.

The translucent particles 7 are those having a particle diameter of 0.3 to 1.2 times the film thickness of the intermediate layer 5. Moreover, it is preferable to set content of the translucent particle 7 so that the volume ratio of the transparent resin 6 and the translucent particle 7 in the intermediate layer 5 may be transparent resin / translucent particle ≦ 5.

  The translucent particles 7 are used by being dispersed in a resin liquid containing the transparent resin 6 forming the intermediate layer 5, and the resin liquid containing the transparent resin 6 and the translucent particles 7 is translucent. The intermediate layer 5 containing the translucent particles 7 can be formed by coating on the surface of the conductive substrate 1. In order to prepare the resin liquid, it is necessary to use a solvent that dissolves or disperses the transparent resin 6 and the translucent particles 7. As this solvent, a resin liquid for applying the transparent conductive film 4 is prepared. Can be used. The coating method is also the same.

And after forming the intermediate | middle layer 5 containing the translucent particle | grains 7 on the transparent base material 1 and forming the transparent conductive film 4 on the intermediate | middle layer 5 like FIG. When the surface of the transparent conductive film 4 is pressed in the same manner as described above, a part of the translucent particles 7 also enter the adjacent transparent conductive film 4 as shown in FIG. For this reason, the presence region of the metal nanowire 2 in the transparent conductive film 4 can be limited by the translucent particles 7, the contact probability of the metal nanowire 2 is increased, and a large number of contacts between the metal nanowires 2 are secured. It is something that can be done. Accordingly, the conductivity of the transparent conductive film 4 can be increased without increasing the content of the metal nanowire 2. In order to obtain the effect of increasing the conductivity of the transparent conductive film 4, the particle size of the translucent particles 7 needs to be not less than 0.3 times the film thickness of the intermediate layer 5. When the particle size of the translucent particles 7 exceeds 1.2 times the film thickness of the intermediate layer 5, the translucent particles 7 affect the surface state of the transparent conductive film 4 and the surface of the transparent conductive film 4 . There is a risk of impairing the smoothness.

  Here, as the translucent particles 7, conductive particles can be used. The conductive particles include indium-tin oxide (ITO) particles, indium-zinc oxide (IZO) particles, tin oxide particles, antimony-doped tin oxide (ATO) and gallium-doped zinc oxide (GZO). ) And the like.

  Thus, since the translucent particles 7 are conductive particles, the metal nanowires 2 contained in the transparent conductive film 4 are in contact with each other, and the translucent particles in which the metal nanowires 2 are contained in the intermediate layer 5. Conductivity can be obtained also by contacting 7, and the conductivity can be increased.

Further, as the light-transmitting particles 7, particles for controlling the refractive index can be used. For refractive index control particles are particles having a transparent resin 6 and different refractive index to form the intermediate layer 5, to select the refractive index of the particles, by or adjust the content ratio of particles, the intermediate layer 5 The refractive index can be controlled.

Such a refractive index control particle is not particularly limited, for example, silica, alumina, magnesium fluoride, calcium fluoride, cerium fluoride, aluminum fluoride, acrylic particles, styrene particles, urethane particles, Styrene acrylic particles and their crosslinked particles, melamine-formalin condensate particles, PTFE (polytetrafluoroethylene) particles, PFA (perfluoroalkoxy resin) particles, FEP (tetrafluoroethylene-hexafluoropropylene copolymer) Examples thereof include particles, PVDF (polyfluorovinylidene) particles, fluorine-containing polymer particles such as ETFE (ethylene-tetrafluoroethylene copolymer), silicone resin particles, glass beads, and the like. As particles having a high refractive index, ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1. _71), SnO _2, ITO (refractive index _1.95), Y 2 _{O 3} (refractive index 1.87), _La 2 _{O 3} (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al There may be mentioned particles such as ₂ O ₃ (refractive index 1.63).

  As described above, since the light-transmitting particles 7 are refractive index control particles, the refractive index of the intermediate layer 5 can be adjusted by the light-transmitting particles 7. For this reason, for example, the refractive index of the intermediate layer 5 is set between the transparent substrate 1 and the transparent conductive film 4, and the difference in refractive index between the substrate 1 and the intermediate layer 5 or the transparent conductive film 4 and the intermediate layer 5 that can reduce the difference in refractive index between the substrate 5 and the interface between the substrate 1 and the intermediate layer 5 and the light reflection at the interface between the transparent conductive film 4 and the intermediate layer 5. Thus, the light transmittance can be increased.

  Next, the present invention will be specifically described with reference to examples.

