Three-dimensional molded body derived from transparent conductive film

Abstract

Provided is a three-dimensional molded body derived from a transparent conductive film. The three-dimensional molded body has excellent conductivity and an excellent appearance despite being derived from a film.　This three-dimensional molded body derived from a transparent conductive film comprises a base material and a transparent conductive layer that is provided on at least one side of the base material. The base material includes a resin A that has a softening point of no more than 200°C, and the transparent conductive layer includes metal nanowires. In one embodiment, the metal nanowires have a fused network structure.

Description

Three-dimensional molded body derived from transparent conductive film

[0001] The present invention relates to a three-dimensional molded article derived from a transparent conductive film.

[0002] Conventionally, transparent conductive films have been widely used for electrodes of touch sensors, etc. In recent years, the forms of devices equipped with touch sensors have become more diverse, and the use of transparent conductive films having an uneven shape, in addition to the conventional flat sheet shape, has been considered. However, when three-dimensionally molded (e.g., press molding) to provide an uneven shape, problems such as destruction of the transparent conductive layer, a significant increase in resistance value, and deterioration of appearance occur.

[0003] Special Publication No. 2009-505358

[0004] The present invention has been made to solve the above-mentioned problems, and its main object is to provide a three-dimensional molded article derived from a transparent conductive film that is a three-dimensional molded article derived from a film and has excellent conductivity and appearance.

[0005] The transparent conductive film-derived three-dimensional object of the present invention comprises a substrate and a transparent conductive layer disposed on at least one side of the substrate, the substrate containing resin A having a softening point of 200°C or less, and the transparent conductive layer containing metal nanowires. In one embodiment, the metal nanowires have a fused network structure. In one embodiment, the transparent conductive film-derived three-dimensional object has a total light transmittance of 80% or more. In one embodiment, the transparent conductive film-derived three-dimensional object has a sheet resistivity of 3000 Ω / □ or less. In another aspect of the present invention, a transparent conductive film is provided. This transparent conductive film can be used to form a transparent conductive film-derived three-dimensional object.

[0006] According to an embodiment of the present invention, it is possible to provide a three-dimensional article derived from a transparent conductive film, which is excellent in conductivity and appearance despite being a three-dimensional article derived from a film.

[0007] 1 is a schematic cross-sectional view of a three-dimensional molded article derived from a transparent conductive film according to one embodiment of the present invention; 2 is a schematic perspective view of a three-dimensional molded article derived from a transparent conductive film according to one embodiment of the present invention; 3 is a schematic perspective view of a three-dimensional molded article derived from a transparent conductive film according to one embodiment of the present invention;

[0008] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0009] A. Overall Configuration of a Three-Dimensional Object Derived from a Transparent Conductive Film FIG. 1 is a schematic cross-sectional view of a three-dimensional object derived from a transparent conductive film according to one embodiment of the present invention. The three-dimensional object 100 derived from a transparent conductive film comprises a substrate 10 and a transparent conductive layer 20 disposed on at least one side of the substrate 10. The substrate 10 contains a resin A having a softening point of 200°C or less. The transparent conductive layer 20 also contains metal nanowires (not shown). Although not shown, the transparent conductive film may further include any other appropriate layers.

[0010] 2 is a schematic perspective view of a three-dimensional object derived from a transparent conductive film according to one embodiment of the present invention. In this specification, the term "three-dimensional object derived from a film" refers to a molded object 100 obtained by subjecting a film to molding (typically press molding) in order to provide concave and convex portions 110 in the thickness direction. In one embodiment, as shown in FIG. 3, a 1 cm square grid pattern (each square has an area of ​​1 cm) is formed on the entire surface of the film before three-dimensional molding. ２ ) is provided, the shape of the squares is changed through molding processing, and the area of ​​the squares with the largest area among the changed shape is 1.1 cm ２ ~10cm ２ (Preferably 1.8 cm ２ ~5cm ２ ) is referred to as a "film-derived three-dimensional molded article" in this specification.

