CN114467156A - Method for producing transparent conductive film - Google Patents

Method for producing transparent conductive film Download PDF

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Publication number
CN114467156A
CN114467156A CN202080069186.XA CN202080069186A CN114467156A CN 114467156 A CN114467156 A CN 114467156A CN 202080069186 A CN202080069186 A CN 202080069186A CN 114467156 A CN114467156 A CN 114467156A
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transparent conductive
substrate
conductive film
conductive layer
coating
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长濑纯一
长原一平
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/30—Drying; Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length

Abstract

The invention provides a method for manufacturing a transparent conductive film with small conductive anisotropy even containing metal nanowires. The method for producing a transparent conductive film of the present invention comprises: a coating step of forming a coating layer by coating a transparent conductive layer forming composition containing metal nanowires on a long base material while conveying the base material; and a drying step of drying the coating layer to form a transparent conductive layer on the substrate, wherein the average tilt angle θ a of the surface of the substrate is 0.5 ° or more.

Description

Method for producing transparent conductive film
Technical Field
The present invention relates to a method for producing a transparent conductive film.
Background
Conventionally, in an image display device having a touch sensor, a transparent conductive film obtained by forming a metal oxide layer such as ITO (indium tin composite oxide) on a transparent resin film has been often used as an electrode of the touch sensor. However, the transparent conductive film including the metal oxide layer is liable to lose conductivity by bending, and thus has a problem that it is difficult to use the transparent conductive film for applications requiring bendability, such as flexible displays.
On the other hand, as a transparent conductive film having high flexibility, a transparent conductive film including metal nanowires is known. The metal nanowire is a linear conductive material having a diameter of a nanometer size. In the transparent conductive film composed of metal nanowires, the metal nanowires are in a mesh shape, and thus a good electrical conduction path is formed with a small amount of metal nanowires, and openings are formed in gaps of the mesh, thereby achieving high light transmittance. On the other hand, since the metal nanowires are linear, they are easily arranged in an oriented state, and thus there is a problem that conductive anisotropy occurs in the transparent conductive film including the metal nanowires.
Documents of the prior art
Patent document
Patent document 1: japanese Kokai publication Hei 2009-505358
Patent document 2: japanese patent No. 6199034
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object thereof is to provide a method for producing a transparent conductive film having small conductive anisotropy even when containing metal nanowires.
Means for solving the problems
The method for producing a transparent conductive film of the present invention comprises: a coating step of forming a coating layer by coating a transparent conductive layer forming composition containing metal nanowires on a long base material while conveying the base material; and a drying step of drying the coating layer to form a transparent conductive layer on the substrate, wherein the average tilt angle θ a of the surface of the substrate is 0.5 ° or more.
In one embodiment, the average interval Sm of the irregularities on the surface of the substrate is 0.4mm or less.
According to another aspect of the present invention, a transparent conductive film is provided. The transparent conductive film comprises a substrate and a transparent conductive layer disposed on one side of the substrate, and the average inclination angle thetaa of the surface of the substrate is 0.6 DEG or more.
Effects of the invention
According to the present invention, a method for manufacturing a transparent conductive film having small conductive anisotropy can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of a transparent conductive film according to an embodiment of the present invention.
Detailed Description
A. Method for producing transparent conductive film
The method for producing a transparent conductive film of the present invention comprises: a coating step of forming a coating layer by coating a transparent conductive layer forming composition containing metal nanowires on a long base material while conveying the base material; and a drying step of drying the coating layer to form a transparent conductive layer on the substrate. Typically, the coating step and the drying step are performed while the base material in a rolled state is fed and conveyed, and a long transparent conductive film 100 including the base material 10 and the transparent conductive layer 20 disposed on one side of the base material 10 is formed as shown in fig. 1. In one embodiment, the transparent conductive film is wound after the drying step.