Example 1
4. Acrylic particles (manufactured by Soken Chemical Co., Ltd., particle size: 300 nm) are used as the light-transmitting particles, UV-curable acrylic resin (“A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.) and acrylic particles 00 parts by mass was dispersed and dissolved in a mixed solvent of 42.14 parts by mass of methyl ethyl ketone and 42.14 parts by mass of methyl isobutyl ketone. Further, 0.72 parts by mass of a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (“Irgacure 184” manufactured by Ciba Geigy) was added and mixed well, followed by stirring and mixing in a constant temperature atmosphere at 25 ° C. for 1 hour. An intermediate layer forming material having a content of 15% by mass was prepared.

  Further, as a metal nanowire, a silver nanowire prepared according to the paper “Materials Chemistry and Physics vol. 114 p333-338“ Preparation of Ag nanoswith high yield by poly process ”” was used. This silver nanowire has an average diameter of 50 nm and an average length of 5 μm. On the other hand, 28.53 parts by mass of silicone resin (“MS51” manufactured by Mitsubishi Chemical Corporation, 51 mass% in terms of oxide) was dissolved in 53.82 parts by mass of IPA. Next, silver nanowire was mix | blended with this solution. The silver nanowire was used as a dispersion having a solid content of 3.0% by mass using IPA as a dispersion medium, and 15.0 parts by mass of this dispersion was added to the above solution and mixed well. Further, 2.65 parts by mass of 0.1H nitric acid is added and mixed well, followed by stirring and mixing in a constant temperature atmosphere at 25 ° C. for 1 hour, whereby a transparent conductive film having a solid content of 15% by mass containing 3% by mass of silver nanowires. A forming material was prepared.

  Then, using a film base material (made of PET, thickness 125 μm) as a transparent base material, the intermediate layer forming material is applied to the surface of the transparent base material with a wire bar coater # 4 and dried at room temperature (23 ° C.) for 2 minutes. Then, an intermediate layer made of a semi-cured film having a thickness of 0.5 μm was formed by heating at 120 ° C. for 3 minutes and drying. Next, the transparent conductive film forming material is applied onto the intermediate layer by the wire bar coater # 2, dried at room temperature (23 ° C.) for 2 minutes, and then heated at 120 ° C. for 3 minutes to dry, A transparent conductive film was formed.

Then, it passes through the biaxial roll press heated at 160 degreeC, and pressurizes with the pressure of 1 Mpa, Furthermore, an ultraviolet-ray is irradiated with the intensity | strength of 500 mJ / cm < ² >, and the semi-hardened film | membrane of an intermediate | middle layer is hardened. By this, the base material with a transparent conductive film was obtained.

(Example 2)
An amorphous polyethylene terephthalate sheet was used as a sheet for forming the intermediate layer. First, the transparent conductive film-forming material used in Example 1 was applied onto the sheet by using a wire bar coater # 2, and room temperature (23 ° C.). After drying for 2 minutes, a transparent conductive film was formed by heating and drying at 120 ° C. for 3 minutes. Next, a biaxial roll in which a film base material (made of PET, thickness 125 μm) is used as a transparent base material, an amorphous polyethylene terephthalate sheet on which a transparent conductive film is formed is superimposed on the surface of the transparent base material, and heated to 160 ° C. A substrate with a transparent conductive film in which an intermediate layer made of an amorphous polyethylene terephthalate sheet and a transparent conductive film were laminated on a transparent substrate was obtained by passing through a press machine and applying a pressure treatment at a pressure of 1 MPa.

(Example 3)
Using ITO particles (particle size 100 nm) as translucent particles, UV-curable acrylic resin (“A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.) 10.00 parts by mass and ITO particles 5.00 parts by mass, It was dispersed and dissolved in a mixed solvent of 42.14 parts by mass of methyl ethyl ketone and 42.14 parts by mass of methyl isobutyl ketone. Further, 0.72 parts by mass of a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (“Irgacure 184” manufactured by Ciba Geigy) was added and mixed well, followed by stirring and mixing in a constant temperature atmosphere at 25 ° C. for 1 hour. An intermediate layer forming material having a content of 15% by mass was prepared.

Then, using a film base material (made of PET, thickness 125 μm) as a transparent base material, the intermediate layer forming material is applied to the surface of the transparent base material with a wire bar coater # 2, and the temperature is normal temperature (23 ° C.) for 2 minutes. After drying, the film was dried by heating at 120 ° C. for 3 minutes, and further irradiated with ultraviolet rays at an intensity of 100 mJ / cm ² to form an intermediate layer made of a semi-cured film having a thickness of 0.3 μm. Next, the transparent conductive film-forming material used in Example 1 was applied onto the intermediate layer with a wire bar coater # 2, dried at room temperature (23 ° C.) for 2 minutes, and then heated at 120 ° C. for 3 minutes to dry. By doing so, a transparent conductive film was formed.

Then, it passes through the biaxial roll press heated at 160 degreeC, and pressurizes with the pressure of 1 Mpa, Furthermore, an ultraviolet-ray is irradiated with the intensity | strength of 500 mJ / cm < ² >, and the semi-hardened film | membrane of an intermediate | middle layer is hardened. By this, the base material with a transparent conductive film was obtained.

