WO2015177963A1 - 塗工方法 - Google Patents

塗工方法 Download PDF

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Publication number
WO2015177963A1
WO2015177963A1 PCT/JP2015/001967 JP2015001967W WO2015177963A1 WO 2015177963 A1 WO2015177963 A1 WO 2015177963A1 JP 2015001967 W JP2015001967 W JP 2015001967W WO 2015177963 A1 WO2015177963 A1 WO 2015177963A1
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Prior art keywords
coating
transparent conductive
conductive film
aqueous
aqueous coating
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PCT/JP2015/001967
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English (en)
French (fr)
Japanese (ja)
Inventor
井上　純一
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デクセリアルズ株式会社
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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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • 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
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • 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

Definitions

  • the present invention relates to a coating method, and relates to a coating method in which an aqueous coating solution containing at least one of metal nanowires and carbon nanotubes is coated on a substrate using a die coater.
  • a transparent conductive film provided on the display surface of the display panel, and a transparent conductive film such as a transparent conductive film of an information input device arranged on the display surface side of the display panel, such as a transparent conductive film, includes indium tin oxide.
  • Metal oxides such as (ITO) have been used.
  • transparent conductive films using metal oxides are expensive to produce because they are sputtered in a vacuum environment, and cracks and delamination are likely to occur due to deformation such as bending and deflection. .
  • a transparent conductive film using a metal oxide instead of a transparent conductive film using a metal oxide, a transparent conductive film using metal nanowires or carbon nanotubes that can be formed by coating or printing and has high resistance to bending and bending has been studied.
  • Transparent conductive films using metal nanowires and carbon nanotubes are also attracting attention as next-generation transparent conductive films that do not use indium, which is a rare metal (see, for example, Patent Documents 1 and 2).
  • a coating solution such as a photoresist solution is applied by flat plate slit die coating (for example, Patent Documents 3 and 4).
  • the coating liquid is an aqueous coating liquid whose main solvent is water
  • the surface tension of water with respect to a solvent system such as isopropyl alcohol (IPA) or ethanol (EtOH)
  • IPA isopropyl alcohol
  • EtOH ethanol
  • the wettability is poor, and coating defects such as coating repelling may occur.
  • the aqueous coating liquid containing metal nanowires and / or carbon nanotubes is applied, the in-plane distribution of the sheet resistance value may become uneven due to poor coating.
  • an object of the present invention is to provide a coating method capable of producing a transparent conductive film in which the coating failure is prevented and the in-plane distribution of the sheet resistance value is uniform.
  • the present inventor uses a die coater for an aqueous coating solution containing at least one of metal nanowires and carbon nanotubes and a solvent containing water as a main solvent.
  • the viscosity of the aqueous coating solution is 1 mPa ⁇ s to 50 mPa ⁇ s
  • the surface tension of the aqueous coating solution is 20 mN / m to 60 mN.
  • the number of capillaries Ca is 0.03 or less, thereby preventing coating failure and producing a transparent conductive film having a uniform in-plane distribution of sheet resistance values.
  • a coating liquid preparation step of preparing an aqueous coating liquid containing at least one of metal nanowires and carbon nanotubes and a solvent containing water as a main solvent, and the aqueous coating liquid using a die coater A coating step of coating on a substrate, wherein the aqueous coating solution has a viscosity of 1 mPa ⁇ s to 50 mPa ⁇ s, and the aqueous coating solution has a surface tension of 20 mN / second.
  • the coating method is characterized in that it is m to 60 mN / m, and the capillary number Ca represented by the following formula (1) is 0.03 or less.
  • Ca ⁇ U / ⁇ (1)
  • ⁇ represents the viscosity (Pa ⁇ s) of the aqueous coating solution
  • U represents the coating speed (m / s) of the aqueous coating solution
  • ⁇ represents the aqueous coating solution.
  • N represents the surface tension (N / m) of the coating solution.)
  • an aqueous coating solution containing at least one of metal nanowires and carbon nanotubes and a solvent containing water as a main solvent is applied onto a substrate using a die coater.
  • the viscosity of the aqueous coating solution is 1 mPa ⁇ s to 50 mPa ⁇ s
  • the surface tension of the aqueous coating solution is 20 mN / m to 60 mN / m
  • Capillary number Ca is 0.03 or less.
  • the coating method according to ⁇ 2> since the coating speed of the aqueous coating solution is 100 mm / sec or less, it is possible to prevent coating stripes and coating leakage.
  • the ratio of the coating gap between the die coater and the substrate to the wet coating thickness of the aqueous coating solution (coating gap / wet coating thickness) is 1.5 to 4.5.
  • the ratio of the coating gap between the die coater and the substrate to the wet coating thickness of the aqueous coating solution (coating gap / wet coating thickness) is 1. Since it is .5 to 4.5, it is possible to prevent coating streaks and coating leakage and to perform coating satisfactorily.
  • ⁇ 4> The coating method according to any one of ⁇ 1> to ⁇ 3>, wherein the wet coating thickness of the aqueous coating solution is 3 ⁇ m to 20 ⁇ m.
  • the coating method according to ⁇ 4> since the wet coating thickness of the aqueous coating solution is 3 ⁇ m to 20 ⁇ m, the coating can be performed satisfactorily and the in-plane distribution of the sheet resistance value is made uniform.
  • a transparent conductive film can be manufactured.
  • ⁇ 5> The coating method according to any one of ⁇ 1> to ⁇ 4>, wherein a slit gap of the die coater is 30 ⁇ m to 150 ⁇ m.
  • the slit gap of the die coater is 30 ⁇ m to 150 ⁇ m, the water-based coating liquid can be prevented from clogging in the die coater and the water-based coating can be prevented. Liquid dripping can be prevented.