[0011] In the present invention, by providing a transparent conductive layer containing metal nanowires on a substrate containing resin A having a softening point of 200°C or less, a three-dimensional molded article derived from a transparent conductive film can be obtained that has high conductivity, excellent appearance, and excellent transparency even after three-dimensional molding.

[0012] The sheet resistivity of the transparent conductive film-derived three-dimensional molded article is preferably 3000 Ω / □ or less, more preferably 1000 Ω / □ or less, and even more preferably 500 Ω / □ or less. The smaller the sheet resistance value of the transparent conductive film-derived three-dimensional molded article, the better, with the lower limit being, for example, 200 Ω / □ (preferably 100 Ω / □, more preferably 50 Ω / □). In this specification, the "sheet resistivity of the transparent conductive film-derived three-dimensional molded article" refers to the sheet resistivity of the transparent conductive film-derived three-dimensional molded article, which is obtained by three-dimensionally molding a transparent conductive film (i.e., a film before three-dimensional molding) after making 1 cm square grids on the entire surface. The maximum sheet resistivity among the grids is defined as the sheet resistivity of the transparent conductive film-derived three-dimensional molded article. In the three-dimensional molding, the transparent conductive film is molded, for example, into a hemispherical shape.

[0013] The haze value of the transparent conductive film-derived three-dimensional molded article is preferably 1% or less, more preferably 0.7% or less, and even more preferably 0.5% or less. The smaller the haze value, the better, but the lower limit is, for example, 0.05%. Within this range, a transparent conductive film-derived three-dimensional molded article suitable for use as a transparent electrode can be obtained.

[0014] The total light transmittance of the transparent conductive film-derived three-dimensional article is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. Within such a range, a transparent conductive film-derived three-dimensional article suitable for use as a transparent electrode can be obtained.

[0015] The thickness of the transparent conductive film is preferably 10 μm to 500 μm, more preferably 15 μm to 300 μm, and even more preferably 20 μm to 200 μm.

[0016] B. Transparent Conductive Layer In one embodiment, the transparent conductive layer comprises metal nanowires and a polymer matrix. By forming a transparent conductive layer comprising metal nanowires, a three-dimensional article derived from a transparent conductive film having excellent flexibility and light transmittance can be obtained. The metal nanowires are protected by the polymer matrix. As a result, corrosion of the metal nanowires is prevented, and a three-dimensional article derived from a transparent conductive film having excellent durability can be obtained.

[0017] The thickness of the transparent conductive layer is preferably 10 nm to 1000 nm, and more preferably 20 nm to 500 nm.

[0018] The total light transmittance of the transparent conductive layer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more.

[0019] The sheet resistance of the transparent conductive layer is preferably 3000 Ω / □ or less, more preferably 1000 Ω / □ or less, and even more preferably 500 Ω / □ or less. The lower the sheet resistance of the transparent conductive layer, the better, but the lower limit is, for example, 200 Ω / □ (preferably 100 Ω / □, more preferably 50 Ω / □).

[0020] (Metal Nanowires) Metal nanowires are conductive materials made of metal, shaped like needles or threads, and having a diameter on the order of nanometers. Metal nanowires may be linear or curved. By using a transparent conductive layer composed of metal nanowires, the metal nanowires form a mesh, allowing even a small amount of metal nanowires to form a good electrical conduction path, resulting in a three-dimensional object derived from a transparent conductive film with low electrical resistance. Furthermore, the mesh-like shape of the metal nanowires allows openings to be formed in the gaps between the meshes, resulting in a three-dimensional object derived from a transparent conductive film with high light transmittance.

[0021] The ratio of the thickness d to the length L of the metal nanowire (aspect ratio: L / d) is preferably 10 to 100,000, more preferably 50 to 100,000, and particularly preferably 100 to 10,000. By using metal nanowires with such a high aspect ratio, the metal nanowires can be well intersected, enabling high conductivity to be achieved with a small number of metal nanowires. As a result, a three-dimensional molded article derived from a transparent conductive film with high light transmittance can be obtained. In this specification, the "thickness of the metal nanowire" refers to the diameter of the metal nanowire when the cross section is circular, the minor axis of the metal nanowire when the cross section is elliptical, and the longest diagonal of the metal nanowire when the cross section is polygonal. The thickness and length of the metal nanowire can be confirmed using a scanning electron microscope or a transmission electron microscope.