A-1. coating Process
As described above, in the coating step, while the long-sized base material is conveyed, the composition for forming a transparent conductive layer containing the metal nanowires is coated on the base material to form the coating layer.
(substrate)
The average inclination angle thetaa of the surface of the substrate is 0.5 DEG or more. In the present invention, by using a base material whose surface shape is specified as described above, the metal nanowires are favorably dispersed in the coating layer, and the orientation of the metal nanowires is disturbed, and as a result, a transparent conductive film having low conductive anisotropy can be produced. In the present specification, the surface of the substrate refers to a surface on which a coating layer is to be formed.
The average inclination angle θ a of the surface of the substrate is preferably 0.8 ° or more, more preferably 1 ° or more, further preferably 1.2 ° or more, and particularly preferably 1.4 ° or more. Within such a range, the above-described effects of the present invention become more significant. The upper limit of the average inclination angle θ a is, for example, 3 ° (preferably 2.5 °, more preferably 2 °). In the present specification, the average inclination angle θ a is defined by the following formula (1).
θa＝tan-1Δa (1)
In the above formula (1), Δ a is a value obtained by dividing the reference length L by the sum (h1+ h2+ h3 … … + hn) of differences (height h) between the peaks and the valleys of adjacent peaks in the reference length L of the roughness curve defined in JIS B0601(1994 version) as shown in the following formula (2). The roughness curve is a curve obtained by removing a surface waveform component longer than a predetermined wavelength from a cross-sectional curve by a phase difference compensation type high-pass filter. The cross-sectional curve is a contour appearing at a notch when the target surface is cut on a plane perpendicular to the target surface.
Δa＝(h1+h2+h3···+hn)/L (2)
The average interval Sm of irregularities on the surface of the substrate is preferably 0.4mm or less, more preferably 0.3mm or less, even more preferably 0.25mm or less, particularly preferably 0.2mm or less, and most preferably 0.15mm or less. The larger the average spacing Sm of the irregularities is, the smaller the orientation of the metal nanowires can be, and a transparent conductive film particularly having small conductive anisotropy can be produced. Further, when the average interval Sm of the irregularities is increased, a significant effect of reducing the conductive anisotropy can be obtained even if the average inclination angle θ a is small (for example, the average inclination angle θ a is 0.6 ° to 1 °). The lower limit of the average spacing Sm of the irregularities is, for example, 0.03mm (preferably 0.04 mm). The definition of the average inclination angle θ a is based on JIS B0601(1994 version).
The arithmetic average surface roughness Ra of the surface of the base material is preferably 0.05 to 3 μm, and more preferably 0.1 to 1.5. mu.m. Within such a range, a transparent conductive film having particularly low conductive anisotropy can be produced. The definition of the arithmetic average surface roughness Ra is based on JIS B0601(1994 version).
The thickness of the substrate is preferably 20 to 200. mu.m, more preferably 30 to 150. mu.m.
The total light transmittance of the substrate is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more.
Any suitable material may be used for the material constituting the substrate. Specifically, for example, a polymer substrate such as a film or a plastic substrate can be preferably used. This is because the smoothness of the substrate and the wettability with respect to the composition for forming a transparent conductive layer are excellent, and the productivity can be greatly improved by continuous production using a roll.
The material constituting the substrate is typically a polymer film containing a thermoplastic resin as a main component. Examples of the thermoplastic resin include: polyester resins, cycloolefin resins such as polynorbornene, acrylic resins, polycarbonate resins, cellulose resins, and the like. Among them, polyester-based resins, cycloolefin-based resins, or acrylic-based resins are preferable. These resins are excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and the like. The thermoplastic resins may be used alone or in combination of two or more. In addition, an optical film used for a polarizing plate, for example, a low retardation substrate, a high retardation substrate, a retardation plate, a luminance improving film, or the like may be used as the substrate.
As a method of conveying the substrate, any suitable method may be adopted. Examples thereof include conveyance by a conveyance roller, conveyance by a conveyance belt, and a combination thereof. The transport speed is, for example, 5 m/min to 50 m/min.