  • ⁇ 6> The coating method according to any one of ⁇ 1> to ⁇ 5>, wherein the dry coating thickness of the aqueous coating solution is 30 nm to 70 nm. In the coating method according to ⁇ 6>, since the dry coating thickness of the aqueous coating solution is 30 nm to 70 nm, a transparent conductive film having sufficient conductivity and transparency can be obtained.
  • ⁇ 7> The coating method according to any one of ⁇ 1> to ⁇ 6>, wherein in the coating step, the coating temperature of the aqueous coating solution is 10 ° C. to 60 ° C.
  • the coating temperature of the aqueous coating solution is 10 ° C. to 60 ° C.
  • the viscosity of the aqueous coating solution can be easily adjusted.
  • the present invention it is possible to solve the conventional problems and achieve the object, and to manufacture a transparent conductive film in which the in-plane distribution of the sheet resistance value is prevented by preventing poor coating.
  • the coating method which can be provided can be provided.
  • FIG. 1 is a schematic diagram for explaining a die coater used in the coating method of the present invention.
  • FIG. 2 is a schematic diagram for explaining a calendar processing step (pressure treatment step) performed after the coating method of the present invention (No. 1).
  • Drawing 3 is a mimetic diagram for explaining the calendar processing process (pressurization processing process) performed after the coating method of the present invention (the 2).
  • the coating method of the present invention includes at least a coating liquid preparation step and a coating step, and further includes other steps appropriately selected as necessary.
  • the coating liquid preparation step is a step of preparing an aqueous coating solution.
  • the aqueous coating solution contains at least one of metal nanowires and carbon nanotubes and a solvent, and further contains a transparent resin material (binder), a dispersant, and other components as necessary. It becomes.
  • the dispersion method of the aqueous coating liquid is not particularly limited and can be appropriately selected depending on the purpose. For example, stirring, ultrasonic dispersion, bead dispersion, kneading, homogenizer treatment, pressure dispersion treatment, etc. Are preferable.
  • the total amount of metal nanowires and carbon nanotubes in the aqueous coating solution is not particularly limited and can be appropriately selected according to the purpose.
  • the mass of the aqueous coating solution is 100 parts by mass. In this case, the amount is preferably 0.01 parts by mass to 10.00 parts by mass.
  • the basis weight (0.001 g) sufficient for the metal nanowires and / or carbon nanotubes in the finally obtained transparent conductive film. / M 2 to 1.000 g / m 2 ) may not be obtained, and if it exceeds 10.00 parts by mass, the dispersibility of the metal nanowires and / or carbon nanotubes may be deteriorated.
  • the metal nanowire is made of metal and is a fine wire having a diameter on the order of nm.
  • the constituent element of the metal nanowire is not particularly limited as long as it is a metal element, and can be appropriately selected according to the purpose.
  • Ag, Au, Ni, Cu, Pd, Pt, Rh, Ir examples include Ru, Os, Fe, Co, Sn, Al, Tl, Zn, Nb, Ti, In, W, Mo, Cr, Fe, V, Ta, and the like. These may be used individually by 1 type and may use 2 or more types together.
  • Ag and Cu are preferable in terms of high conductivity.
  • the average minor axis diameter of the metal nanowire is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably more than 1 nm and not more than 500 nm, and more preferably 10 nm to 100 nm.
  • the average minor axis diameter of the metal nanowire is 1 nm or less, the conductivity of the metal nanowire deteriorates, and the transparent conductive film containing the metal nanowire may not function as a conductive film. If it exceeds, the total light transmittance and haze of the transparent conductive film containing the metal nanowires may deteriorate.
  • the average minor axis diameter of the metal nanowire is within the more preferable range, it is advantageous in that the transparent conductive film including the metal nanowire has high conductivity and high transparency.
  • the average major axis length of the metal nanowire is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably more than 1 ⁇ m and not more than 1000 ⁇ m, and more preferably 10 ⁇ m to 300 ⁇ m.
  • the metal nanowires are not easily connected to each other, and the transparent conductive film containing the metal nanowires may not function as a conductive film.
  • the total light transmittance and haze of the transparent conductive film containing the metal nanowire may deteriorate, or the dispersibility of the metal nanowire in the aqueous coating solution used when forming the transparent conductive film may deteriorate. .
  • the metal nanowire may have a wire shape in which metal nanoparticles are connected in a bead shape.
  • the length of the metal nanowire is not limited.
  • the weight per unit area of the metal nanowires is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.001g / m 2 ⁇ 1.000g / m 2, 0.003g / m 2 ⁇ 0.3 g / m 2 is more preferable.
  • the basis weight of the metal nanowire is less than 0.001 g / m 2 , the metal nanowire is not sufficiently present in the metal nanowire layer, and the conductivity of the transparent conductive film may be deteriorated. If it exceeds .000 g / m 2 , the total light transmittance and haze of the transparent conductive film may deteriorate.
  • the basis weight of the metal nanowire is within the more preferable range, it is advantageous in that the conductivity of the transparent conductive film is high and the transparency is high.
  • the metal nanowire network means a network structure formed by connecting a plurality of metal nanowires to each other in a network.
  • the metal nanowire network is formed through a pressure treatment process described later and a heat curing treatment process described later.
  • combined by the conventional synthesis method may be sufficient, and a commercially available thing may be used.
  • combining method of the said carbon nanotube According to the objective, it can select suitably, For example, an arc discharge method, a laser evaporation method, a thermal CVD method etc. are mentioned.
  • limiting in particular as said carbon nanotube According to the objective, it can select suitably, A single-walled carbon nanotube (SWNT) may be sufficient, and a multi-walled carbon nanotube (MWNT) may be sufficient. However, the single-walled carbon nanotube is preferable.