[0022] The thickness of the metal nanowires is preferably less than 500 nm, more preferably less than 200 nm, particularly preferably 10 to 100 nm, and most preferably 10 to 50 nm. Within such a range, a transparent conductive layer with high light transmittance can be formed.

[0023] The length of the metal nanowires is preferably 1 μm to 1000 μm, more preferably 10 μm to 500 μm, and particularly preferably 10 μm to 100 μm. Within this range, a three-dimensional article derived from a transparent conductive film having high conductivity can be obtained.

[0024] Any suitable metal can be used as the metal constituting the metal nanowires, as long as it is a conductive metal. Examples of metals constituting the metal nanowires include silver, gold, copper, and nickel. Materials obtained by plating these metals (e.g., gold plating) may also be used. Among these, silver, copper, or gold are preferred from the viewpoint of conductivity, and silver is more preferred.

[0025] Any suitable method can be used to produce the metal nanowires. Examples include a method of reducing silver nitrate in solution, and a method of continuously forming metal nanowires by applying a voltage or current from the tip of a probe to the surface of a precursor and drawing the metal nanowires from the tip of the probe. In the method of reducing silver nitrate in solution, silver nanowires can be synthesized by liquid-phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone. Uniformly sized silver nanowires can be mass-produced, for example, according to the methods described in Xia, Y. et al., Chem. Mater. (2002), 14, 4736-4745 and Xia, Y. et al., Nano Letters (2003), 3(7), 955-960.

[0026] The transparent conductive layer containing the metal nanowires can be formed by applying a dispersion of the metal nanowires in a solvent onto the transparent substrate, and then drying the applied layer.

[0027] Examples of the solvent include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, etc. From the viewpoint of reducing the environmental load, it is preferable to use water.

[0028] The dispersion concentration of the metal nanowires in the metal nanowire dispersion liquid is preferably 0.1% by weight to 1% by weight, which allows the formation of a transparent conductive layer that is excellent in conductivity and light transmittance.

[0029] The metal nanowire dispersion may further contain any appropriate additive depending on the purpose. Examples of the additive include a corrosion inhibitor that prevents corrosion of the metal nanowires, a surfactant that prevents aggregation of the metal nanowires, etc. The type, number, and amount of the additives used may be appropriately determined depending on the purpose.

[0030] Any appropriate method can be adopted as a method for applying the metal nanowire dispersion liquid. Examples of the application method include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing, intaglio printing, and gravure printing. Any appropriate drying method (e.g., natural drying, air drying, and heat drying) can be adopted as a method for drying the coating layer. For example, in the case of heat drying, the drying temperature is typically 50°C to 200°C, and the drying time is typically 1 to 10 minutes.

[0031] The content of the metal nanowires in the transparent conductive layer is preferably 30 to 90% by weight, more preferably 45 to 80% by weight, based on the total weight of the transparent conductive layer. Within this range, a three-dimensional article derived from the transparent conductive film having excellent electrical conductivity and light transmittance can be obtained.

[0032] When the metal nanowires are silver nanowires, the density of the transparent conductive layer is preferably 1.3 g / cm ３ ~10.5g / cm ３ and more preferably 1.5 g / cm ３ ~3.0 g / cm ３ Within such a range, a three-dimensional molded article derived from a transparent conductive film having excellent electrical conductivity and light transmittance can be obtained.