(Metal nanowire)
The metal nanowire is a conductive material having a material of metal, a needle-like or wire-like shape, and a diameter of nanometer. The metal nanowire may be linear or curved. When the transparent conductive layer made of the metal nanowires is used, the metal nanowires are formed into a mesh shape, whereby a good electrical conduction path can be formed even with a small amount of the metal nanowires, and a transparent conductive film with low resistance can be obtained. Further, by forming the metal nanowires in a mesh shape and forming openings in gaps of the mesh, a transparent conductive film having high light transmittance can be obtained.
The ratio of the thickness d to the length L (aspect ratio: L/d) of the metal nanowire is preferably 10 to 100000, more preferably 50 to 100000, and particularly preferably 100 to 10000. When such a metal nanowire having a large aspect ratio is used, the metal nanowire is favorably crossed, and high conductivity can be exhibited by a small amount of the metal nanowire. As a result, a transparent conductive film having high light transmittance can be obtained. In the present specification, the "thickness of the metal nanowire" means a diameter of the metal nanowire when the cross section of the metal nanowire is circular, a short diameter of the metal nanowire when the metal nanowire is elliptical, and a longest diagonal line when the metal nanowire is polygonal. The thickness and length of the metal nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.
The thickness of the metal nanowires is preferably less than 500nm, more preferably less than 200nm, particularly preferably 10 to 100nm, and most preferably 10 to 50 nm. In such a range, a transparent conductive layer having high light transmittance can be formed.
The length of the metal nanowire is preferably 1 to 1000. mu.m, more preferably 10 to 500. mu.m, and particularly preferably 10 to 100. mu.m. Within such a range, a transparent conductive film having high conductivity can be obtained. When the length of the metal nanowire is in the above range, the effect obtained by specifying the surface shape of the base material as described above becomes large.
As the metal constituting the metal nanowire, any appropriate metal may be used as long as it is a conductive metal. Examples of the metal constituting the metal nanowire include silver, gold, copper, and nickel. In addition, a material obtained by subjecting these metals to plating treatment (for example, gold plating treatment) may be used. Among them, silver, copper, or gold is preferable, and silver is more preferable, from the viewpoint of conductivity.
As the method for producing the metal nanowire, any appropriate method can be used. For example, a method of reducing silver nitrate in a solution; and a method of applying a voltage or a current from the tip of the probe to the surface of the precursor, drawing the metal nanowire from the tip of the probe, and continuously forming the metal nanowire. In the method of reducing silver nitrate in a solution, silver nanowires can be synthesized by reducing a silver salt such as silver nitrate in a liquid phase in the presence of a polyhydric alcohol such as ethylene glycol and polyvinylpyrrolidone. Silver nanowires of uniform size can be produced in large quantities, for example, according to the methods described in Xia, Y.et al, chem.Mater. (2002), 14, 4736-.
(composition for Forming transparent conductive layer)
The composition for forming a transparent conductive layer contains metal nanowires. In one embodiment, the composition for forming a transparent conductive layer is prepared by dispersing metal nanowires in any suitable solvent. Examples of the solvent include: water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, and the like. The composition for forming a transparent conductive layer may further contain additives such as a conductive material (for example, conductive particles) other than the resin (binder resin) and the metal nanowires, and a leveling agent. The composition for forming a transparent conductive layer may further contain additives such as a plasticizer, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, an antistatic agent, a compatibilizer, a crosslinking agent, a thickener, inorganic particles, a surfactant, and a dispersant.
The viscosity of the composition for forming a transparent conductive layer is preferably 5 mPs/25 to 300 mPs/25 ℃, and more preferably 10 mPs/25 to 100 mPs/25 ℃. Within such a range, the effect obtained by specifying the surface shape of the base material as described above becomes large. The viscosity of the composition for forming a transparent conductive layer can be measured by a rheometer (for example, MCR302 by Anton Paar).