  • the carbon nanotube may be a mixture of metallic and semiconducting carbon nanotubes, or may be a selectively separated semiconducting carbon nanotube.
  • the carbon nanotube network means a network structure formed by connecting a plurality of carbon nanotubes in a network.
  • the carbon nanotube network is formed through a pressure treatment step described later and a heat curing treatment step described later.
  • the solvent is not particularly limited as long as it contains water as a main solvent, and can be appropriately selected depending on the purpose. It may or may not contain a solvent other than water.
  • the solvent other than water is not particularly limited and may be appropriately selected depending on the intended purpose.
  • methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol examples thereof include alcohols such as tert-butanol; ketones such as cyclohexanone, cyclopentanone and anone; amides such as N, N-dimethylformamide (DMF); sulfides such as dimethyl sulfoxide (DMSO). These may be used individually by 1 type and may use 2 or more types together.
  • a high boiling point solvent may be further added to the aqueous coating solution. Thereby, the evaporation rate of the solvent from the aqueous coating solution can be controlled.
  • the high boiling point solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the transparent resin material (binder) is for dispersing the metal nanowires and / or the carbon nanotubes.
  • transparent resin material (binder) There is no restriction
  • the thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • thermosetting (photo) curable resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silicon resins such as melamine acrylate, urethane acrylate, isocyanate, epoxy resin, polyimide resin, and acrylic-modified silicate. And a polymer in which a photosensitive group such as an azide group or a diazirine group is introduced into at least one of a main chain and a side chain.
  • the dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyvinyl pyrrolidone (PVP); amino group-containing compounds such as polyethyleneimine; sulfo groups (including sulfonates) and sulfonyl groups.
  • PVP polyvinyl pyrrolidone
  • amino group-containing compounds such as polyethyleneimine
  • sulfo groups including sulfonates
  • Sulfonamide group carboxylic acid group (including carboxylate), amide group, phosphate group (including phosphate and phosphate ester), phosphino group, silanol group, epoxy group, isocyanate group, cyano group, vinyl group,
  • a compound having a functional group such as a thiol group or a carbinol group, which can be adsorbed to a metal; These may be used alone or in combination of two or more.
  • the dispersant may be adsorbed on the surface of the metal nanowire or the carbon nanotube. Thereby, the dispersibility of the said metal nanowire or the said carbon nanotube can be improved.
  • the dispersant when added to the aqueous coating solution, it is preferable to add the dispersant so as not to deteriorate the conductivity of the finally obtained transparent conductive film.
  • the said dispersing agent can be made to adsorb
  • the other components are not particularly limited and may be appropriately selected depending on the intended purpose.
  • surfactants for example, surfactants, viscosity modifiers, curing accelerators, plasticity, stabilizers such as antioxidants and sulfidizing agents, and the like. , Etc.
  • the coating step is a step of coating the prepared aqueous coating solution on a substrate.
  • the aqueous coating solution is as described above.
  • the coating method is not particularly limited as long as it is a coating using a die coater, and can be appropriately selected according to the purpose.
  • a flat plate slit die 1 includes a die head 2, a coating liquid supply pump (not shown) for supplying the coating liquid X to the die head 2, and a coating liquid tank (not shown) for storing the coating liquid. Z)).
  • the coating liquid supplied to the die head 2 is applied onto the substrate 4 through the slits 3 formed in the die head 2.
  • the base material 4 is placed on the transport table 5 and transported at a predetermined speed. In this case, the conveyance speed of the base material 4 becomes a coating speed.
  • W represents a slit gap (width of the slit 3)
  • H represents a coating gap (distance between the lower surface of the die head 2 and the upper surface of the substrate 4)
  • h represents a coating liquid ( Coated film)
  • X represents the wet coating thickness.
  • Coating liquid supply using a closed type coater such as the flat-plate slit die 1 allows temperature adjustment of the coating liquid compared to coating liquid supply using an open type coater (open system) such as a wire bar or applicator. As a result, the viscosity of the coating liquid can be easily adjusted.
  • the coating gap is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 ⁇ m to 200 ⁇ m, and more preferably 30 ⁇ m to 150 ⁇ m. When the coating gap is less than 20 ⁇ m, meniscus formation may be insufficient, and when it exceeds 200 ⁇ m, coating stripes may occur. On the other hand, when the coating gap is within the more preferable range, it is advantageous in terms of meniscus formation at the coating wetted part.
  • the wet coating thickness is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 ⁇ m to 20 ⁇ m, and more preferably 5 ⁇ m to 15 ⁇ m. When the wet coating thickness is less than 3 ⁇ m, coating may be difficult, and when it exceeds 20 ⁇ m, the in-plane distribution of the sheet resistance value may be uneven. On the other hand, when the wet coating thickness is within the more preferable range, it is advantageous in terms of good coating and uniformity of in-plane distribution of sheet resistance value.
  • the ratio of the coating gap to the wet coating thickness is not particularly limited and may be appropriately selected depending on the intended purpose. 2.0 to 4.0 are more preferable. When the ratio (coating gap / wet coating thickness) is less than 1.5, coating streaks and coating leakage may occur, and when it exceeds 4.5, coating becomes difficult. There is. On the other hand, when the ratio (coating gap / wet coating thickness) is within the more preferable range, it is advantageous in terms of prevention of coating streaks and coating leakage and good coating.
  • the slit gap is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 ⁇ m to 150 ⁇ m, and more preferably 50 ⁇ m to 100 ⁇ m.
  • the slit gap is less than 30 ⁇ m, the aqueous coating solution may be clogged in the die coater, and when the slit gap exceeds 150 ⁇ m, liquid dripping of the aqueous coating solution may occur.