[0033] In one embodiment, the transparent conductive layer is patterned. Any appropriate method can be adopted as the patterning method depending on the form of the transparent conductive layer. The pattern shape of the transparent conductive layer can be any appropriate shape depending on the application. Examples include the patterns described in JP-T-2011-511357, JP-A-2010-164938, JP-A-2008-310550, JP-T-2003-511799, and JP-T-2010-541109. After the transparent conductive layer is formed on the transparent substrate, it can be patterned using any appropriate method depending on the form of the transparent conductive layer.

[0034] In one embodiment, the metal nanowires in the transparent conductive layer have a fused network structure. The metal nanowires having a fused network structure are fused to each other at their contact points. By forming a transparent conductive layer containing metal nanowires having a fused network structure, a three-dimensional article derived from the transparent conductive film with higher conductivity can be obtained without impairing transparency.

[0035] The transparent conductive layer containing the metal nanowires having the fused network structure can be formed, for example, by adding an additive to the metal nanowire dispersion liquid to promote fusion. Examples of the additive include metal halides (e.g., LiCl, CsCl, NaF, NaCl, NaBr, NaI, KCl, MgCl, etc.). ２ , CaCl ２ , AlCl ３ , AgF, etc.), inorganic acids (e.g., nitric acid, nitrous acid, sulfuric acid, etc.), organic acids (e.g., oxalic acid, citric acid, formic acid, acetic acid, lactic acid, propionic acid, butyric acid, acrylic acid, pyruvic acid, trichloroacetic acid, trifluoroacetic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic (lauric) acid, tetradecanoic (myristic) acid, hexadecanoic (palmitic) acid, octadecanoic (stearic) acid, 2-ethylbutyric acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-propylpentanoic acid, pivalic acid, Examples of suitable silver salts include silver salts (e.g., silver nitrate, silver nitrite, silver lactate, silver chloride, silver sulfate, silver oxide, silver acetate, silver chlorate, silver sulfide, silver formate, silver hexanoate, silver octanoate, silver decanoate, silver dodecanoate, silver tetradecanoate, silver hexadecanoate, silver octadecanoate, silver pentanoate, silver pivalate, silver neoheptanoate, silver neononanoate, silver neodecanoate), and compounds containing elements capable of forming silver salts (e.g., chlorine, sulfur) (e.g., hydrogen chloride, sodium chloride). Among these, metal halides are preferred, and NaCl, AgF, LiF, NaBr, or NaF is more preferred. In one embodiment, the transparent conductive layer containing the metal nanowires having a fused network structure can be formed by applying a metal nanowire dispersion containing the additive, followed by a heat treatment and / or a pressure treatment. The temperature of the heat treatment is, for example, 50°C to 200°C.

[0036] The transparent conductive layer containing the metal nanowires having the fused network structure may be formed by exposing a coating layer of the metal nanowire dispersion to an acid halide vapor, such as HCl, HBr, HI, or a mixture thereof.

[0037] Metal nanowires having a fused network structure and a method for producing the same are described, for example, in JP-A-2015-530693, the disclosure of which is incorporated herein by reference.

[0038] (Polymer Matrix) Any appropriate polymer can be used as the polymer constituting the polymer matrix. Examples of such polymers include acrylic polymers; polyester polymers such as polyethylene terephthalate; aromatic polymers such as polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, polyamide, and polyamideimide; polyurethane polymers; epoxy polymers; polyolefin polymers; acrylonitrile-butadiene-styrene copolymers (ABS); cellulose; silicone polymers; polyvinyl chloride; polyacetate; polynorbornene; synthetic rubber; and fluorine-based polymers. Preferably, a curable resin (preferably an ultraviolet-curable resin) composed of a polyfunctional acrylate such as pentaerythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), or trimethylolpropane triacrylate (TMPTA) is used.

[0039] The polymer matrix can be formed by forming a layer of metal nanowires on a transparent substrate, applying a polymer solution onto the layer, and then drying or curing the applied layer, as described above, to form a transparent conductive layer in which the metal nanowires are present in the polymer matrix.

[0040] The polymer solution contains a polymer that constitutes the polymer matrix, or a precursor of the polymer (a monomer that constitutes the polymer).