The dispersion concentration of the metal nanowires in the composition for forming a transparent conductive layer is preferably 0.01 to 5 wt%. Within such a range, the effect of the present invention is remarkable.
As a method for applying the composition for forming a transparent conductive layer, any appropriate method can be used. Examples of the coating method include: spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, relief printing, gravure printing, and the like.
The weight per unit area of the coating layer is preferably 0.3g/m2～30g/m2More preferably 1.6g/m2～16g/m2. Within such a range, the effect obtained by specifying the surface shape of the base material as described above becomes large.
The thickness of the coating layer is preferably 1 to 50 μm, more preferably 2 to 40 μm.
A-2. drying Process
As described above, in the drying step, the coating layer is dried to form the transparent conductive layer on the substrate.
As a method for drying the coating layer, any suitable drying method (for example, natural drying, air-blow drying, and heat drying) can be used. For example, in the case of heat drying, the drying temperature is typically 80 to 150 ℃ and the drying time is typically 1 to 20 minutes.
Any suitable treatment may be performed after the drying process. For example, when a composition for forming a transparent conductive layer containing a binder resin is used, curing treatment by ultraviolet irradiation or the like may be performed.
B. Transparent conductive film
The transparent conductive film is formed by the above-described manufacturing method. Fig. 1 is a schematic cross-sectional view of a transparent conductive film according to an embodiment of the present invention. The transparent conductive film 100 includes: a substrate 10, and a transparent conductive layer 20 disposed on one side of the substrate 10.
The surface resistance value of the transparent conductive film is preferably 0.1. omega./□ to 1000. omega./□, more preferably 0.5. omega./□ to 300. omega./□, and particularly preferably 1. omega./□ to 200. omega./□. The transparent conductive film has a ratio (TD/MD) of a surface resistance value in TD (direction orthogonal to MD) to a surface resistance value in MD (conveyance direction) of preferably 0.7 to 1.5, more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1. The surface resistance value can be measured by "automatic resistivity measuring system MCP-S620 model. MCP-S521 model" of MITSUBISHI CHEMICAL ANALYTECH.
The haze value of the transparent conductive film is preferably 20% or less, more preferably 10% or less, and further preferably 0.1% to 5%.
The total light transmittance of the transparent conductive film is preferably 30% or more, more preferably 35%, and particularly preferably 40% or more.
The average inclination angle θ a of the surface of the substrate is 0.6 ° or more, preferably 0.8 ° or more, more preferably 1 ° or more, further preferably 1.2 ° or more, and particularly preferably 1.4 ° or more. Within such a range, the above-described effects of the present invention become more significant. The upper limit of the average inclination angle θ a is, for example, 3 ° (preferably 2.5 °, more preferably 2 °). The average tilt angle θ a of the surface of the substrate is measured before the transparent conductive layer is formed.
The average interval Sm of irregularities on the surface of the substrate is preferably 0.4mm or less, more preferably 0.3mm or less, even more preferably 0.25mm or less, particularly preferably 0.2mm or less, and most preferably 0.15mm or less. The average interval Sm of the irregularities on the surface of the substrate is measured before the transparent conductive layer is formed.
The arithmetic average surface roughness Ra of the surface of the base material is preferably 0.05 to 3 μm, and more preferably 0.1 to 1.5. mu.m. Further, the above arithmetic average surface roughness Ra of the surface of the base material was measured before the formation of the transparent conductive layer.
The weight per unit area of the transparent conductive layer is preferably 0.001g/m2～0.09g/m2More preferably 0.005g/m2～0.05g/m2。
The content ratio of the metal nanowires in the transparent conductive layer is preferably 0.1 to 50 parts by weight, and more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the binder resin constituting the transparent conductive layer. Within such a range, a transparent conductive film having excellent conductivity and light transmittance can be obtained.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples at all. The evaluation methods of the examples are as follows. The thickness was measured by using a scanning electron microscope "S-4800" manufactured by hitachi high and new technologies, in which a cross section was formed by cutting with a microtome after embedding with an epoxy resin.