  • the slit gap is within the more preferable range, it is advantageous from the viewpoint of clogging of the aqueous coating solution and prevention of dripping.
  • the number of capillaries is within a predetermined range, and the viscosity and surface tension of the aqueous coating liquid are within a predetermined range, depending on the purpose, although it can select suitably, it is preferable that the temperature and coating speed of the said aqueous coating liquid are in a predetermined range.
  • the capillary number Ca is represented by the following formula (1).
  • (Equation 2) Ca ⁇ U / ⁇ (1)
  • ⁇ represents the viscosity (Pa ⁇ s) of the aqueous coating solution
  • U represents the coating speed (m / s) of the aqueous coating solution
  • ⁇ represents the aqueous coating solution.
  • the capillary number Ca is not particularly limited as long as it is 0.03 or less, and can be appropriately selected according to the purpose, but is preferably 0.005 to 0.03.
  • the capillary number Ca exceeds 0.03, poor coating is caused and the in-plane distribution of the sheet resistance value becomes non-uniform.
  • the number of capillaries Ca is within the preferred range, it is advantageous in that a coating film can be prevented and a transparent conductive film having a uniform in-plane distribution of sheet resistance can be produced.
  • Viscosity of aqueous coating liquid is not particularly limited as long as it is 1 mPa ⁇ s to 50 mPa ⁇ s, and can be appropriately selected according to the purpose, but is preferably 10 mPa ⁇ s to 40 mPa ⁇ s.
  • the viscosity of the aqueous coating solution is less than 1 mPa ⁇ s or more than 50 mPa ⁇ s, poor coating is caused and the in-plane distribution of the sheet resistance value is made non-uniform.
  • the viscosity of the aqueous coating liquid is within the preferred range, it is advantageous in that a coating film can be prevented and a transparent conductive film having a uniform in-plane sheet resistance value can be produced. It is.
  • the surface tension of the aqueous coating solution is not particularly limited as long as it is 20 mN / m to 60 mN / m, and can be appropriately selected according to the purpose, but is preferably 25 mN / m to 50 mN / m.
  • the surface tension of the aqueous coating liquid is less than 20 mN / m or exceeds 60 mN / m, a coating failure is caused and the in-plane distribution of the sheet resistance value becomes non-uniform.
  • the surface tension of the aqueous coating liquid is within the preferred range, a coating failure can be prevented and a transparent conductive film having a uniform in-plane distribution of sheet resistance can be produced. It is advantageous.
  • Temperature of aqueous coating liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 40 ° C. If the temperature of the aqueous coating solution is less than 10 ° C or more than 60 ° C, the viscosity of the aqueous coating solution may not be easily adjusted. On the other hand, when the temperature of the aqueous coating liquid is within the more preferable range, it is advantageous in terms of ease of adjusting the viscosity of the aqueous coating liquid.
  • the coating speed usually means the conveyance speed of the substrate during coating.
  • the conveyance speed of the base material at the time of coating suitably, 100 mm / sec or less is preferable, 50 mm / More preferably, sec or less.
  • the coating speed exceeds 100 mm / sec, coating stripes and coating leakage may occur.
  • the coating speed is within the more preferable range, it is advantageous in terms of preventing coating stripes and coating leakage.
  • the transparent base material comprised with the material which has transparency with respect to visible light, such as an inorganic material and a plastic material, is preferable.
  • the transparent substrate has a film thickness required for a transparent electrode having a transparent conductive film.
  • quartz, sapphire, glass, etc. are mentioned.
  • a triacetyl cellulose TAC
  • polyester TPE
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PA polyimide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PE polyacrylate
  • PE polyether sulfone
  • PP polypropylene
  • PP diacetyl cellulose
  • PVC polyvinyl chloride
  • acrylic resin PMMA
  • PC polycarbonate
  • Known polymer materials such as resin, urea resin, urethane resin, melamine resin, and cycloolefin polymer (COP) can be used.
  • the film thickness of the transparent substrate is preferably 5 ⁇ m to 500 ⁇ m from the viewpoint of productivity, but is not particularly limited to this range.
  • the transparent conductive film is prepared, for example, by preparing an aqueous coating solution containing at least one of metal nanowires and carbon nanotubes and a solvent (aqueous coating solution preparation step), and preparing the prepared aqueous coating solution. Coating on the base material (coating process), drying and removing the solvent in the aqueous coating solution (drying process), heat-curing process (heat-curing process process), and then calendering (pressurization) It is obtained by performing (processing).
  • the thickness (dry coating thickness) of the transparent conductive film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 nm to 70 nm, and more preferably 40 nm to 60 nm. If the thickness of the transparent conductive film is less than 30 nm, sufficient conductivity may not be obtained, and if it exceeds 70 nm, in addition to not forming a sufficient network of metal nanowires or carbon nanotubes, transparency May get worse. On the other hand, when the thickness of the transparent conductive film is in the more preferable range, it is advantageous in terms of forming a network of metal nanowires or carbon nanotubes.
  • the drying step is a step of drying and removing the solvent in the aqueous coating solution.
  • the aqueous coating solution and the solvent are as described above.
  • the heat curing process is a process for performing a heat curing process.
  • the heating temperature in the heat curing treatment is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C, and particularly preferably about 120 ° C. .
  • the heating temperature in the heat curing treatment is less than 60 ° C., the time required for drying may become long and workability may deteriorate, and when it exceeds 140 ° C., the balance with the glass transition temperature (Tg) of the substrate The substrate may be distorted.
  • the heating temperature in the heat curing treatment is within the more preferable range or the particularly preferable temperature, it is advantageous in terms of forming a metal nanowire network.
  • the heating time in the heat curing treatment is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably about 5 minutes. .