[0041] The polymer solution may contain a solvent. Examples of the solvent contained in the polymer solution include alcohol-based solvents, ketone-based solvents, tetrahydrofuran, hydrocarbon-based solvents, and aromatic solvents. Preferably, the solvent is volatile. The boiling point of the solvent is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower.

[0042] C. Transparent Substrate The thickness of the transparent substrate is preferably 8 μm to 500 μm, more preferably 10 μm to 250 μm, still more preferably 10 μm to 150 μm, and particularly preferably 15 μm to 100 μm.

[0043] The total light transmittance of the transparent substrate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. Within such a range, a three-dimensional article derived from a transparent conductive film can be obtained that is suitable as a transparent conductive film for use in a touch panel or the like.

[0044] Typically, the resin constituting the transparent substrate is a thermoplastic resin. Examples of the resin constituting the transparent substrate include polycarbonate-based resins, ethylene-based copolymers such as ethylene-vinyl acetate and ethylene-ethyl acrylate, polyamide-based resins such as nylon and dimer acid, polystyrene-based resins such as styrene-butadiene, styrene-isoprene, and styrene-ethylene-butylene, polyester-based resins, polyolefin-based resins, polyvinyl ether-based resins, polymethyl methacrylate-based resins, ionomer resins, cellulose-based resins, polyurethane-based resins, acrylic-based resins, epoxy-based resins, melamine-based resins, and vinyl chloride-based resins.

[0045] As described above, the transparent substrate contains a resin A having a softening point of 200°C or less. The softening point of the resin A is preferably 50°C to 400°C, and more preferably 80°C to 300°C. Within such a range, the effects of the present invention are remarkable. Furthermore, by containing a resin A having a softening point of 80°C or more, deterioration of the transparent substrate during the formation of the transparent conductive layer is prevented, and a three-dimensional molded article derived from the transparent conductive film having excellent heat resistance can be obtained. In this specification, the softening point can be measured by a softening point test (ring and ball method) in accordance with JIS-2817.

[0046] The content of resin A in the transparent substrate is preferably 80 parts by weight or more, more preferably 90 parts by weight or more, even more preferably 95 parts by weight or more, and particularly preferably 100 parts by weight, relative to 100 parts by weight of the resin in the transparent substrate.

[0047] The glass transition temperature of the resin constituting the transparent substrate is preferably 50° C. to 400° C., more preferably 80° C. to 300° C. A transparent substrate having a glass transition temperature in such a range can prevent deterioration during the formation of a transparent conductive layer.

[0048] The transparent substrate may further contain any appropriate additives as necessary. Specific examples of additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, UV absorbers, flame retardants, colorants, antistatic agents, compatibilizers, crosslinkers, and thickeners. The type and amount of additives used may be appropriately determined depending on the purpose.

[0049] As the method for obtaining the transparent substrate, any suitable molding method can be used, and for example, a suitable method can be selected from compression molding, transfer molding, injection molding, extrusion molding, blow molding, powder molding, FRP molding, and solvent casting.Among these manufacturing methods, extrusion molding or solvent casting is preferably used.This is because it can improve the smoothness of the obtained transparent substrate and obtain good optical uniformity.The molding conditions can be appropriately set according to the composition and type of resin used.

[0050] If necessary, the transparent substrate may be subjected to various surface treatments. Any appropriate method may be used for the surface treatment depending on the purpose. Examples of the surface treatment include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, and acid or alkali treatment. In one embodiment, the transparent substrate is surface-treated to make the surface of the transparent substrate hydrophilic.