(Comparative Example 1)
Using a film base material (made of PET, thickness 125 μm) as a transparent base material, the transparent conductive film forming material used in Example 1 was applied to the surface of the transparent base material with a wire bar coater # 2, and room temperature (23 ° C.) After drying for 2 minutes, the film was dried by heating at 120 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays at an intensity of 500 mJ / cm ² to produce a transparent conductive film. Then, the base material with a transparent conductive film was obtained by passing through the biaxial roll press heated at 160 degreeC, and pressurizing with the pressure of 1 Mpa.

(Comparative Example 2)
Using a film base material (made of PET, thickness 125 μm) as a transparent base material, the transparent conductive film forming material used in Example 1 was applied to the surface of the transparent base material with a wire bar coater # 2, and room temperature (23 ° C.) And then dried at 120 ° C. for 3 minutes, and further cured by irradiating and curing ultraviolet rays at an intensity of 500 mJ / cm ² to produce a substrate with a transparent conductive film. Obtained.

  About the base material with a transparent conductive film of Examples 1-3 and Comparative Examples 1-2 obtained as mentioned above, the transmittance | permeability, the surface resistance of the transparent conductive film, and the surface roughness Ra of the transparent conductive film were measured. Here, the transmittance was measured using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech). The surface resistance was measured using a surface resistance meter (“Hiresta IP (MCP-HT260)” manufactured by Mitsubishi Chemical Corporation). Furthermore, the surface roughness Ra was measured according to JIS B 0601. The results are shown in Table 1.

  As can be seen from Table 1, in each of the examples provided with the intermediate layer, the surface smoothness was improved, and the resistance reduction was improved by increasing the contact of the silver nanofibers. In particular, when a substrate with a transparent conductive film is used for an organic EL element or a solar cell, the surface resistance of the transparent conductive film is preferably 100 Ω / □ or less, but the examples in the respective examples satisfy this condition. . On the other hand, in the comparative example in which the intermediate layer is not provided, the surface smoothness and the resistance reduction are insufficient in both of the comparative example 1 in which pressure is applied and the comparative example 2 in which pressure is not applied. .

DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Metal nanowire 3 Transparent coating film 4 Transparent electrically conductive film 5 Intermediate layer 6 Transparent resin 7 Translucent particle

Claims (7)

On a transparent substrate, a substrate with a transparent conductive film provided with a transparent conductive film composed of a transparent coating film containing metal nanowires,
Are intermediate layer is formed made of a transparent resin between the transparent conductive film and the transparent substrate,
The surface of the transparent conductive film is pressed on the surface of the transparent conductive film from which the metal nanowires protrude, and is formed on a smooth surface having a surface roughness Ra of 10 nm or less .
The transparent resin is a resin that exhibits plasticity when pressurizing at least the surface of the transparent conductive film, and the resin exhibiting plasticity is a thermoplastic resin, a thermosetting resin having plasticity in a semi-cured state, or UV curing. with a transparent conductive film substrate, characterized by comprising the resin. The intermediate layer, with a transparent conductive film group according to claim 1, characterized in that light-transmitting particle is contained with a membrane particle size of 0.3-1.2 times the thickness of the intermediate layer Wood. The thermoplastic resin includes polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), and Teflon (registered trademark: polytetrafluoroethylene (PTFE). )), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), polyamide (PA), nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO) ), Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), amorphous polyester resin (PET-G), glass fiber reinforced polyethylene terephthalate (GF-PET), cyclic polyolefin (COP), Rephenylene sulfide (PPS), polysulfone (PSF), polyethersulfone (PES), amorphous polyarylate (PAR), liquid crystal polymer (LCP), polyetheretherketone (PEEK), thermoplastic polyimide (PI), The substrate with a transparent conductive film according to claim 1, wherein the substrate is a polyamideimide (PAI). The substrate with a transparent conductive film according to claim 2 , wherein the translucent particles are conductive particles. The substrate with a transparent conductive film according to claim 2 or 4 , wherein the translucent particles are particles for controlling a refractive index. On the transparent substrate, an intermediate layer made of a transparent resin exhibiting plasticity and a transparent conductive film made of a transparent coating film containing metal nanowires are provided in this order,
Pressurizing the surface of the transparent conductive film from which the metal nanowires are protruding to form a smooth surface with a surface roughness Ra of 10 nm or less,
The method for producing a substrate with a transparent conductive film, wherein the transparent resin exhibiting plasticity comprises a thermoplastic resin, a thermosetting resin having plasticity in a semi-cured state, or a UV curable resin . The pressurization, pressurization by hot roll of pressure by hot pressing, a transparent conductive method for producing film-coated substrate according to claim 6, characterized in that performing at least one.

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