  • the heating time in the heat curing treatment is less than 1 minute, drying may be insufficient, and when it exceeds 30 minutes, workability may be deteriorated.
  • the heating time in the heat curing treatment is within the more preferable range or the particularly preferable time, it is advantageous in terms of network formation and workability of metal nanowires or carbon nanotubes.
  • the calendering process is a process of calendering (pressurizing) the transparent conductive film.
  • a pressed body 30 including a base material 10 and a transparent conductive film 20 formed on the base material 10 is applied to a press roll ( It is sandwiched and pressed by a roll pair 60 composed of a first roll 40 and a back roll (second roll) 50.
  • a roll used for the said pressurization process there is no restriction
  • the surface pressure, line width, pressurization (load), and conveyance speed in the pressurization process are appropriately adjusted according to the type of roll used in the pressurization process.
  • the press roll 40 and the back roll 50 may rotate the surface of the transparent conductive film 20 once or a plurality of times.
  • the transparent conductive film is heated, for example, at 80 ° C. to 250 ° C. for 10 minutes or less, more preferably at 100 ° C. to 160 ° C. for 10 seconds to 2 minutes.
  • the transparent conductive film can be heated to a temperature higher than 250 ° C. depending on the type of substrate, and can be heated to a temperature of 400 ° C.
  • the glass substrate can be heat-treated at a temperature in the range of 350 ° C. to 400 ° C.
  • post-treatment at higher temperatures may require the presence of a non-oxidizing atmosphere such as nitrogen or a noble gas.
  • the heating can be performed either online or offline.
  • the transparent conductive film can be placed in an oven set at a predetermined temperature for a predetermined time.
  • the conductivity of the transparent conductive film can be improved.
  • the roll may be heated (roll temperature control).
  • the roll is preferably heated to 30 ° C. to 200 ° C., more preferably 40 ° C. to 100 ° C.
  • the material of the elastic roll is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the main component is a chloroprene polymer rubber, acrylonitrile butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM). Such as rubber; resin; and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, rubber having high hardness and solvent resistance is preferable.
  • the material of the said elastic roll is not rubber
  • the diameter of the elastic roll is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 mm to 1,000 mm, more preferably 40 mm to 500 mm, and particularly preferably 50 mm to 300 mm.
  • the diameter of the elastic roll is less than 30 mm, it is difficult to wind the rubber around the metal roll, and it may be difficult to produce the elastic roll, and when it exceeds 1,000 mm, it may be difficult to handle the roll. .
  • the diameter of the elastic roll is within the more preferable range or the particularly preferable range, it is advantageous in terms of roll production and handling.
  • Metal roll >> There is no restriction
  • the metal may be subjected to, for example, hard chrome plating. Among these, a metal with high workability and solvent resistance is preferable.
  • the diameter of the metal roll is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 mm to 1,000 mm, more preferably 40 mm to 500 mm, and particularly preferably 50 mm to 300 mm. If the diameter of the metal roll is less than 30 mm, it may be difficult to produce the roll, and if it exceeds 1,000 mm, handling of the roll may be difficult. On the other hand, when the diameter of the metal roll is within the more preferable range or the particularly preferable range, it is advantageous in terms of roll production and handling.
  • a metal roll having a diameter of less than 200 mm is preferably used as the press roll (first roll), and an elastic roll having a diameter of 200 mm or more is preferably used as the back roll (second roll).
  • the cushioning action is increased by using a metal roll having a diameter of less than 200 mm as the press roll (first roll) and using an elastic roll having a diameter of 200 mm or more as the back roll (second roll).
  • the pressure can be suitably released.
  • Silver nanowire ink (aqueous coating liquid) 1 was prepared with the following composition.
  • Metal nanowire Silver nanowire (manufactured by Seashell Technology, AgNW-25, average diameter 25 nm, average length 23 ⁇ m): compounding amount 0.050 part by mass
  • binder hydroxypropylmethylcellulose (manufactured by Aldrich, Viscosity of 2% aqueous solution at 20 ° C. 80 cP to 120 cP (document value)): blending amount 0.125 parts by mass
  • solvent (i) water: blending amount 89.825 parts by mass, (ii) ethanol: blending amount 10 .000 parts by mass
  • a silver nanowire transparent conductive film was prepared by the following procedure. First, the produced silver nanowire ink (aqueous coating liquid) 1 was applied onto a transparent substrate (PET: Toray Industries, U34, film thickness 125 ⁇ m) with a flat plate die coater manufactured by Daimon Co., Ltd. Thus, a silver nanowire coating film was formed. Here, the basis weight of the silver nanowires was set to about 0.01 g / m 2 .
  • the coating conditions were as follows.
  • ⁇ Coating conditions (1) Slit gap of flat plate die coater: 50 ⁇ m (2) Coating gap between flat plate die coater and transparent substrate: 30 ⁇ m (3) Wet coating thickness of silver nanowire coating film: 15 ⁇ m (4) Coating speed: 15mm / sec (5) Water-based coating solution temperature: 25 ° C (6) Viscosity of aqueous coating solution: 6 mPa ⁇ s (7) Surface tension of aqueous coating solution: 45 mN / m (8) Number of capillaries: 0.0020 Here, the wet coating thickness was calculated from the coating area and the coating liquid discharge liquid per unit time.
  • ⁇ Pressure treatment of silver nanowire transparent conductive film> Using the calendar processing apparatus (refer FIG.2 and FIG.3) provided with a cylindrical press roll (1st roll) and a back roll (2nd roll) with respect to the produced silver nanowire transparent conductive film, a calendar process is carried out. (Pressurizing treatment) was performed. At the time of calendering (pressure treatment), both the press roll (first roll) and the back roll (second roll) are made of steel (manufacturer name: Miyagawa Roller), and the pressure (load) is 4 kN. The conveyance speed was 1 m / min.