(1) Shape of the surface of the substrate
The average distance Sm (mm) between irregularities and the arithmetic average surface roughness Ra (. mu.m) were measured in accordance with JIS B0601(1994 version). Specifically, a glass plate (MICRO SLIDE GLASS manufactured by MATSUNAMI, product No. S, thickness 1.3mm, 45X 50mm) was bonded to the surface opposite to the measurement surface with an adhesive to prepare a sample. Using a stylus-type surface roughness measuring instrument (product name "SURFCODER ET 4000") having a measuring stylus with a radius of curvature R of 2 μm at the tip (diamond), the surface shape of the antiglare layer of the above sample was measured in a certain direction at a scanning speed of 0.1 mm/sec, a cutoff value of 0.8mm, and a measurement length of 4mm, and an average interval Sm of unevenness was determined, and an average inclination angle θ a (°) was determined from the obtained surface roughness curve.
(2) Surface resistance value
The surface resistance values (surface resistance values of MD and TD) of the transparent conductive film were measured by a vortex current method using a non-contact surface resistance tester manufactured by NAPSON corporation, trade name "EC-80". The measurement temperature was set at 23 ℃.
Production example 1 preparation of composition for Forming transparent conductive layer
Silver nanowires were synthesized based on the method described in chem. mater.2002,14, 4736-.
The silver nanowires obtained above were dispersed in pure water to a concentration of 0.2 wt% and 0.1 wt% of dodecyl pentaethylene glycol, to obtain a composition for forming a transparent conductive layer.
[ example 1]
A PET film (trade name "U40" manufactured by TORAY, thickness: 23 μm) was coated with a coating liquid containing 100 parts by weight of an acrylic monomer (trade name "Viscoat # 300" manufactured by Osaka organic chemical industries, Inc., solid content 56%), 30 parts by weight of particles (trade name "TECHNOLYMER SSX-105" manufactured by waterlogging chemical industries, Inc.), 0.5 part by weight of an initiator (trade name "Irgacure 127" manufactured by BASF), and 35 parts by weight of butyl acetate, dried at 100 ℃ for 2 minutes, and irradiated with 300mJ of ultraviolet light to form a substrate A (thickness: 20 μm) on the PET film.
The composition for forming a transparent conductive layer prepared in production example 1 was applied to the substrate a peeled from the PET film by using a bar coater (product name "bar coater No. 16", manufactured by first lacco corporation), and dried in a 120 ℃ air dryer for 2 minutes to form a transparent conductive layer, and a transparent conductive film including a substrate and a transparent conductive layer was obtained. The average tilt angle θ a of the surface of the substrate a on which the transparent conductive layer was formed was 1.5 °, and the average interval Sm of irregularities was 0.05 mm.
The obtained transparent conductive film was subjected to the above evaluation (2). The results are shown in Table 1.
[ example 2]
A base material B (thickness: 20 μm) was formed in the same manner as in example 1 except that 5 parts by weight of particles (trade name "SX-350H", manufactured by general chemical Co., Ltd.) were used in place of 30 parts by weight of particles (trade name "TECHPOMER SSX-105", manufactured by waterlogging chemical Co., Ltd.) and 0.2 part by weight of a thixotropic agent (trade name "SAN", manufactured by Kongfeng industries Co., Ltd.) was added to the coating liquid. Then, a transparent conductive layer was formed in the same manner as in example 1 to obtain a transparent conductive film including a substrate and a transparent conductive layer. The average inclination angle θ a of the surface of the substrate D on which the transparent conductive layer was formed was 0.9 °, and the average interval Sm of irregularities was 0.15 mm.
The obtained transparent conductive film was subjected to the above evaluation (2). The results are shown in table 1.