[0051] The present invention will be described in detail below using examples, but the present invention is not limited to these examples. The measurement methods for each property are as follows. Unless otherwise specified, "parts" and "%" in the examples and comparative examples are based on weight. (1) Initial Resistance: The sheet resistance of the transparent conductive film (i.e., the film before three-dimensional molding) was measured using a NAPSON product under the trade name "EC-80." The measurement temperature was 23°C. (2) Moldability: A block-shaped metal mold having a hemispherical depression (radius: 5 cm) in the center was placed facing the surface opposite the conductor side, and molding was performed using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.) at a set temperature of 160°C to obtain a three-dimensional molded article derived from the transparent conductive film molded into a hemispherical shape. The moldability of the obtained three-dimensional molded article derived from the transparent conductive film was evaluated based on its appearance. (3) Resistance after molding (sheet resistance) After 1 cm square grids were cut on the entire surface of the transparent conductive film (i.e., the film before three-dimensional molding), three-dimensional molding was performed using the method described in (2) above. Numbers were written on the grids after molding, and each was cut out. Silver paste was applied to a width of 3 mm on side A, which was perpendicular to the longest side of each cut-out portion (for each number), and on the side opposite side A. After drying the silver paste, the resistance was measured using a tester, and the sheet resistance was calculated. (4) Transmittance After 1 cm square grids were cut on the entire surface of the transparent conductive film (i.e., the film before three-dimensional molding), three-dimensional molding was performed using the method described in (2) above. The transmittance of the transparent conductive film (i.e., the film before three-dimensional molding) and the transparent conductive film after three-dimensional molding (three-dimensional molded product derived from the transparent conductive film) was measured using a Hitachi U-4100 spectrophotometer. The three-dimensional molded article derived from the transparent conductive film was cut into samples in each grid, and the transmittance was measured.

[0052] [Production Example 1] (Synthesis of Silver Nanowires and Preparation of Silver Nanowire Dispersion) In a reaction vessel equipped with a stirrer, 5 ml of anhydrous ethylene glycol, PtCl ２ anhydrous ethylene glycol solution (concentration: 1.5 × 10 －４ After 4 minutes, 0.5 ml of AgNO was added to the resulting solution. ３ 2.5 ml of anhydrous ethylene glycol solution (concentration: 0.12 mol / L) of AgNO3 and 5 ml of anhydrous ethylene glycol solution (concentration: 0.36 mol / L) of polyvinylpyrrolidone (MW: 55000) were simultaneously added dropwise over 6 minutes. After this addition, the mixture was heated to 160°C and stirred for 1 hour or more. ３ The reaction was carried out until the silver nanowires were completely reduced, producing silver nanowires. Next, acetone was added to the reaction mixture containing the silver nanowires obtained as described above until the volume of the reaction mixture was five times that of the reaction mixture, and the reaction mixture was then centrifuged (2000 rpm, 20 minutes) to obtain silver nanowires. The resulting silver nanowires had a minor axis of 30 nm to 40 nm, a major axis of 30 nm to 50 nm, and a length of 5 μm to 50 μm. The silver nanowires (concentration: 0.2 wt %) and pentaethylene glycol dodecyl ether (concentration: 0.1 wt %) were dispersed in pure water to prepare silver nanowire dispersion I.

[0053] Example 1 A polycarbonate resin film (manufactured by Teijin Chemicals Limited, product name "PC1151", thickness 100 μm, softening point: 130° C.) was used as a substrate. Silver nanowire dispersion liquid I was applied to this substrate and dried. Next, as a material for forming an overcoat layer, resin composition A was prepared by blending 80 parts by weight of DIC Corporation's product name "Unidic ELS-888" and 20 parts by weight of DIC Corporation's product name "Unidic RS28-605". This resin composition A was applied to the conductive layer, and ultraviolet light was irradiated at an exposure dose of 230 mJ / cm. ２ The film was irradiated with light at a wavelength of 1000 nm to form a polymer matrix, thereby obtaining a transparent conductive film. The surface resistance of the transparent conductive film was 30 Ω, and the thickness of the transparent conductive layer was 1.0 μm. The obtained transparent conductive film was subjected to the above evaluations. The results are shown in Table 1.

[0054] [Example 2] A transparent conductive film was obtained in the same manner as in Example 1, except that a nylon film (manufactured by Mitsubishi Chemical Corporation, product name "Superneal", thickness 40 μm, softening point: 100°C) was used instead of the polycarbonate-based resin film. The obtained transparent conductive film was subjected to the above-mentioned evaluations. The results are shown in Table 1.