  • the resistance value of the silver nanowire transparent conductive film was measured as follows. The surface of the silver nanowire transparent conductive film is contacted with a measurement probe of a manual nondestructive resistance measuring device (Napson Co., Ltd., EC-80P), and any 12 on the surface of the transparent conductive film (silver nanowire layer) The resistance value was measured at each location, and the average value was taken as the resistance value. The resistance value was 118 ⁇ / ⁇ . The measurement results are shown in Table 1A.
  • ⁇ Evaluation of resistance distribution> The standard deviation ⁇ was calculated using the values of any 12 locations measured in the measurement of the resistance value, and the resistance distribution of the silver nanowire transparent conductive film was evaluated according to the following evaluation criteria.
  • the standard deviation ⁇ was 7 ⁇ / ⁇ . Table 1 shows the calculation results and the evaluation results.
  • Example 2 In Example 1, instead of setting the coating speed to 15 mm / sec and setting the number of capillaries to 0.0020, the coating speed was set to 30 mm / sec and the number of capillaries was set to 0.0040. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1A.
  • Example 3 In Example 1, instead of setting the coating speed to 15 mm / sec and setting the number of capillaries to 0.0020, the coating speed was set to 50 mm / sec and the number of capillaries was set to 0.0067. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1A.
  • Example 4 In Example 1, a silver nanowire ink (aqueous coating liquid) 1 was prepared, the aqueous coating liquid viscosity was 6 mPa ⁇ s, the aqueous coating liquid surface tension was 45 mN / m, and the capillary number was 0.0020.
  • the silver nanowire ink (aqueous coating liquid) 2 is prepared with the following composition, the aqueous coating liquid viscosity is 24 mPa ⁇ s, the aqueous coating liquid surface tension is 43 mN / m, and the number of capillaries is Except having been set to 0.0084, a silver nanowire transparent conductive film was prepared in the same manner as in Example 1, and the prepared silver nanowire transparent conductive film was subjected to pressure treatment, followed by pressure treatment. The resistance value was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 1A. ⁇ Preparation of silver nanowire ink (aqueous coating liquid) 2> Silver nanowire ink (aqueous coating liquid) 2 was prepared with the following composition.
  • Metal nanowire Silver nanowire (manufactured by Seashell Technology, AgNW-25, average diameter 25 nm, average length 23 ⁇ m): compounding amount 0.050 part by mass
  • binder hydroxypropylmethylcellulose (manufactured by Aldrich, Viscosity of 2% aqueous solution at 20 ° C. 80 cP to 120 cP (document value)): blending amount 0.125 parts by mass
  • Thickener thickener (Toa Gosei Co., Ltd., A-20L): blending amount 0.075 Parts by mass
  • solvent (i) water: blending amount 89.750 parts by weight, (ii) ethanol: blending amount 10.000 parts by weight
  • Example 5 In Example 4, instead of setting the coating speed to 15 mm / sec and setting the number of capillaries to 0.0084, the coating speed was set to 30 mm / sec and the number of capillaries was set to 0.0167. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1A.
  • Example 6 In Example 4, instead of setting the coating speed to 15 mm / sec and setting the number of capillaries to 0.0084, the coating speed was set to 50 mm / sec and the number of capillaries was set to 0.0279. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1A.
  • Example 1 a silver nanowire ink (aqueous coating liquid) 1 was prepared, the aqueous coating liquid viscosity was 6 mPa ⁇ s, the aqueous coating liquid surface tension was 45 mN / m, and the capillary number was 0.0020.
  • the silver nanowire ink (aqueous coating liquid) 3 is prepared with the following composition, the aqueous coating liquid viscosity is 52 mPa ⁇ s, the aqueous coating liquid surface tension is 46 mN / m, and the number of capillaries is A silver nanowire transparent conductive film was produced in the same manner as in Example 1 except that the thickness was 0.0170, and the silver nanowire transparent conductive film thus produced was subjected to pressure treatment, followed by pressure treatment. The resistance value was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 1B. ⁇ Preparation of silver nanowire ink (aqueous coating liquid) 3> Silver nanowire ink (aqueous coating liquid) 3 was prepared with the following composition.
  • Metal nanowire Silver nanowire (manufactured by Seashell Technology, AgNW-25, average diameter 25 nm, average length 23 ⁇ m): compounding amount 0.050 part by mass
  • binder hydroxypropylmethylcellulose (manufactured by Aldrich, Viscosity of 2% aqueous solution at 20 ° C. 80 cP to 120 cP (document value)): Blending amount 0.125 parts by mass
  • Thickener Thickener (A-20L, manufactured by Toagosei Co., Ltd.): Blending amount 0.150 Parts by mass
  • solvent (i) water: blending amount 89.675 parts by mass, (ii) ethanol: blending amount 10.000 parts by mass
  • Comparative Example 2 In Comparative Example 1, the coating speed was set to 15 mm / sec and the number of capillaries was set to 0.0170, but the coating speed was set to 30 mm / sec and the number of capillaries was set to 0.0339. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1B.
  • Comparative Example 3 In Comparative Example 1, instead of setting the coating speed to 15 mm / sec and setting the number of capillaries to 0.0170, the coating speed was set to 50 mm / sec and the number of capillaries was set to 0.0565. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1B.
  • Example 4 a silver nanowire ink (aqueous coating liquid) 1 was prepared, the aqueous coating liquid viscosity was 6 mPa ⁇ s, the aqueous coating liquid surface tension was 45 mN / m, and the capillary number was 0.0020.