[ example 3]
A base material C (thickness: 20 μm) was formed in the same manner as in example 2, except that the amount of particles (product name "SX-350H", manufactured by general chemical Co., Ltd.) was changed to 10 parts by weight. Then, a transparent conductive layer was formed in the same manner as in example 1 to obtain a transparent conductive film including a substrate and a transparent conductive layer. The average tilt angle θ a of the surface of the substrate C on which the transparent conductive layer was formed was 1.5 °, and the average interval Sm of irregularities was 0.12 mm.
The obtained transparent conductive film was subjected to the above evaluation (2). The results are shown in table 1.
Comparative example 1
A transparent conductive film was obtained in the same manner as in example 1, except that a PET film (trade name "U40", manufactured by TORAY Co., Ltd., thickness: 23 μm, average tilt angle: 0.1 ℃ and average spacing of irregularities Sm: 0.04mm) was used as the substrate B in place of the substrate A. The obtained transparent conductive film was subjected to the above evaluation (2). The results are shown in table 1.
Comparative example 2
A base material D (thickness: 20 μm) was formed in the same manner as in example 1, except that 15 parts by weight of particles (trade name "TECHNOPOLYMER SSX-101", manufactured by hydroprocess chemical Co., Ltd.) were used in place of 30 parts by weight of particles (trade name "TECHPOMER SSX-105", manufactured by hydroprocess chemical Co., Ltd.). Then, a transparent conductive layer was formed in the same manner as in example 1, and a transparent conductive film including a substrate and a transparent conductive layer was obtained. The average tilt angle θ a of the surface of the substrate D on which the transparent conductive layer was formed was 0.3 °, and the average interval Sm of irregularities was 0.19 mm.
The obtained transparent conductive film was subjected to the above evaluation (2). The results are shown in table 1.
TABLE 1
Figure BDA0003574551240000101
[ reference example 1]
A coating liquid containing 100 parts by weight of an acrylic monomer (trade name "Viscoat # 300" manufactured by Osaka organic chemical industry Co., Ltd., and 56% by weight of a solid content), 10 parts by weight of particles (trade name "TECHNOLYMER SSX-101" manufactured by hydroprocess chemical Co., Ltd.), 0.5 part by weight of an initiator (trade name "Irgacure 127" manufactured by BASF) and 35 parts by weight of butyl acetate was applied to a PET film, the film was dried at 100 ℃ for 2 minutes, and then irradiated with ultraviolet rays of 300mJ to form a substrate C (thickness: 20 μm) on the PET film.
The composition for forming a transparent conductive layer prepared in production example 1 was applied to the substrate C peeled from the PET film by using a bar coater (product name "bar coater No. 16", manufactured by first lacco corporation), and dried in a 120 ℃ air dryer for 2 minutes to form a transparent conductive layer, thereby obtaining a transparent conductive film including a substrate and a transparent conductive layer. The average tilt angle θ a of the surface of the substrate C on which the transparent conductive layer was formed was 0.1 °, and the average interval Sm of irregularities was 0.27 mm.
The obtained transparent conductive film was subjected to the above evaluation (2), and as a result, the surface resistance value of MD was 41 Ω and the surface resistance value of TD was 62 Ω.
Description of the symbols
10 base material
20 transparent conductive layer
100 transparent conductive film.

Claims (3)

1. A method for manufacturing a transparent conductive film, comprising:
a coating step of forming a coating layer by coating a transparent conductive layer forming composition containing metal nanowires on a long base material while conveying the base material; and
a drying step of drying the coating layer to form a transparent conductive layer on the substrate,
the average inclination angle thetaa of the surface of the substrate is 0.5 DEG or more.
2. The method for manufacturing a transparent conductive film according to claim 1,
the average interval Sm of the irregularities on the surface of the substrate is 0.4mm or less.
3. A transparent conductive film comprising a substrate and a transparent conductive layer disposed on one side of the substrate,
the average inclination angle thetaa of the surface of the substrate is 0.5 DEG or more.
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