[0055] [Example 3] A transparent conductive film was obtained in the same manner as in Example 1, except that an acrylic resin film (manufactured by Mitsubishi Chemical Corporation, product name "ACRYPLEN", thickness 40 μm, softening point: 100°C) was used instead of the polycarbonate resin film. The obtained transparent conductive film was subjected to the above evaluations. The results are shown in Table 1.

[0056] Comparative Example 1 A transparent conductive film was obtained in the same manner as in Example 1, except that a PET film (manufactured by Toray Industries, Inc., product name "Lumirror," thickness 40 μm, softening point: 210° C.) was used instead of the polycarbonate-based resin film. The obtained transparent conductive film was subjected to the above-mentioned evaluations. The results are shown in Table 1.

[0057] Comparative Example 2 A transparent conductive film was obtained in the same manner as in Example 1, except that a cycloolefin resin film (manufactured by Zeon Corporation, product name "ZF16", thickness 40 μm, softening point: 250° C.) was used instead of the polycarbonate resin film. The obtained transparent conductive film was subjected to the above-mentioned evaluations. The results are shown in Table 1.

[0058] Comparative Example 3 A polycarbonate resin film (manufactured by Teijin Chemicals, product name "PC1151", thickness 100 μm, softening point: 130° C.) was used as a substrate. This substrate was coated with "Denatron" product manufactured by Nagase ChemteX Corporation and dried to obtain a conductive film having a PEDOT conductive layer. The obtained transparent conductive film was subjected to the above evaluations. The results are shown in Table 1.

[0059] Comparative Example 4 A polycarbonate resin film (manufactured by Teijin Chemicals, product name "PC1151", thickness 100 μm, softening point: 130° C.) was used as a substrate. A transparent conductive film was obtained by vacuum film formation on the substrate using ITO as a target. The obtained transparent conductive film was subjected to the above evaluations. The results are shown in Table 1.

[0060]

[0061] As is clear from Table 1, the present invention provides a three-dimensional article derived from a transparent conductive film, which has excellent conductivity and appearance despite being a three-dimensional article derived from a film. On the other hand, when a substrate with a high softening point is used, it is not possible to mold it into a good appearance (Comparative Examples 1 and 2). Furthermore, when a conductive layer not composed of metal nanowires is provided, the initial resistance is high, and a significant decrease in resistivity is observed upon molding (Comparative Examples 3 and 4). In Comparative Example 4, cracks occurred in the conductive layer upon molding.

[0062] 10: Substrate 20: Transparent conductive layer 100: Transparent conductive film

Claims

1. Substrate and The substrate comprises a transparent conductive layer disposed on at least one side thereof, The base material contains resin A with a softening point of 200°C or lower. The transparent conductive layer contains metal nanowires, A three-dimensional molded body derived from transparent conductive film.

2. The three-dimensional molded body derived from a transparent conductive film according to claim 1, wherein the metal nanowires have a fused network structure.

3. A three-dimensional molded body derived from a transparent conductive film according to claim 1, wherein the total light transmittance is 80% or more.

4. A three-dimensional molded body derived from a transparent conductive film according to claim 2, wherein the total light transmittance is 80% or more.

5. A three-dimensional molded body derived from a transparent conductive film according to claim 1, wherein the sheet resistivity is 3000 Ω / □ or less.

6. A three-dimensional molded body derived from a transparent conductive film according to claim 2, wherein the sheet resistivity is 3000 Ω / □ or less.

7. A three-dimensional molded article derived from a transparent conductive film according to claim 3, wherein the sheet resistivity is 3000 Ω / □ or less.

8. A three-dimensional molded article derived from a transparent conductive film according to claim 4, wherein the sheet resistivity is 3000 Ω / □ or less.

9. A transparent conductive film for forming a three-dimensional molded article derived from a transparent conductive film according to any one of claims 1 to 8.