  • the silver nanowire ink (aqueous coating liquid) 4 is prepared with the following composition, the aqueous coating liquid viscosity is 23 mPa ⁇ s, the aqueous coating liquid surface tension is 68 mN / m, and the number of capillaries is Except having been set to 0.0051, a silver nanowire transparent conductive film was prepared in the same manner as in Example 1, and the prepared silver nanowire transparent conductive film was subjected to pressure treatment, followed by pressure treatment of the silver nanowire transparent conductive film. The resistance value was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 1B.
  • Silver nanowire ink (aqueous coating liquid) 4 was prepared with the following composition.
  • Metal nanowire Silver nanowire (manufactured by Seashell Technology, AgNW-25, average diameter 25 nm, average length 23 ⁇ m): compounding amount 0.050 part by mass
  • binder hydroxypropylmethylcellulose (manufactured by Aldrich, Viscosity of 2% aqueous solution at 20 ° C.
  • Comparative Example 5 In Comparative Example 4, instead of setting the coating speed to 15 mm / sec and setting the number of capillaries to 0.0051, the coating speed was set to 30 mm / sec and the number of capillaries was set to 0.0101. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1B.
  • Comparative Example 6 In Comparative Example 4, the coating speed was set to 15 mm / sec, the number of capillaries was set to 0.0051, and the coating speed was set to 50 mm / sec and the number of capillaries was set to 0.0169. Similarly, a silver nanowire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and coating appearance Was evaluated. The results are shown in Table 1B.
  • Example 7 (Comparative Example 7)
  • the coating speed was set to 200 mm / sec, and the aqueous coating liquid was A silver nanowire transparent conductive film was produced in the same manner as in Example 4 except that the surface tension was 42 mN / m and the number of capillaries was 0.1143, and the produced silver nanowire transparent conductive film was subjected to pressure treatment.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 2.
  • Example 7 In Example 4, instead of setting the surface tension of the aqueous coating solution to 43 mN / m and the number of capillaries to 0.0084, the amount of solvent added is increased, or a surfactant (eg, Triton X manufactured by Sigma-Aldrich) -100), a silver nanowire transparent conductive film was prepared in the same manner as in Example 4 except that the surface tension of the aqueous coating solution was 29 mN / m and the number of capillaries was 0.0124. The produced silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 3.
  • a surfactant eg, Triton X manufactured by Sigma-Aldrich
  • Example 8 In Example 4, instead of setting the surface tension of the aqueous coating solution to 43 mN / m and the number of capillaries to 0.0084, the amount of solvent added is increased, or a surfactant (eg, Triton X manufactured by Sigma-Aldrich) -100), a silver nanowire transparent conductive film was prepared in the same manner as in Example 4 except that the surface tension of the aqueous coating solution was 22 mN / m and the number of capillaries was 0.0164. The produced silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 3.
  • a surfactant eg, Triton X manufactured by Sigma-Aldrich
  • Example 9 In Example 1, instead of setting the viscosity of the aqueous coating solution to 6 mPa ⁇ s, the surface tension of the aqueous coating solution to 45 mN / m, and the number of capillaries to 0.0020, the amount of the binder is increased or the thickener. In the same manner as in Example 1 except that the viscosity of the aqueous coating solution was 37 mPa ⁇ s, the surface tension of the aqueous coating solution was 44 mN / m, and the number of capillaries was 0.0126.
  • a wire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. .
  • the results are shown in Table 4.
  • Example 10 In Example 1, instead of setting the viscosity of the aqueous coating solution to 6 mPa ⁇ s, the surface tension of the aqueous coating solution to 45 mN / m, and the number of capillaries to 0.0020, the amount of the binder is increased or the thickener. In the same manner as in Example 1, except that the viscosity of the aqueous coating solution was 46 mPa ⁇ s, the surface tension of the aqueous coating solution was 43 mN / m, and the number of capillaries was 0.0160.
  • a wire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. .
  • the results are shown in Table 4.
  • Example 8 In Example 1, instead of setting the viscosity of the aqueous coating solution to 6 mPa ⁇ s, the surface tension of the aqueous coating solution to 45 mN / m, and the number of capillaries to 0.0020, the amount of the binder is increased or the thickener. In the same manner as in Example 1, except that the viscosity of the aqueous coating solution is 58 mPa ⁇ s, the surface tension of the aqueous coating solution is 43 mN / m, and the number of capillaries is 0.0202.
  • a wire transparent conductive film was prepared, the prepared silver nanowire transparent conductive film was subjected to pressure treatment, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. .
  • the results are shown in Table 4.
  • Example 11 In Example 4, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 15 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2, the coating gap is set to 10 ⁇ m and the wet coating thickness is set to A silver nanowire transparent conductive film was prepared in the same manner as in Example 4 except that the thickness was 3 ⁇ m and the ratio (coating gap / wet coating thickness) was 3.3. The resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 5.
  • Example 12 In Example 4, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 15 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2, the coating gap is set to 15 ⁇ m and the wet coating thickness is set to A silver nanowire transparent conductive film was produced in the same manner as in Example 4 except that the ratio (coating gap / wet coating thickness) was 3, and the produced silver nanowire transparent conductive film was pressurized. The resistance value of the processed and pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 5.
  • Example 13 In Example 4, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 15 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2, the coating gap is set to 20 ⁇ m and the wet coating thickness is set to A silver nanowire transparent conductive film was prepared in the same manner as in Example 4 except that the ratio (coating gap / wet coating thickness) was 2, and the produced silver nanowire transparent conductive film was pressurized. The resistance value of the processed and pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 5.
  • Example 14 In Example 4, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 15 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2, the coating gap was set to 30 ⁇ m and the wet coating thickness was A silver nanowire transparent conductive film was produced in the same manner as in Example 4 except that the ratio (coating gap / wet coating thickness) was 3, and the produced silver nanowire transparent conductive film was pressurized. The resistance value of the processed and pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 5.
  • Example 15 In Example 4, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 15 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2, the coating gap was set to 30 ⁇ m and the wet coating thickness was A silver nanowire transparent conductive film was prepared in the same manner as in Example 4 except that the ratio was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 1.5. The resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 5.
  • Example 16 In Example 4, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 15 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2, the coating gap is set to 45 ⁇ m and the wet coating thickness is set to A silver nanowire transparent conductive film was prepared in the same manner as in Example 4 except that the thickness was 10 ⁇ m and the ratio (coating gap / wet coating thickness) was 4.5. The resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 5.
  • Example 17 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 40 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 2.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 18 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 50 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 2.5. The film was pressure treated, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 19 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 70 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 3.5. The film was pressure treated, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 20 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 100 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 5.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 21 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 120 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 6.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 22 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 150 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 7.5. The film was pressure treated, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 23 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 180 ⁇ m, and wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 20 ⁇ m and the ratio (coating gap / wet coating thickness) was 9.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 6.
  • Example 24 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 30 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 5 ⁇ m and the ratio (coating gap / wet coating thickness) was 6.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 7.
  • Example 25 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 30 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 10 ⁇ m and the ratio (coating gap / wet coating thickness) was 3.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 7.
  • Example 26 In Example 15, instead of setting the coating gap to 30 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 1.5, the coating gap was set to 30 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 15 except that the thickness was 15 ⁇ m and the ratio (coating gap / wet coating thickness) was 2.
  • the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 7.
  • Example 27 In Example 18, instead of setting the coating gap to 50 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2.5, the coating gap was set to 50 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 18 except that the thickness was 30 ⁇ m and the ratio (coating gap / wet coating thickness) was 1.7.
  • the film was pressure treated, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 8.
  • Example 28 In Example 18, instead of setting the coating gap to 50 ⁇ m, the wet coating thickness to 20 ⁇ m, and the ratio (coating gap / wet coating thickness) to 2.5, the coating gap was set to 50 ⁇ m and the wet coating was performed.
  • a silver nanowire transparent conductive film was prepared in the same manner as in Example 18 except that the thickness was 40 ⁇ m and the ratio (coating gap / wet coating thickness) was 1.3. The film was pressure treated, the resistance value of the pressure-treated silver nanowire transparent conductive film was measured, and the resistance distribution and the coating film appearance were evaluated. The results are shown in Table 8.
  • Viscosity of aqueous coating solution 1 mPa ⁇ s to 50 mPa ⁇ s
  • (iii) Capillary number Ca Examples 1 to 28 satisfying all three conditions of 0.03 or less are: (i) Viscosity of aqueous coating solution 1 mPa ⁇ s to 50 mPa ⁇ s, (ii) Surface tension of aqueous coating solution 20 mN / m Compared with Comparative Examples 1 to 8 that do not satisfy at least one of the three conditions of ⁇ 60 mN / m and (iii) Capillary number Ca of 0.03 or less, the coating resistance is prevented and the sheet resistance value is reduced. It can be seen that a transparent conductive film having a uniform in-plane distribution can be produced.
  • the transparent conductive film manufactured using the coating method of the present invention is an alternative to a transparent conductive film using metal oxide such as indium tin oxide (ITO) used in electronic devices such as notebook computers and smartphones. It can be suitably used as a product.
  • ITO indium tin oxide

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220203738A1 (en) * 2019-05-31 2022-06-30 Showa Denko K.K. Method for producing transparent conducting film
US20220344072A1 (en) * 2019-12-27 2022-10-27 Showa Denko K.K. Method for producing transparent conducting film

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3098821B1 (fr) * 2019-07-19 2023-05-26 Isorg Encre pour une couche d’injection d’électrons
JP2022541306A (ja) * 2019-07-19 2022-09-22 イソルグ 電子注入層を堆積する方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08243476A (ja) * 1995-03-10 1996-09-24 Chugai Ro Co Ltd ダイコータによるガラス基板への塗布方法
JP2011090878A (ja) * 2009-10-22 2011-05-06 Fujifilm Corp 透明導電体の製造方法
JP2011090879A (ja) * 2009-10-22 2011-05-06 Fujifilm Corp 透明導電体の製造方法
JP2012056788A (ja) * 2010-09-08 2012-03-22 Toray Ind Inc カーボンナノチューブ水分散液
JP2013056291A (ja) * 2011-09-07 2013-03-28 Fujifilm Corp 紐状フィラー含有塗布物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08243476A (ja) * 1995-03-10 1996-09-24 Chugai Ro Co Ltd ダイコータによるガラス基板への塗布方法
JP2011090878A (ja) * 2009-10-22 2011-05-06 Fujifilm Corp 透明導電体の製造方法
JP2011090879A (ja) * 2009-10-22 2011-05-06 Fujifilm Corp 透明導電体の製造方法
JP2012056788A (ja) * 2010-09-08 2012-03-22 Toray Ind Inc カーボンナノチューブ水分散液
JP2013056291A (ja) * 2011-09-07 2013-03-28 Fujifilm Corp 紐状フィラー含有塗布物の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220203738A1 (en) * 2019-05-31 2022-06-30 Showa Denko K.K. Method for producing transparent conducting film
US11535047B2 (en) * 2019-05-31 2022-12-27 Showa Denko K.K. Method for producing transparent conducting film
US20220344072A1 (en) * 2019-12-27 2022-10-27 Showa Denko K.K. Method for producing transparent conducting film
US11538603B2 (en) * 2019-12-27 2022-12-27 Showa Denko K.K. Method for producing transparent conducting film

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